WO2022163139A1 - Secondary battery - Google Patents
Secondary battery Download PDFInfo
- Publication number
- WO2022163139A1 WO2022163139A1 PCT/JP2021/044941 JP2021044941W WO2022163139A1 WO 2022163139 A1 WO2022163139 A1 WO 2022163139A1 JP 2021044941 W JP2021044941 W JP 2021044941W WO 2022163139 A1 WO2022163139 A1 WO 2022163139A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- negative electrode
- electrolyte layer
- layer
- liquid
- Prior art date
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- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
Definitions
- This technology relates to secondary batteries.
- the secondary battery includes a positive electrode, a negative electrode, and an electrolyte layer, and the electrolyte layer contains an electrolytic solution and a polymer compound.
- a secondary battery of an embodiment of the present technology includes a first electrolyte layer containing a first electrolyte solution and a first polymer compound, electrodes and separators facing each other via the first electrolyte layer, and the electrodes and separators is adjacent to the first electrolyte layer in a direction intersecting the direction facing each other with the first electrolyte layer interposed therebetween, and includes a second electrolyte layer containing a second electrolytic solution and a second polymer compound.
- the ratio of the weight of the second electrolytic solution to the weight of the second polymer compound is greater than the ratio of the weight of the first electrolytic solution to the weight of the first polymer compound.
- the electrode and the separator face each other via the first electrolyte layer (the first electrolytic solution and the first polymer compound), and the electrode and the separator face the first
- a second electrolyte layer (second electrolytic solution and second polymer compound) is adjacent to the first electrolyte layer in a direction intersecting the direction facing each other with the electrolyte layer interposed therebetween, and the weight of the second polymer compound is Since the weight ratio of the second electrolytic solution is greater than the weight ratio of the first electrolytic solution to the weight of the first polymer compound, excellent cycle characteristics can be obtained.
- FIG. 2 is a cross-sectional view showing an enlarged configuration of the battery element (wound electrode body) shown in FIG. 1.
- FIG. 14 is a cross-sectional view showing the configuration of a secondary battery in Modification 5.
- FIG. 4 is a cross-sectional view showing an enlarged configuration of the battery element (laminated electrode body) shown in FIG. 3.
- FIG. 3 is a block diagram showing the configuration of an application example of a secondary battery;
- the secondary battery described here is a secondary battery in which battery capacity is obtained by utilizing the absorption and release of electrode reactants, and is equipped with a positive electrode, a negative electrode, and an electrolytic solution, which is a liquid electrolyte.
- the charge capacity of the negative electrode is larger than the discharge capacity of the positive electrode. That is, the electrochemical capacity per unit area of the negative electrode is set to be larger than the electrochemical capacity per unit area of the positive electrode. This is to prevent electrode reactants from depositing on the surface of the negative electrode during charging.
- the type of electrode reactant is not particularly limited, but specifically light metals such as alkali metals and alkaline earth metals.
- Alkali metals include lithium, sodium and potassium
- alkaline earth metals include beryllium, magnesium and calcium.
- lithium ion secondary battery A secondary battery whose battery capacity is obtained by utilizing the absorption and release of lithium is a so-called lithium ion secondary battery.
- lithium ion secondary battery lithium is intercalated and deintercalated in an ionic state.
- Configuration> 1 shows a perspective configuration of a secondary battery
- FIG. 2 shows an enlarged cross-sectional configuration of the battery element 20 shown in FIG.
- FIG. 1 shows a state in which the exterior film 10 and the battery element 20 are separated from each other, and the cross section of the battery element 20 along the XZ plane is indicated by a broken line.
- FIG. 2 shows a cross section of the battery element 20 along the YZ plane.
- this secondary battery includes an exterior film 10, a battery element 20, a positive electrode lead 31, a negative electrode lead 32, and sealing films 41 and 42.
- the secondary battery described here is a laminated film type secondary battery using a flexible (or flexible) exterior film 10 .
- the "thickness” described later is the dimension in the vertical direction (Z-axis direction) in FIG. 2, and the “width” described later is the dimension in the horizontal direction (Y-axis direction) in FIG.
- the exterior film 10 is a flexible exterior member that houses the battery element 20, and has a sealed bag-like structure with the battery element 20 housed inside. is doing.
- the exterior film 10 is a single film-like member and is folded in the folding direction F.
- the exterior film 10 is provided with a recessed portion 10U (so-called deep drawn portion) for housing the battery element 20 .
- the exterior film 10 is a three-layer laminate film in which a fusion layer, a metal layer, and a surface protection layer are laminated in this order from the inside. Outer peripheral edge portions of the fusion layer are fused together.
- the fusible layer contains a polymer compound such as polypropylene.
- the metal layer contains a metal material such as aluminum.
- the surface protective layer contains a polymer compound such as nylon.
- the configuration (number of layers) of the exterior film 10 is not particularly limited, and may be one layer, two layers, or four layers or more.
- the sealing film 41 is inserted between the exterior film 10 and the positive electrode lead 31
- the sealing film 42 is inserted between the exterior film 10 and the negative electrode lead 32 .
- one or both of the sealing films 41 and 42 may be omitted.
- the sealing film 41 is a sealing member that prevents outside air from entering the exterior film 10 . Further, the sealing film 41 contains a polymer compound such as polyolefin having adhesiveness to the positive electrode lead 31, and the polyolefin is polypropylene or the like.
- the structure of the sealing film 42 is the same as the structure of the sealing film 41 except that it is a sealing member having adhesion to the negative electrode lead 32 . That is, the sealing film 42 contains a high molecular compound such as polyolefin having adhesiveness to the negative electrode lead 32 .
- the battery element 20 includes a positive electrode 21, a negative electrode 22, a separator 23, a positive electrode electrolyte layer 24, a negative electrode electrolyte layer 25, a positive electrode liquid retaining layer 26, and a negative electrode retaining liquid. layer 27 and housed inside the exterior film 10 .
- This battery element 20 is a so-called wound electrode assembly. That is, in the battery element 20, the positive electrode 21 and the negative electrode 22 are mainly laminated with the separator 23, the positive electrode electrolyte layer 24, and the negative electrode electrolyte layer 25 interposed therebetween. A positive electrode 21 , a negative electrode 22 , a separator 23 , a positive electrode electrolyte layer 24 , and a negative electrode electrolyte layer 25 are wound around a rotation axis P. Since the positive electrode retaining liquid layer 26 is arranged next to the positive electrode electrolyte layer 24 , it is adjacent to the positive electrode electrolyte layer 24 , and the negative electrode retaining liquid layer 27 is arranged next to the negative electrode electrolyte layer 25 . Therefore, it is adjacent to the negative electrode electrolyte layer 25 . Thus, the positive electrode 21 and the negative electrode 22 are wound while facing each other with the separator 23, the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25 interposed therebetween.
- the three-dimensional shape of the battery element 20 is not particularly limited.
- the cross section of the battery element 20 intersecting the winding axis P (the cross section along the XZ plane) has a flat shape defined by the long axis J1 and the short axis J2. have.
- the major axis J1 is a virtual axis that extends in the X-axis direction and has a length greater than that of the minor axis J2.
- the cross-sectional shape of the battery element 20 is a flat, substantially elliptical shape.
- the positive electrode 21 is an electrode for advancing charge/discharge reactions.
- This positive electrode 21 includes a positive electrode current collector 21A and a positive electrode active material layer 21B, as shown in FIG.
- the positive electrode current collector 21A has a pair of surfaces on which the positive electrode active material layer 21B is provided.
- This positive electrode current collector 21A contains a conductive material such as a metal material, and the metal material is aluminum or the like.
- the width of the positive electrode current collector 21A is set so as not to be larger than the width of the positive electrode active material layer 21B, and more specifically, it is the same as the width of the positive electrode active material layer 21B. This is because an increase in the volume of the positive electrode current collector 21A is prevented, so that the energy density per volume of the battery element 20 increases.
- the positive electrode active material layer 21B is provided on both sides of the positive electrode current collector 21A, and contains one or more of positive electrode active materials capable of intercalating and deintercalating lithium.
- the positive electrode active material layer 21B may be provided only on one side of the positive electrode current collector 21A on the side where the positive electrode 21 faces the negative electrode 22 .
- the positive electrode active material layer 21B may further contain one or more of other materials such as a positive electrode binder and a positive electrode conductive agent.
- a method for forming the positive electrode active material layer 21B is not particularly limited, but specifically, one or more of coating methods and the like are used.
- the type of the positive electrode active material is not particularly limited, specific examples thereof include lithium-containing compounds.
- This lithium-containing compound is a compound containing lithium and one or more transition metal elements as constituent elements, and may further contain one or more other elements as constituent elements.
- the type of the other element is not particularly limited as long as it is an element other than lithium and transition metal elements, but specifically, it is an element belonging to Groups 2 to 15 in the long period periodic table.
- the type of lithium-containing compound is not particularly limited, but specific examples include oxides, phosphoric acid compounds, silicic acid compounds and boric acid compounds.
- oxides include LiNiO2 , LiCoO2 , LiNi0.8Co0.15Al0.05O2 , LiNi0.33Co0.33Mn0.33O2 and LiMn2O4 .
- phosphoric acid compounds include LiFePO4 and LiMnPO4 .
- the positive electrode binder contains one or more of synthetic rubber and polymer compounds.
- Synthetic rubbers include styrene-butadiene-based rubber, fluorine-based rubber, and ethylene propylene diene.
- Polymer compounds include polyvinylidene fluoride, polyimide and carboxymethyl cellulose.
- the positive electrode conductive agent contains one or more of conductive materials such as carbon materials, and the carbon materials include graphite, carbon black, acetylene black, and ketjen black.
- the conductive material may be a metal material, a polymer compound, or the like.
- the negative electrode 22 is another electrode for advancing charge/discharge reactions.
- the negative electrode 22 includes a negative electrode current collector 22A and a negative electrode active material layer 22B, as shown in FIG.
- the negative electrode current collector 22A has a pair of surfaces on which the negative electrode active material layer 22B is provided.
- This negative electrode current collector 22A contains a conductive material such as a metal material, and the metal material is copper or the like.
- the width of the negative electrode current collector 22A is set so as not to be larger than the width of the negative electrode active material layer 22B, and more specifically, it is the same as the width of the negative electrode active material layer 22B. This is because an increase in the volume of the negative electrode current collector 22A is prevented, so that the energy density per volume of the battery element 20 increases.
- the negative electrode active material layer 22B is provided on both surfaces of the negative electrode current collector 22A, and contains one or more of negative electrode active materials capable of intercalating and deintercalating lithium.
- the negative electrode active material layer 22B may be provided only on one side of the negative electrode current collector 22A on the side where the negative electrode 22 faces the positive electrode 21 .
- the negative electrode active material layer 22B may further contain one or more of other materials such as a negative electrode binder and a negative electrode conductor.
- the method of forming the negative electrode active material layer 22B is not particularly limited, but specifically, any one of a coating method, a vapor phase method, a liquid phase method, a thermal spraying method, a firing method (sintering method), or the like, or Two or more types.
- the type of negative electrode active material is not particularly limited, but specifically, one or both of a carbon material and a metal-based material. This is because a high energy density can be obtained.
- Carbon materials include graphitizable carbon, non-graphitizable carbon and graphite (natural graphite and artificial graphite).
- a metallic material is a material containing as constituent elements one or more of metallic elements and semi-metallic elements capable of forming an alloy with lithium. , one or both of silicon and tin, and the like. This metallic material may be a single substance, an alloy, a compound, a mixture of two or more of them, or a material containing two or more of these phases. Specific examples of metallic materials include TiSi 2 and SiO x (0 ⁇ x ⁇ 2, or 0.2 ⁇ x ⁇ 1.4).
- each of the negative electrode binder and the negative electrode conductive agent is the same as those of the positive electrode binder and the positive electrode conductive agent.
- the width of the negative electrode active material layer 22B is larger than the width of the positive electrode active material layer 21B. This is to prevent lithium released from the positive electrode 21 from unintentionally depositing on the negative electrode 22 .
- the separator 23 is an insulating porous film interposed between the positive electrode 21 and the negative electrode 22, as shown in FIG. Allows lithium ions to pass through.
- This separator 23 contains a polymer compound such as polyethylene.
- the positive electrode electrolyte layer 24 is a first electrolyte layer that functions as an intermediary for lithium that is occluded and released in the positive electrode 21, and is arranged between the positive electrode 21 and the separator 23 as shown in FIG. That is, the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween.
- the positive electrode electrolyte layer 24 is sandwiched between the positive electrode 21 and the separator 23 and is adjacent to the positive electrode 21 and the separator 23 respectively.
- the positive electrode electrolyte layer 24 is a gel electrolyte containing an electrolytic solution and a polymer compound, and the electrolytic solution is held by the polymer compound.
- the positive electrode electrolyte layer 24, which is a gel electrolyte leakage of the electrolyte is prevented unlike the case where the electrolyte, which is a liquid electrolyte, is used as it is.
- the electrolytic solution described here is the first electrolytic solution contained in the positive electrode electrolyte layer 24 .
- the type of the electrolytic solution may be one type, or two or more types.
- the electrolyte contains a solvent and an electrolyte salt.
- the solvent contains one or more of non-aqueous solvents (organic solvents), and the electrolytic solution containing the non-aqueous solvent is the so-called non-aqueous electrolytic solution.
- the non-aqueous solvents are esters, ethers, and the like, and more specifically, carbonate compounds, carboxylic acid ester compounds, lactone compounds, and the like.
- Specific examples of carbonate ester compounds include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate.
- Specific examples of carboxylic acid ester compounds include ethyl acetate, ethyl propionate and propyl propionate.
- Specific examples of lactone compounds include ⁇ -butyrolactone and ⁇ -valerolactone.
- the electrolyte salt contains one or more of light metal salts such as lithium salts.
- lithium salts include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(fluorosulfonyl)imide (LiN (FSO2) 2 ), lithium bis(trifluoromethanesulfonyl)imide (LiN( CF3SO2 ) 2 ) , lithium tris(trifluoromethanesulfonyl)methide (LiC(CF3SO2)3 ) and bis ( oxalato)boron.
- LiPF 6 lithium hexafluorophosphate
- LiBF 4 lithium tetrafluoroborate
- LiCF 3 SO 3 lithium trifluoromethanesulfonate
- LiN (FSO2) 2 lithium bis(fluorosulfonyl
- Examples include lithium oxide (LiB(C 2 O 4 ) 2 ).
- the content of the electrolyte salt is not particularly limited, but is specifically 0.3 mol/kg to 3.0 mol/kg with respect to the solvent. This is because high ionic conductivity can be obtained.
- the electrolytic solution may further contain one or more of additives.
- the additive includes an unsaturated cyclic carbonate, a halogenated cyclic carbonate, a sulfonate, a phosphate, an acid anhydride, a nitrile compound, an isocyanate compound, and the like.
- unsaturated cyclic carbonates include vinylene carbonate, vinylethylene carbonate and methyleneethylene carbonate.
- halogenated cyclic carbonates include ethylene monofluorocarbonate and ethylene difluorocarbonate.
- sulfonate esters include propane sultone and propene sultone.
- phosphate esters include trimethyl phosphate and triethyl phosphate.
- acid anhydrides include succinic anhydride, 1,2-ethanedisulfonic anhydride and 2-sulfobenzoic anhydride.
- nitrile compounds include succinonitrile.
- isocyanate compounds include hexamethylene diisocyanate.
- the polymer compound described here is the first polymer compound contained in the positive electrode electrolyte layer 24 .
- the number of types of the polymer compound may be one, or two or more.
- the polymer compound contains one or both of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer. This is because excellent physical strength and excellent electrochemical stability can be obtained in the positive electrode electrolyte layer 24 .
- Homopolymers of vinylidene fluoride are so-called polyvinylidene fluoride.
- the vinylidene fluoride copolymer is a copolymer of vinylidene fluoride and one or more polymerizable components (monomers), and the types of the polymerizable components are not particularly limited.
- the copolymer of vinylidene fluoride preferably contains hexafluoropropylene as a polymerization component. That is, the polymer compound is preferably a copolymer of vinylidene fluoride and hexafluoropropylene. This is because the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 increases.
- the vinylidene fluoride copolymer preferably further contains one or both of unsaturated dibasic acid and unsaturated dibasic acid monoester as polymerizable components. That is, the polymer compound is a copolymer of vinylidene fluoride, hexafluoropropylene, and an unsaturated dibasic acid, or a copolymer of vinylidene fluoride, hexafluoropropylene, and an unsaturated dibasic acid monoester. or a copolymer of vinylidene fluoride, hexafluoropropylene, unsaturated dibasic acid, and unsaturated dibasic acid monoester. This is because the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 is further increased.
- unsaturated dibasic acids include maleic acid, fumaric acid, itaconic acid and citraconic acid.
- Specific examples of unsaturated dibasic acid monoesters are maleic acid monomethyl ester, maleic acid monoethyl ester, fumaric acid monomethyl ester, fumaric acid monoethyl ester, itaconic acid monomethyl ester, itaconic acid monoethyl ester, citraconic acid monomethyl ester and and citraconic acid monoethyl ester.
- the positive electrode electrolyte layer 24 preferably further contains a plurality of insulating particles. This is because the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 is further increased.
- the insulating particles contain one or both of an inorganic material and a polymer compound.
- inorganic materials include aluminum oxide, zirconium oxide, titanium oxide and magnesium oxide.
- polymer compounds include acrylic resins and styrene resins.
- the negative electrode electrolyte layer 25 is another first electrolyte layer that functions as an intermediary for lithium that is intercalated and deintercalated in the negative electrode 22 , and is arranged between the negative electrode 22 and the separator 23 as shown in FIG. 2 . That is, the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween.
- the negative electrode electrolyte layer 25 is sandwiched between the negative electrode 22 and the separator 23 and is adjacent to the negative electrode 22 and the separator 23 respectively.
- the negative electrode electrolyte layer 25 has the same configuration as the positive electrode electrolyte layer 24 . That is, the negative electrode electrolyte layer 25 is a gel electrolyte containing an electrolytic solution and a polymer compound, and the electrolytic solution is held by the polymer compound. By using the negative electrode electrolyte layer 25, electrolyte leakage is prevented.
- the electrolyte solution described here is the other first electrolyte solution contained in the negative electrode electrolyte layer 25, and the polymer compound described here is the other first electrolyte solution contained in the negative electrode electrolyte layer 25. It is a molecular compound.
- the details of the electrolytic solution and the polymer compound contained in the negative electrode electrolyte layer 25 are the same as the details of the electrolytic solution and the polymer compound contained in the positive electrode electrolyte layer 24 .
- the negative electrode electrolyte layer 25 may contain a plurality of insulating particles.
- the type of electrolytic solution contained in the negative electrode electrolyte layer 25 and the type of electrolytic solution contained in the positive electrode electrolyte layer 24 may be the same or different.
- the type of polymer compound contained in negative electrode electrolyte layer 25 and the type of polymer compound contained in positive electrode electrolyte layer 24 may be the same or different.
- the positive electrode electrolyte layer 26 is a second electrolyte layer that supplies an electrolytic solution to the positive electrode electrolyte layer 24, and is adjacent to the positive electrode electrolyte layer 24 as shown in FIG. More specifically, the positive electrode liquid-retaining layer 26 extends along the direction (Y-axis direction) intersecting the direction (Z-axis direction) in which the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween. 24 are adjacent.
- the positive electrode liquid retaining layer 26 is not sandwiched between the positive electrode 21 and the separator 23 but is in contact with the side surface of the positive electrode electrolyte layer 24 .
- the positive electrode liquid-retaining layers 26 are arranged on both sides of the positive electrode electrolyte layer 24 , so the battery element 20 includes two positive electrode liquid-retaining layers 26 . That is, the first positive electrode liquid retaining layer 26 is arranged on the right side of the positive electrode electrolyte layer 24 , so it is adjacent to the right side surface of the positive electrode electrolyte layer 24 . The second positive electrode liquid-retaining layer 26 is arranged on the left side of the positive electrode electrolyte layer 24 , so it is adjacent to the left side surface of the positive electrode electrolyte layer 24 .
- the positive electrode liquid-retaining layer 26 is arranged on one surface of the separator 23 and thus supported by the separator 23 .
- the cathode liquid retaining layer 26 has the same configuration as the cathode electrolyte layer 24 . That is, the positive electrode liquid retaining layer 26 is a gel electrolyte containing an electrolytic solution and a polymer compound, and the electrolytic solution is held by the polymer compound. This is because the positive electrode liquid-retaining layer 26 can hold the electrolytic solution and the positive electrode liquid-retaining layer 26 can supply the electrolytic solution to the positive electrode electrolyte layer 24 .
- the electrolyte solution described here is the second electrolyte solution contained in the positive electrode liquid-retaining layer 26, and the polymer compound described here is the second polymer compound contained in the positive electrode liquid-retaining layer 26. is.
- the details of the electrolytic solution and the polymer compound contained in the positive electrode electrolyte layer 26 are the same as the details of the electrolytic solution and the polymer compound contained in the positive electrode electrolyte layer 24 .
- the positive electrode liquid retaining layer 26 may contain a plurality of insulating particles.
- the type of electrolytic solution contained in the positive electrode liquid retaining layer 26 and the type of electrolytic solution contained in the positive electrode electrolyte layer 24 may be the same or different.
- the type of polymer compound contained in the positive electrode liquid-retaining layer 26 and the type of polymer compound contained in the positive electrode electrolyte layer 24 may be the same or different.
- the weight ratio R1 is a parameter that represents the content of the electrolyte in the positive electrode electrolyte layer 24, and the weight ratio R2 is a parameter that represents the content of the electrolyte in the positive electrode liquid-retaining layer .
- the positive electrode electrolyte layer 24 is recovered by disassembling the secondary battery, and then the positive electrode electrolyte layer 24 is analyzed using thermogravimetric differential thermal analysis (TG-DTA). As a result, the weight of the electrolytic solution and the weight of the polymer compound are each measured, so the weight ratio R1 can be calculated based on the measurement results.
- TG-DTA thermogravimetric differential thermal analysis
- the procedure for obtaining the weight ratio R2 is the same as the procedure for obtaining the weight ratio R1, except that the positive electrode liquid-retaining layer 26 is recovered and analyzed instead of the positive electrode electrolyte layer 24.
- the thickness T2 of the positive electrode liquid-retaining layer 26 is not particularly limited and can be set arbitrarily. Above all, the thickness T2 of the positive electrode liquid retaining layer 26 is preferably larger than the thickness T1 of the positive electrode electrolyte layer 24 . This is because the amount of the electrolytic solution held by the positive electrode liquid-retaining layer 26 increases, and the amount of the electrolytic solution supplied from the positive electrode liquid-retaining layer 26 to the positive electrode electrolyte layer 24 increases.
- the battery element 20 is collected by disassembling the secondary battery. Subsequently, by cutting the battery element 20 along the YZ plane, the cross section of the battery element 20 is exposed (see FIG. 2). In this case, it is preferable to cut the battery element 20 at the flat portion of the battery element 20 having a flat three-dimensional shape. Subsequently, the thickness of the positive electrode electrolyte layer 24 is measured by observing the cross section of the battery element 20 using a microscope such as a scanning electron microscope (SEM). In this case, the distance between the positive electrode active material layer 21B and the separator 23 is measured, and the distance is taken as the thickness of the positive electrode electrolyte layer 24 . Note that the observation magnification can be arbitrarily set. Finally, after measuring the thickness of the positive electrode electrolyte layer 24 at 30 different locations, the thickness T1 is obtained by calculating the average value of the 30 thicknesses.
- SEM scanning electron microscope
- the procedure for obtaining the thickness T2 is the same as the procedure for obtaining the thickness T1, except that the thickness of the positive electrode liquid-retaining layer 26 is measured based on the observation result of the cross section of the battery element 20.
- the width of the positive electrode current collector 21A is the same as the width of the positive electrode active material layer 21B.
- the positive electrode liquid retaining layer 26 is adjacent not only to the side surface of the positive electrode electrolyte layer 24 but also to a part of the side surface of the positive electrode active material layer 21B. Accordingly, the positive electrode liquid retaining layer 26 is not adjacent to the positive electrode current collector 21A and is separated from the positive electrode current collector 21A.
- the negative electrode electrolyte layer 27 is another second electrolyte layer that supplies the electrolyte to the negative electrode electrolyte layer 25, and is adjacent to the negative electrode electrolyte layer 25 as shown in FIG. More specifically, the negative electrode liquid-retaining layer 27 extends along the direction (Y-axis direction) intersecting the direction (Z-axis direction) in which the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween. 25 are adjacent.
- the negative electrode liquid retaining layer 27 is not sandwiched between the negative electrode 22 and the separator 23 but is in contact with the side surface of the negative electrode electrolyte layer 25 .
- the battery element 20 since the negative electrode liquid-retaining layers 27 are arranged on both sides of the negative electrode electrolyte layer 25 , the battery element 20 includes two negative electrode liquid-retaining layers 27 . That is, the first negative electrode retaining liquid layer 27 is arranged on the right side of the negative electrode electrolyte layer 25 , so it is adjacent to the right side surface of the negative electrode electrolyte layer 25 . Since the second negative electrode liquid retaining layer 27 is arranged on the left side of the negative electrode electrolyte layer 25 , it is adjacent to the left side surface of the negative electrode electrolyte layer 25 .
- the negative electrode liquid-retaining layer 27 is arranged on one surface of the separator 23 (the surface opposite to the surface on which the positive electrode liquid-retaining layer 26 is formed), and thus is supported by the separator 23 .
- the negative electrode liquid retaining layer 27 has the same configuration as the negative electrode electrolyte layer 25 . That is, the negative electrode liquid retaining layer 27 is a gel electrolyte containing an electrolyte and a polymer compound, and the electrolyte is retained by the polymer compound. This is because the negative electrode liquid-retaining layer 27 can hold the electrolytic solution and the negative electrode liquid-retaining layer 27 can supply the electrolytic solution to the negative electrode electrolyte layer 25 .
- the electrolyte solution described here is the other second electrolyte solution contained in the negative electrode liquid-retaining layer 27
- the polymer compound described here is the other second electrolyte solution contained in the negative electrode liquid-retaining layer 27
- 2 is a polymer compound.
- the details of the electrolytic solution and the polymer compound contained in the negative electrode electrolyte layer 27 are the same as the details of the electrolytic solution and the polymer compound contained in the negative electrode electrolyte layer 25 .
- the negative electrode liquid retaining layer 27 may contain a plurality of insulating particles.
- the type of electrolytic solution contained in the negative electrode liquid retaining layer 27 and the type of electrolytic solution contained in the negative electrode electrolyte layer 25 may be the same or different.
- the type of polymer compound contained in the negative electrode liquid-retaining layer 27 and the type of polymer compound contained in the negative electrode electrolyte layer 25 may be the same or different.
- the weight ratio R3 is a parameter representing the content of the electrolyte in the negative electrode electrolyte layer 25, and the weight ratio R4 is a parameter representing the content of the electrolyte in the negative electrode liquid-retaining layer 27.
- the procedure for obtaining the weight ratio R3 is the same as the procedure for obtaining the weight ratio R1, except that the negative electrode electrolyte layer 25 is collected and analyzed instead of the positive electrode electrolyte layer 24.
- the procedure for obtaining the weight ratio R4 is the same as the procedure for obtaining the weight ratio R1, except that the negative electrode liquid-retaining layer 27 is collected and analyzed instead of the positive electrode electrolyte layer 24 .
- the thickness T4 of the negative electrode liquid-retaining layer 27 is not particularly limited and can be set arbitrarily. Among them, the thickness T4 of the negative electrode liquid retaining layer 27 is preferably larger than the thickness T3 of the negative electrode electrolyte layer 25 . This is because the amount of the electrolytic solution held by the negative electrode liquid-retaining layer 27 increases, and the amount of the electrolytic solution supplied from the negative electrode liquid-retaining layer 27 to the negative electrode electrolyte layer 25 increases.
- the procedure for obtaining the thickness T3 is the thickness T3 except for measuring the thickness of the negative electrode electrolyte layer 25 (the distance between the negative electrode active material layer 22B and the separator 23) based on the observation result of the cross section of the battery element 20.
- the procedure for determining the thickness T1 is the same.
- the procedure for determining the thickness T4 is the same as the procedure for determining the thickness T1, except that the thickness of the negative electrode liquid-retaining layer 27 is measured based on the observation result of the cross section of the battery element 20 .
- the width of the negative electrode current collector 22A is the same as the width of the negative electrode active material layer 22B.
- the negative electrode liquid retaining layer 27 is adjacent not only to the side surface of the negative electrode electrolyte layer 25 but also to a part of the side surface of the negative electrode active material layer 22B. Thus, the negative electrode liquid retaining layer 27 is not adjacent to the negative electrode current collector 22A and is separated from the negative electrode current collector 22A.
- the positive electrode lead 31 is a positive electrode terminal connected to the positive electrode 21, as shown in FIG. 1, and more specifically connected to the positive current collector 21A.
- the positive electrode lead 31 extends from the inside of the exterior film 10 to the outside, and contains a conductive material such as aluminum.
- the shape of the positive electrode lead 31 is not particularly limited, but specifically, it is either a thin plate shape, a mesh shape, or the like.
- the negative electrode lead 32 is a negative electrode terminal connected to the negative electrode 22, as shown in FIG. 1, and more specifically connected to the negative electrode current collector 22A.
- the negative electrode lead 32 is led out from the interior of the exterior film 10 and contains a conductive material such as copper.
- the lead-out direction of the negative lead 32 is the same as the lead-out direction of the positive lead 31 .
- Details regarding the shape of the negative electrode lead 32 are the same as those regarding the shape of the positive electrode lead 31 .
- the electrolyte in the positive electrode electrolyte layer 24 is consumed and the electrolyte in the negative electrode electrolyte layer 25 is consumed, the electrolyte is transferred from the positive electrode liquid retaining layer 26 to the positive electrode electrolyte layer 24 .
- the electrolytic solution is supplied from the negative electrode liquid retaining layer 27 to the negative electrode electrolyte layer 25 .
- the positive electrode 21, the negative electrode 22, the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 are each manufactured by the procedure described below. , to produce a secondary battery using them.
- a paste-like positive electrode mixture slurry is prepared by putting a mixture (positive electrode mixture) in which a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent are mixed together into a solvent.
- This solvent may be an aqueous solvent or an organic solvent.
- the cathode active material layer 21B is formed by applying the cathode mixture slurry to both surfaces of the cathode current collector 21A.
- the cathode active material layer 21B may be compression-molded using a roll press machine or the like. In this case, the positive electrode active material layer 21B may be heated, or compression molding may be repeated multiple times. As a result, the cathode active material layers 21B are formed on both surfaces of the cathode current collector 21A, so that the cathode 21 is produced.
- a negative electrode 22 is formed by the same procedure as that of the positive electrode 21 described above. Specifically, first, a mixture (negative electrode mixture) in which a negative electrode active material, a negative electrode binder, and a negative electrode conductive agent are mixed together is put into a solvent to prepare a pasty negative electrode mixture slurry. Prepare. Subsequently, the anode active material layer 22B is formed by applying the anode mixture slurry to both surfaces of the anode current collector 22A. After that, the negative electrode active material layer 22B may be compression molded. As a result, the negative electrode 22 is manufactured because the negative electrode active material layers 22B are formed on both surfaces of the negative electrode current collector 22A.
- the electrolyte salt is added to the solvent.
- the electrolyte salt is dissolved or dispersed in the solvent to prepare an electrolytic solution.
- a precursor solution is prepared by mixing together the electrolytic solution, the polymer compound, and optionally additional solvent.
- the positive electrode electrolyte layer 24 is formed by applying the precursor solution to the surface of the positive electrode 21 .
- the negative electrode electrolyte layer 25 is formed by the same procedure as that for forming the positive electrode electrolyte layer 24 described above. Specifically, an electrolytic solution is prepared, a precursor solution is prepared using the electrolytic solution and a polymer compound, and then the precursor solution is applied to the surface of the negative electrode 22 to form the negative electrode electrolyte layer 25 .
- an electrolytic solution is prepared by adding an electrolytic salt to a solvent. Subsequently, the electrolytic solution, the polymer compound, and, if necessary, an additional solvent are mixed with each other to prepare a precursor solution. A layer 26 is formed. In this case, the surface of the separator 23 may be masked with a polymer film such as a polypropylene film.
- the negative electrode liquid-retaining layer 27 is formed by the same procedure as that for forming the positive electrode liquid-retaining layer 26 described above. Specifically, after preparing an electrolytic solution and preparing a precursor solution using the electrolytic solution and a polymer compound, one surface of the separator 23 (the opposite side to the surface on which the positive electrode liquid holding layer 26 is formed) surface), the negative electrode liquid-retaining layer 27 is formed.
- the positive electrode lead 31 is connected to the positive electrode current collector 21A of the positive electrode 21 by welding or the like, and the negative electrode lead 32 is connected to the negative electrode current collector 22A of the negative electrode 22 by welding or the like.
- the positive electrode 21 formed with the positive electrode electrolyte layer 24 and the negative electrode 22 formed with the negative electrode electrolyte layer 25 are separated through the separator 23 formed with the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27. are stacked on top of each other.
- the positive electrode retaining liquid layer 26 is adjacent to the positive electrode electrolyte layer 24 and the negative electrode retaining liquid layer 27 is adjacent to the negative electrode electrolyte layer 25 .
- the positive electrode 21 , the negative electrode 22 , the separator 23 , the positive electrode electrolyte layer 24 , the negative electrode electrolyte layer 25 , the positive electrode liquid-retaining layer 26 , and the negative electrode liquid-retaining layer 27 are wound to form the battery element 20 .
- the battery element 20 is molded into a flat shape.
- the exterior films 10 (bonding layer/metal layer/surface protective layer) are folded so that the exterior films 10 face each other.
- the outer peripheral edges of three sides of the exterior films 10 (fusion layers) facing each other are joined together.
- a sealing film 41 is inserted between the packaging film 10 and the positive electrode lead 31 and a sealing film 42 is inserted between the packaging film 10 and the negative electrode lead 32 .
- the battery element 20 is enclosed inside the bag-shaped exterior film 10, so that the secondary battery is assembled.
- the secondary battery after assembly is charged and discharged.
- Various conditions such as environmental temperature, number of charge/discharge times (number of cycles), and charge/discharge conditions can be arbitrarily set.
- films are formed on the respective surfaces of the positive electrode 21 and the negative electrode 22, so that the state of the secondary battery is electrochemically stabilized.
- a laminated film type secondary battery using the exterior film 10 is completed.
- the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween, and the direction in which the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween (the Z-axis direction).
- the positive electrode electrolyte layer 24 is adjacent to the positive electrode electrolyte layer 24 in the direction (Y-axis direction) intersecting the , and the weight ratio R2 of the positive electrode electrolyte layer 26 is larger than the weight ratio R1 of the positive electrode electrolyte layer 24.
- the electrolyte in the positive electrode electrolyte layer 24 is consumed during charging and discharging, the electrolyte is supplied from the positive electrode liquid-retaining layer 26 to the positive electrode electrolyte layer 24, so that the positive electrode electrolyte layer 24 It becomes difficult for the amount of electrolyte inside to decrease.
- the weight ratio R2 of the positive electrode retaining liquid layer 26 is larger than the weight ratio R1 of the positive electrode electrolyte layer 24, a sufficient amount of electrolyte is supplied from the positive electrode retaining liquid layer 26 to the positive electrode electrolyte layer 24. be done. Therefore, even if charging and discharging are repeated, a decrease in discharge capacity is suppressed, and excellent cycle characteristics can be obtained.
- the effect obtained based on the positive electrode electrolyte layer 24 and the positive electrode liquid-retaining layer 26 described above can also be similarly obtained based on the negative electrode electrolyte layer 25 and the negative electrode liquid-retaining layer 27 . That is, the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween, and the direction (the Z-axis direction) in which the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween (the direction Y).
- the negative electrode electrolyte layer 25 is adjacent to the negative electrode electrolyte layer 25 in the axial direction), and the weight ratio R4 of the negative electrode electrolyte layer 27 is larger than the weight ratio R3 of the negative electrode electrolyte layer 25 .
- the thickness T2 of the positive electrode liquid-retaining layer 26 is greater than the thickness T1 of the positive electrode electrolyte layer 24, the amount of electrolyte retained by the positive electrode liquid-retaining layer 26 increases. Therefore, the amount of the electrolytic solution supplied from the positive electrode liquid retaining layer 26 to the positive electrode electrolyte layer 24 is increased, so that a higher effect can be obtained.
- the effect obtained based on the thickness T1 of the positive electrode electrolyte layer 24 and the thickness T2 of the positive electrode liquid-retaining layer 26 is also based on the thickness T3 of the negative electrode electrolyte layer 25 and the thickness T4 of the negative electrode liquid-retaining layer 27. similarly obtained. That is, if the thickness T4 of the negative electrode liquid-retaining layer 27 is larger than the thickness T3 of the negative electrode electrolyte layer 25, the amount of electrolyte retained by the negative electrode liquid-retaining layer 27 increases. Therefore, the amount of the electrolytic solution supplied from the negative electrode liquid retaining layer 27 to the negative electrode electrolyte layer 25 is increased, so that a higher effect can be obtained.
- the positive electrode electrolyte layer 24 contains one or both of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer, the positive electrode electrolyte layer 24 is excellent. Higher effect can be obtained due to physical strength and excellent electrochemical stability.
- the vinylidene fluoride copolymer contains hexafluoropropylene as a polymerization component, the amount of electrolyte retained by the positive electrode electrolyte layer 24 increases, so that a higher effect can be obtained. Further, if the vinylidene fluoride copolymer further contains one or both of unsaturated dibasic acid and unsaturated dibasic acid monoester as polymerization components, the amount of electrolytic solution retained by positive electrode electrolyte layer 24 is increased. Since it increases more, a higher effect can be obtained.
- the positive electrode electrolyte layer 24 contains a plurality of insulating particles, the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 increases, so that a higher effect can be obtained.
- the secondary battery is a lithium-ion secondary battery
- a sufficient battery capacity can be stably obtained by utilizing the absorption and release of lithium, so a higher effect can be obtained.
- the positive electrode liquid-retaining layers 26 are arranged on both sides of the positive electrode electrolyte layer 24 , so the battery element 20 includes two positive electrode liquid-retaining layers 26 .
- the battery element 20 may include only one positive electrode liquid-retaining layer 26 . In this case as well, compared with the case where the battery element 20 does not include the positive electrode liquid retaining layer 26, the decrease in discharge capacity is suppressed even after repeated charging and discharging, and the same effect can be obtained.
- the above-described modification regarding the placement location of the positive electrode liquid-retaining layer 26 is the same for the placement location of the negative electrode liquid-retaining layer 27 . That is, since the negative electrode liquid-retaining layers 27 are arranged on both sides of the negative electrode electrolyte layer 25, the battery element 20 includes two negative electrode liquid-retaining layers 27. Since the liquid layer 27 is arranged, the battery element 20 may include only one negative electrode liquid-retaining layer 27 . Also in this case, compared with the case where the battery element 20 does not include the negative electrode liquid retaining layer 27, the decrease in the discharge capacity is suppressed even after repeated charging and discharging, so that the same effect can be obtained.
- the positive electrode electrolyte layer 24 is adjacent to the positive electrode liquid-retaining layer 26
- the negative electrode electrolyte layer 25 is adjacent to the negative electrode liquid-retaining layer 27 .
- the positive electrode electrolyte layer 24 is adjacent to the positive electrode electrolyte layer 26
- the negative electrode electrolyte layer 25 may not be adjacent to the negative electrode electrolyte layer 27 .
- the positive electrode electrolyte layer 24 is not adjacent to the positive electrode electrolyte layer 26
- the negative electrode electrolyte layer 25 may be adjacent to the negative electrode electrolyte layer 27 .
- the discharge capacity is lower even after repeated charging and discharging. Since the decrease in is suppressed, a similar effect can be obtained.
- the modification of the manufacturing method of the battery element 20 including the positive electrode liquid-retaining layer 26 described above also applies to the manufacturing method of the battery element 20 including the negative electrode liquid-retaining layer 27 . That is, after the negative electrode liquid-retaining layer 27 is formed on one surface of the separator 23, the separator 23 having the negative electrode liquid-retaining layer 27 formed thereon is wound. A negative electrode liquid retaining layer 27 may be formed on one surface of 23 . Even in this case, since the battery element 20 including the negative electrode liquid-retaining layer 27 can be produced, a similar effect can be obtained.
- a separator 23 which is a porous membrane, was used. However, although not specifically illustrated here, a laminated separator including a polymer compound layer may be used.
- a laminated separator includes a porous membrane having a pair of surfaces and a polymer compound layer disposed on one or both sides of the porous membrane. This is because the adhesiveness of the separator to each of the positive electrode 21 and the negative electrode 22 is improved, so that positional deviation (winding deviation) of the battery element 20 is suppressed. As a result, swelling of the secondary battery is suppressed even if a decomposition reaction or the like of the electrolytic solution occurs.
- the polymer compound layer contains a polymer compound such as polyvinylidene fluoride. This is because polyvinylidene fluoride or the like has excellent physical strength and is electrochemically stable.
- One or both of the porous film and the polymer compound layer may contain one or more of a plurality of insulating particles. This is because the plurality of insulating particles dissipate heat when the secondary battery generates heat, thereby improving the safety (heat resistance) of the secondary battery. Details regarding the plurality of insulating particles are provided above.
- the precursor solution is applied to one or both sides of the porous membrane.
- a plurality of insulating particles may be added to the precursor solution.
- the battery element 20, which is a wound electrode body is used.
- a battery element 50 that is a laminated electrode body may be used.
- FIGS. 1 and 2 which have already been described, from time to time.
- the laminated film type secondary battery shown in FIGS. 27 and instead of the positive electrode lead 31 and the negative electrode lead 32, the battery element 50 (the positive electrode 51, the negative electrode 52, the separator 53, the positive electrode electrolyte layer 54, the negative electrode electrolyte layer 55, the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57) and It has substantially the same configuration as the laminated film type secondary battery shown in FIGS.
- the configurations of the positive electrode 51, the negative electrode 52, the separator 53, the positive electrode electrolyte layer 54, the negative electrode electrolyte layer 55, the positive electrode retaining liquid layer 56, the negative electrode retaining liquid layer 57, the positive electrode lead 58, and the negative electrode lead 59 will be described below. Except for the above, the positive electrode 21 , the negative electrode 22 , the separator 23 , the positive electrode electrolyte layer 24 , the negative electrode electrolyte layer 25 , the positive electrode liquid layer 26 , the negative electrode liquid layer 27 , the positive electrode lead 31 and the negative electrode lead 32 have the same configuration.
- the relationship between the weight ratio R1 of the positive electrode electrolyte layer 54 and the weight ratio R2 of the positive electrode liquid-retaining layer 56 and the relationship between the weight ratio R3 of the negative electrode electrolyte layer 55 and the weight ratio R4 of the negative electrode liquid-retaining layer 57 are as described above. is. Further, the relationship between the thickness T1 of the positive electrode electrolyte layer 54 and the thickness T2 of the positive electrode electrolyte layer 56 and the relationship between the thickness T3 of the negative electrode electrolyte layer 55 and the thickness T of the negative electrode electrolyte layer 57 are as described above. is.
- positive electrodes 51 and negative electrodes 52 are alternately laminated with separators 53, positive electrode electrolyte layers 54, and negative electrode electrolyte layers 55 interposed therebetween.
- the positive electrode retaining liquid layer 56 is adjacent to the positive electrode electrolyte layer 54
- the negative electrode retaining liquid layer 57 is adjacent to the negative electrode electrolyte layer 55 .
- the number of layers of the positive electrode 51, the negative electrode 52, the separator 53, the positive electrode electrolyte layer 54, and the negative electrode electrolyte layer 55 is not particularly limited, and can be set arbitrarily.
- the positive electrode 51 includes a positive electrode current collector 51A and a positive electrode active material layer 51B corresponding to the positive electrode current collector 21A and the positive electrode active material layer 21B
- the negative electrode 52 includes the negative electrode current collector 22A and the negative electrode active material layer 22B. and a negative electrode current collector 52A and a negative electrode active material layer 52B corresponding to .
- the positive electrode current collector 51A includes protrusions 51AT on which the positive electrode active material layer 51B is not formed, and the negative electrode current collector 52A includes the negative electrode active material layer.
- 52B includes projections 52AT that are not formed.
- the projecting portion 52AT is arranged at a position not overlapping the projecting portion 51AT. Since the plurality of projecting portions 51AT are joined to each other, they form one lead-shaped joint portion 51Z. A joint portion 52Z is formed.
- the positive lead 58 is connected to the joint 51Z, and the negative lead 59 is connected to the joint 52Z.
- the battery element 50 is produced instead of the battery element 20, and the positive electrode lead 58 and the negative electrode lead 59 are used instead of the positive electrode lead 31 and the negative electrode lead 32.
- the manufacturing method of the secondary battery shown in FIGS. 1 and 2 is the same except that the secondary battery is assembled.
- a negative electrode 52 having negative electrode active material layers 52B formed on both surfaces thereof is manufactured.
- a positive electrode electrolyte layer 54 is formed on the surface of the positive electrode 51 and a negative electrode electrolyte layer 55 is formed on the surface of the negative electrode 52 .
- a positive electrode liquid-retaining layer 56 and a negative electrode liquid-retaining layer 57 are formed on both surfaces of the separator 53 .
- the positive electrode 51 formed with the positive electrode electrolyte layer 54 and the negative electrode 52 formed with the negative electrode electrolyte layer 55 are alternately arranged with the separator 53 formed with the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57 interposed therebetween.
- the battery element 50 is produced by stacking the layers.
- the plurality of projecting portions 51AT are joined to each other using a welding method or the like to form the joining portion 51Z
- the plurality of projecting portions 52AT are joined to each other using a welding method or the like to form the joining portion 52Z.
- a welding method or the like is used to connect the positive electrode lead 58 to the projecting portion 51AT
- a welding method or the like is used to connect the negative electrode lead 59 to the projecting portion 52AT.
- a secondary battery used as a power source may be a main power source for electronic devices and electric vehicles, or may be an auxiliary power source.
- a main power source is a power source that is preferentially used regardless of the presence or absence of other power sources.
- An auxiliary power supply is a power supply that is used in place of the main power supply or that is switched from the main power supply.
- Secondary battery applications are as follows. Electronic devices such as video cameras, digital still cameras, mobile phones, laptop computers, headphone stereos, portable radios and portable information terminals. Backup power and storage devices such as memory cards. Power tools such as power drills and power saws. It is a battery pack mounted on an electronic device. Medical electronic devices such as pacemakers and hearing aids. It is an electric vehicle such as an electric vehicle (including a hybrid vehicle). It is a power storage system such as a home or industrial battery system that stores power in preparation for emergencies. In these uses, one secondary battery may be used, or a plurality of secondary batteries may be used.
- the battery pack may use a single cell or an assembled battery.
- An electric vehicle is a vehicle that operates (runs) using a secondary battery as a drive power source, and may be a hybrid vehicle that also includes a drive source other than the secondary battery.
- electric power stored in a secondary battery which is an electric power storage source, can be used to use electric appliances for home use.
- Fig. 5 shows the block configuration of the battery pack.
- the battery pack described here is a battery pack (a so-called soft pack) using one secondary battery, and is mounted in an electronic device such as a smart phone.
- This battery pack includes a power supply 61 and a circuit board 62, as shown in FIG.
- This circuit board 62 is connected to a power supply 61 and includes a positive terminal 63 , a negative terminal 64 and a temperature detection terminal 65 .
- the power supply 61 includes one secondary battery.
- the positive lead is connected to the positive terminal 63 and the negative lead is connected to the negative terminal 64 .
- the power source 61 can be connected to the outside through a positive terminal 63 and a negative terminal 64, and can be charged and discharged.
- the circuit board 62 includes a control section 66 , a switch 67 , a thermal resistance element (PTC element) 68 and a temperature detection section 69 .
- the PTC element 68 may be omitted.
- the control unit 66 includes a central processing unit (CPU), memory, etc., and controls the operation of the entire battery pack. This control unit 66 detects and controls the use state of the power source 61 as necessary.
- CPU central processing unit
- memory etc.
- the overcharge detection voltage is not particularly limited, but is specifically 4.2V ⁇ 0.05V, and the overdischarge detection voltage is not particularly limited, but is specifically 2.4V ⁇ 0.1V. is.
- the switch 67 includes a charge control switch, a discharge control switch, a charge diode, a discharge diode, and the like, and switches connection/disconnection between the power supply 61 and an external device according to instructions from the control unit 66 .
- the switch 67 includes a field effect transistor (MOSFET) using a metal oxide semiconductor, etc., and the charge/discharge current is detected based on the ON resistance of the switch 67 .
- MOSFET field effect transistor
- the temperature detection unit 69 includes a temperature detection element such as a thermistor, measures the temperature of the power supply 61 using the temperature detection terminal 65 , and outputs the temperature measurement result to the control unit 66 .
- the measurement result of the temperature measured by the temperature detection unit 69 is used when the control unit 66 performs charging/discharging control at the time of abnormal heat generation and when the control unit 66 performs correction processing when calculating the remaining capacity.
- a laminated film type lithium ion secondary battery including the battery element 20 (wound electrode body) shown in FIGS. 1 and 2 was produced by the following procedure.
- a positive electrode active material LiNi 0.80 Co 0.15 Al 0.05 O 2 which is a lithium-containing compound (oxide)
- 3 parts by mass of a positive electrode binder polyvinylidene fluoride
- a positive electrode conductor carbon black
- the organic solvent was stirred to prepare a pasty positive electrode mixture slurry.
- the positive electrode mixture slurry is applied to both surfaces of the positive electrode current collector 21A (aluminum foil having a thickness of 15 ⁇ m) using a coating device, and then the positive electrode mixture slurry is dried to form a positive electrode active material layer. 21B. Finally, the positive electrode active material layer 21B was compression-molded using a roll press, and then the positive electrode current collector 21A on which the positive electrode active material layer 21B was formed was cut into strips (48 mm ⁇ 300 mm). Thus, the positive electrode 21 was produced.
- the positive electrode current collector 21A aluminum foil having a thickness of 15 ⁇ m
- a negative electrode active material artificial graphite that is a carbon material
- a negative electrode binder polyvinylidene fluoride
- the organic solvent was stirred to prepare a pasty negative electrode mixture slurry.
- the negative electrode mixture slurry is applied to both surfaces of the negative electrode current collector 22A (copper foil having a thickness of 15 ⁇ m) using a coating device, and then the negative electrode mixture slurry is dried to form a negative electrode active material layer.
- the negative electrode active material layer 22B was compression-molded using a roll press, and then the negative electrode current collector 22A on which the negative electrode active material layer 22B was formed was cut into strips (50 mm ⁇ 310 mm). Thus, the negative electrode 22 was produced.
- PVDF polyvinylidene fluoride
- VH copolymer of vinylidene fluoride and hexafluoropropylene
- unsaturated dibasic acid maleic acid
- VHMA Polymer (VHMA), copolymer (VHMMM) of vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic acid monoester (monomethyl maleate), vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic a copolymer (VHMME) with an acid monoester (monoethyl maleate) and a copolymer (VHCMM) with vinylidene fluoride, hexafluoropropylene, and an unsaturated dibasic acid monoester (citraconic acid monomethyl ester); and a copolymer (VHCME) of vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic acid monoester (citraconic acid monoethyl ester).
- VHMME copolymer with an acid monoester (monoethyl maleate)
- VHCMM copo
- the weight ratio R1 is controlled by adjusting the mixing ratio of the electrolyte and the polymer compound, and the thickness T1 is adjusted by adjusting the coating amount of the precursor solution. ( ⁇ m) was controlled. Details of each of the weight ratio R1 and the thickness T1 are shown in Table 1.
- a negative electrode electrolyte layer 25 was formed in the same manner as the positive electrode electrolyte layer 24 except that the precursor solution was applied to the surface of the negative electrode 22 . Details of each of the weight ratio R3 and the thickness T3 are shown in Table 1.
- a positive electrode liquid-retaining layer 26 was formed in the same manner as the positive electrode electrolyte layer 24, except that the precursor solution was applied to one surface of the separator 23 (a microporous polypropylene film having a thickness of 11 ⁇ m).
- the weight ratio R2 of the positive electrode liquid retaining layer 26 was made larger than the weight ratio R1 of the positive electrode electrolyte layer 24 by adjusting the mixing ratio of the electrolytic solution and the polymer compound. Details of each of the weight ratio R2 and thickness T2 are shown in Table 1.
- a negative electrode liquid-retaining layer was formed by the same procedure as that for forming the positive electrode electrolyte layer 24, except that the precursor solution was applied to one surface of the separator 23 (the surface opposite to the surface on which the positive electrode liquid-retaining layer 26 was formed). 27 was formed.
- the weight ratio R4 of the negative electrode liquid retaining layer 27 was made larger than the weight ratio R3 of the negative electrode electrolyte layer 25 by adjusting the mixing ratio of the electrolyte and the polymer compound. Details of each of the weight ratio R4 and the thickness T4 are shown in Table 1.
- Examples 1 to 10 and Comparative Examples 1 to 3 in order to form the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27, respectively, electrolytic solutions having compositions common to each other were used. was used, and a common type of polymer compound was used. Table 1 shows only one column of "polymer compound" because, as described above, each of the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 This indicates that a common type of polymer compound was used.
- Example 11 the types of polymer compounds used to form the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25, respectively, and the types of polymer compounds used to form the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27, respectively.
- the types of polymer compounds were made different from each other. Specifically, PVDF was used to form each of the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25, and VHMMM was used to form each of the positive electrode electrolyte layer 26 and the negative electrode electrolyte layer 27.
- the positive electrode liquid-retaining layer 26 was formed such that the weight ratio R2 was equal to or less than the weight ratio R1
- the negative electrode liquid-retaining layer 27 was formed such that the weight ratio R4 was equal to or less than the weight ratio R3.
- the positive electrode lead 31 made of aluminum was welded to the positive electrode current collector 21A of the positive electrode 21, and the negative electrode lead 32 made of copper was welded to the negative electrode current collector 22A of the negative electrode 22. As shown in FIG.
- the positive electrode 21 formed with the positive electrode electrolyte layer 24 and the negative electrode 22 formed with the negative electrode electrolyte layer 25 are separated through the separator 23 formed with the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27. were stacked on top of each other. Subsequently, the positive electrode 21, the negative electrode 22, the separator 23, the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 were wound to produce the battery element 20. Subsequently, the battery element 20 was molded into a flat shape by pressing the battery element 20 using a pressing machine.
- the exterior films 10 (bonding layer/metal layer/surface protective layer) were folded to face each other.
- the exterior film 10 includes a fusion layer (polypropylene film with a thickness of 30 ⁇ m), a metal layer (aluminum foil with a thickness of 40 ⁇ m), and a surface protective layer (nylon film with a thickness of 25 ⁇ m). Aluminum laminate films laminated in this order from the inside were used.
- the battery element 20 was sealed inside the bag-shaped exterior film 10, and thus the secondary battery was assembled.
- constant-current charging was performed at a current of 0.1C until the voltage reached 4.2V
- constant-voltage charging was performed at the voltage of 4.2V until the current reached 0.05C.
- constant current discharge was performed at a current of 0.1C until the voltage reached 3.0V.
- 0.1C is a current value that can fully discharge the battery capacity (theoretical capacity) in 10 hours
- 0.05C is a current value that fully discharges the battery capacity in 20 hours.
- the discharge capacity discharge capacity in the first cycle
- the secondary battery was repeatedly charged and discharged in the same environment until the number of cycles reached 300 cycles, thereby measuring the discharge capacity (discharge capacity at the 300th cycle).
- the charge/discharge conditions were the same as the charge/discharge conditions during stabilization of the secondary battery, except that the current during charging and the current during discharging were each changed to 0.5C.
- 0.5C is a current value that can discharge the battery capacity in 2 hours.
- the capacity retention rate was further increased.
- the amount of the insulating particles added was 2.5% by weight with respect to the sum of the weight of the electrolytic solution and the weight of the polymer compound.
- the manufacturing procedure of the secondary battery having the battery element 50 is the same as the manufacturing procedure of the secondary battery having the battery element 20, except for the following description.
- the positive electrode 51 formed with the positive electrode electrolyte layer 54 and the negative electrode 52 formed with the negative electrode electrolyte layer 55 are alternately laminated with the separator 53 formed with the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57 interposed therebetween.
- a battery element 50 was produced.
- the plurality of projecting portions 51AT were welded together to form joint portions 51Z
- the plurality of projecting portions 52AT were welded together to form joint portions 52Z.
- the positive electrode lead 58 was welded to the projecting portion 51AT
- the negative electrode lead 59 was welded to the projecting portion 52AT.
- the positive electrode electrolyte layer 24 is arranged between the positive electrode 21 and the separator 23, the positive electrode electrolyte layer 24 is adjacent to the positive electrode liquid retaining layer 26, and the positive electrode retaining layer 26 is adjacent to the positive electrode electrolyte layer 24.
- the weight ratio R2 of the liquid layer 26 was larger than the weight ratio R1 of the positive electrode electrolyte layer 24, the capacity retention rate was significantly improved. Therefore, excellent cycle characteristics were obtained in the secondary battery.
- a negative electrode electrolyte layer 25 is arranged between the negative electrode 22 and the separator 23, and a negative electrode electrolyte layer 25 is adjacent to the negative electrode electrolyte layer 27.
- the weight ratio R4 of the negative electrode liquid retaining layer 27 is Even when the weight ratio of the electrolyte layer 25 was greater than R3, the capacity retention rate was significantly improved, and thus the secondary battery had excellent cycle characteristics.
- the type of battery structure is not particularly limited.
- the battery structure may be cylindrical, rectangular, coin-shaped, button-shaped, and the like.
- the configuration of the battery element is the wound type and the laminated type has been described, but the configuration of the battery element is not particularly limited.
- the configuration of the battery element may be a ninety-nine fold type in which the positive electrode and the negative electrode are folded in a zigzag pattern.
- the type of the electrode reactant is not particularly limited.
- the electrode reactants may be other alkali metals such as sodium and potassium, or alkaline earth metals such as beryllium, magnesium and calcium, as described above.
- the electrode reactant may be other light metals such as aluminum.
Abstract
This secondary battery comprises: a first electrolyte layer including a first electrolyte and a first polymer compound; an electrode and a separator facing each other with the first electrolyte layer interposed therebetween; and a second electrolyte layer that is adjacent to the first electrolyte layer in the direction intersecting the direction in which the electrode and the separator face each other with the first electrolyte layer interposed therebetween, and that contains a second electrolyte and a second polymer compound. The ratio of the second electrolyte weight to the second polymer compound weight is greater than the ratio of the first electrolyte weight to the first polymer compound weight.
Description
本技術は、二次電池に関する。
This technology relates to secondary batteries.
携帯電話機などの多様な電子機器が普及しているため、小型かつ軽量であると共に高エネルギー密度を有する電源として二次電池の開発が進められている。この二次電池は、正極および負極と共に電解質層を備えており、その電解質層は、電解液および高分子化合物を含んでいる。
Due to the widespread use of various electronic devices such as mobile phones, secondary batteries are being developed as power sources that are compact, lightweight, and have high energy density. The secondary battery includes a positive electrode, a negative electrode, and an electrolyte layer, and the electrolyte layer contains an electrolytic solution and a polymer compound.
電解質層を備えた二次電池の構成に関しては、様々な検討がなされている。具体的には、高温信頼性を向上させるために、正極とセパレータとの間にゲル状の電解質膜が設けられていると共に、負極とセパレータとの間にゲル状の電解質膜が設けられている（例えば、特許文献１参照。）。
Various studies have been conducted on the configuration of a secondary battery with an electrolyte layer. Specifically, in order to improve high-temperature reliability, a gel electrolyte film is provided between the positive electrode and the separator, and a gel electrolyte film is provided between the negative electrode and the separator. (See Patent Document 1, for example).
二次電池の電池特性に関する様々な検討がなされているが、その二次電池のサイクル特性は未だ十分でないため、改善の余地がある。
Various studies have been conducted on the battery characteristics of secondary batteries, but the cycle characteristics of the secondary batteries are still insufficient, so there is room for improvement.
よって、優れたサイクル特性を得ることが可能である二次電池が望まれている。
Therefore, a secondary battery capable of obtaining excellent cycle characteristics is desired.
本技術の一実施形態の二次電池は、第１電解液および第１高分子化合物を含む第１電解質層と、その第１電解質層を介して互いに対向する電極およびセパレータと、その電極およびセパレータが第１電解質層を介して互いに対向する方向と交差する方向において第１電解質層に隣接され、第２電解液および第２高分子化合物を含む第２電解質層とを備えたものである。第２高分子化合物の重量に対する第２電解液の重量の比は、第１高分子化合物の重量に対する第１電解液の重量の比よりも大きい。
A secondary battery of an embodiment of the present technology includes a first electrolyte layer containing a first electrolyte solution and a first polymer compound, electrodes and separators facing each other via the first electrolyte layer, and the electrodes and separators is adjacent to the first electrolyte layer in a direction intersecting the direction facing each other with the first electrolyte layer interposed therebetween, and includes a second electrolyte layer containing a second electrolytic solution and a second polymer compound. The ratio of the weight of the second electrolytic solution to the weight of the second polymer compound is greater than the ratio of the weight of the first electrolytic solution to the weight of the first polymer compound.
本技術の一実施形態の二次電池によれば、電極およびセパレータが第１電解質層（第１電解液および第１高分子化合物）を介して互いに対向しており、その電極およびセパレータが第１電解質層を介して互いに対向する方向と交差する方向において第１電解質層に第２電解質層（第２電解液および第２高分子化合物）が隣接されており、その第２高分子化合物の重量に対する第２電解液の重量の比が第１高分子化合物の重量に対する第１電解液の重量の比よりも大きいので、優れたサイクル特性を得ることができる。
According to the secondary battery of one embodiment of the present technology, the electrode and the separator face each other via the first electrolyte layer (the first electrolytic solution and the first polymer compound), and the electrode and the separator face the first A second electrolyte layer (second electrolytic solution and second polymer compound) is adjacent to the first electrolyte layer in a direction intersecting the direction facing each other with the electrolyte layer interposed therebetween, and the weight of the second polymer compound is Since the weight ratio of the second electrolytic solution is greater than the weight ratio of the first electrolytic solution to the weight of the first polymer compound, excellent cycle characteristics can be obtained.
なお、本技術の効果は、必ずしもここで説明された効果に限定されるわけではなく、後述する本技術に関連する一連の効果のうちのいずれの効果でもよい。
It should be noted that the effects of the present technology are not necessarily limited to the effects described here, and may be any of a series of effects related to the present technology described below.
以下、本技術の一実施形態に関して、図面を参照しながら詳細に説明する。なお、説明する順序は、下記の通りである。
１．二次電池
１－１．構成
１－２．動作
１－３．製造方法
１－４．作用および効果
２．変形例
３．二次電池の用途
Hereinafter, one embodiment of the present technology will be described in detail with reference to the drawings. The order of explanation is as follows.
1. Secondary Battery 1-1. Configuration 1-2. Operation 1-3. Manufacturing method 1-4. Action and effect 2 . Modification 3. Applications of secondary batteries
１．二次電池
１－１．構成
１－２．動作
１－３．製造方法
１－４．作用および効果
２．変形例
３．二次電池の用途
Hereinafter, one embodiment of the present technology will be described in detail with reference to the drawings. The order of explanation is as follows.
1. Secondary Battery 1-1. Configuration 1-2. Operation 1-3. Manufacturing method 1-4. Action and effect 2 . Modification 3. Applications of secondary batteries
＜１．二次電池＞
まず、本技術の一実施形態の二次電池に関して説明する。 <1. Secondary battery>
First, a secondary battery according to an embodiment of the present technology will be described.
まず、本技術の一実施形態の二次電池に関して説明する。 <1. Secondary battery>
First, a secondary battery according to an embodiment of the present technology will be described.
ここで説明する二次電池は、電極反応物質の吸蔵放出を利用して電池容量が得られる二次電池であり、正極および負極と共に、液状の電解質である電解液を備えている。
The secondary battery described here is a secondary battery in which battery capacity is obtained by utilizing the absorption and release of electrode reactants, and is equipped with a positive electrode, a negative electrode, and an electrolytic solution, which is a liquid electrolyte.
この二次電池では、負極の充電容量が正極の放電容量よりも大きくなっている。すなわち、負極の単位面積当たりの電気化学容量は、正極の単位面積当たりの電気化学容量よりも大きくなるように設定されている。充電途中において負極の表面に電極反応物質が析出することを防止するためである。
In this secondary battery, the charge capacity of the negative electrode is larger than the discharge capacity of the positive electrode. That is, the electrochemical capacity per unit area of the negative electrode is set to be larger than the electrochemical capacity per unit area of the positive electrode. This is to prevent electrode reactants from depositing on the surface of the negative electrode during charging.
電極反応物質の種類は、特に限定されないが、具体的には、アルカリ金属およびアルカリ土類金属などの軽金属である。アルカリ金属は、リチウム、ナトリウムおよびカリウムなどであると共に、アルカリ土類金属は、ベリリウム、マグネシウムおよびカルシウムなどである。
The type of electrode reactant is not particularly limited, but specifically light metals such as alkali metals and alkaline earth metals. Alkali metals include lithium, sodium and potassium, and alkaline earth metals include beryllium, magnesium and calcium.
以下では、電極反応物質がリチウムである場合を例に挙げる。リチウムの吸蔵放出を利用して電池容量が得られる二次電池は、いわゆるリチウムイオン二次電池である。このリチウムイオン二次電池では、リチウムがイオン状態で吸蔵放出される。
In the following, the case where the electrode reactant is lithium will be taken as an example. A secondary battery whose battery capacity is obtained by utilizing the absorption and release of lithium is a so-called lithium ion secondary battery. In this lithium ion secondary battery, lithium is intercalated and deintercalated in an ionic state.
＜１－１．構成＞
図１は、二次電池の斜視構成を表していると共に、図２は、図１に示した電池素子２０の断面構成を拡大して表している。ただし、図１では、外装フィルム１０と電池素子２０とが互いに分離された状態を示していると共に、ＸＺ面に沿った電池素子２０の断面を破線で示している。図２では、ＹＺ面に沿った電池素子２０の断面を示している。 <1-1. Configuration>
1 shows a perspective configuration of a secondary battery, and FIG. 2 shows an enlarged cross-sectional configuration of thebattery element 20 shown in FIG. However, FIG. 1 shows a state in which the exterior film 10 and the battery element 20 are separated from each other, and the cross section of the battery element 20 along the XZ plane is indicated by a broken line. FIG. 2 shows a cross section of the battery element 20 along the YZ plane.
図１は、二次電池の斜視構成を表していると共に、図２は、図１に示した電池素子２０の断面構成を拡大して表している。ただし、図１では、外装フィルム１０と電池素子２０とが互いに分離された状態を示していると共に、ＸＺ面に沿った電池素子２０の断面を破線で示している。図２では、ＹＺ面に沿った電池素子２０の断面を示している。 <1-1. Configuration>
1 shows a perspective configuration of a secondary battery, and FIG. 2 shows an enlarged cross-sectional configuration of the
この二次電池は、図１および図２に示したように、外装フィルム１０と、電池素子２０と、正極リード３１および負極リード３２と、封止フィルム４１，４２とを備えている。ここで説明する二次電池は、可撓性（または柔軟性）を有する外装フィルム１０を用いたラミネートフィルム型の二次電池である。
As shown in FIGS. 1 and 2, this secondary battery includes an exterior film 10, a battery element 20, a positive electrode lead 31, a negative electrode lead 32, and sealing films 41 and 42. The secondary battery described here is a laminated film type secondary battery using a flexible (or flexible) exterior film 10 .
なお、後述する「厚さ」は、図２中の上下方向（Ｚ軸方向）の寸法であると共に、後述する「幅」は、図２中の左右方向（Ｙ軸方向）の寸法である。
The "thickness" described later is the dimension in the vertical direction (Z-axis direction) in FIG. 2, and the "width" described later is the dimension in the horizontal direction (Y-axis direction) in FIG.
［外装フィルムおよび封止フィルム］
外装フィルム１０は、図１に示したように、電池素子２０を収納する可撓性の外装部材であり、その電池素子２０が内部に収納された状態において封止された袋状の構造を有している。 [Exterior film and sealing film]
As shown in FIG. 1, theexterior film 10 is a flexible exterior member that houses the battery element 20, and has a sealed bag-like structure with the battery element 20 housed inside. is doing.
外装フィルム１０は、図１に示したように、電池素子２０を収納する可撓性の外装部材であり、その電池素子２０が内部に収納された状態において封止された袋状の構造を有している。 [Exterior film and sealing film]
As shown in FIG. 1, the
ここでは、外装フィルム１０は、１枚のフィルム状の部材であり、折り畳み方向Ｆに折り畳まれている。この外装フィルム１０には、電池素子２０を収容するための窪み部１０Ｕ（いわゆる深絞り部）が設けられている。
Here, the exterior film 10 is a single film-like member and is folded in the folding direction F. The exterior film 10 is provided with a recessed portion 10U (so-called deep drawn portion) for housing the battery element 20 .
具体的には、外装フィルム１０は、融着層、金属層および表面保護層が内側からこの順に積層された３層のラミネートフィルムであり、その外装フィルム１０が折り畳まれた状態では、互いに対向する融着層のうちの外周縁部同士が互いに融着されている。融着層は、ポリプロピレンなどの高分子化合物を含んでいる。金属層は、アルミニウムなどの金属材料を含んでいる。表面保護層は、ナイロンなどの高分子化合物を含んでいる。
Specifically, the exterior film 10 is a three-layer laminate film in which a fusion layer, a metal layer, and a surface protection layer are laminated in this order from the inside. Outer peripheral edge portions of the fusion layer are fused together. The fusible layer contains a polymer compound such as polypropylene. The metal layer contains a metal material such as aluminum. The surface protective layer contains a polymer compound such as nylon.
ただし、外装フィルム１０の構成（層数）は、特に、限定されないため、１層または２層でもよいし、４層以上でもよい。
However, the configuration (number of layers) of the exterior film 10 is not particularly limited, and may be one layer, two layers, or four layers or more.
封止フィルム４１は、外装フィルム１０と正極リード３１との間に挿入されていると共に、封止フィルム４２は、外装フィルム１０と負極リード３２との間に挿入されている。ただし、封止フィルム４１，４２のうちの一方または双方は、省略されてもよい。
The sealing film 41 is inserted between the exterior film 10 and the positive electrode lead 31 , and the sealing film 42 is inserted between the exterior film 10 and the negative electrode lead 32 . However, one or both of the sealing films 41 and 42 may be omitted.
この封止フィルム４１は、外装フィルム１０の内部に外気などが侵入することを防止する封止部材である。また、封止フィルム４１は、正極リード３１に対して密着性を有するポリオレフィンなどの高分子化合物を含んでおり、そのポリオレフィンは、ポリプロピレンなどである。
The sealing film 41 is a sealing member that prevents outside air from entering the exterior film 10 . Further, the sealing film 41 contains a polymer compound such as polyolefin having adhesiveness to the positive electrode lead 31, and the polyolefin is polypropylene or the like.
封止フィルム４２の構成は、負極リード３２に対して密着性を有する封止部材であることを除いて、封止フィルム４１の構成と同様である。すなわち、封止フィルム４２は、負極リード３２に対して密着性を有するポリオレフィンなどの高分子化合物を含んでいる。
The structure of the sealing film 42 is the same as the structure of the sealing film 41 except that it is a sealing member having adhesion to the negative electrode lead 32 . That is, the sealing film 42 contains a high molecular compound such as polyolefin having adhesiveness to the negative electrode lead 32 .
［電池素子］
電池素子２０は、図１および図２に示したように、正極２１と、負極２２と、セパレータ２３と、正極電解質層２４と、負極電解質層２５と、正極保液層２６と、負極保液層２７とを含む発電素子であり、外装フィルム１０の内部に収納されている。 [Battery element]
1 and 2, thebattery element 20 includes a positive electrode 21, a negative electrode 22, a separator 23, a positive electrode electrolyte layer 24, a negative electrode electrolyte layer 25, a positive electrode liquid retaining layer 26, and a negative electrode retaining liquid. layer 27 and housed inside the exterior film 10 .
電池素子２０は、図１および図２に示したように、正極２１と、負極２２と、セパレータ２３と、正極電解質層２４と、負極電解質層２５と、正極保液層２６と、負極保液層２７とを含む発電素子であり、外装フィルム１０の内部に収納されている。 [Battery element]
1 and 2, the
この電池素子２０は、いわゆる巻回電極体である。すなわち、電池素子２０では、主に、正極２１および負極２２がセパレータ２３、正極電解質層２４および負極電解質層２５を介して互いに積層されていると共に、Ｙ軸方向に延在する仮想軸である巻回軸Ｐを中心として正極２１、負極２２、セパレータ２３、正極電解質層２４および負極電解質層２５が巻回されている。正極保液層２６は、正極電解質層２４の隣に配置されているため、その正極電解質層２４に隣接されていると共に、負極保液層２７は、負極電解質層２５の隣に配置されているため、その負極電解質層２５に隣接されている。これにより、正極２１および負極２２は、セパレータ２３、正極電解質層２４および負極電解質層２５を介して互いに対向しながら巻回されている。
This battery element 20 is a so-called wound electrode assembly. That is, in the battery element 20, the positive electrode 21 and the negative electrode 22 are mainly laminated with the separator 23, the positive electrode electrolyte layer 24, and the negative electrode electrolyte layer 25 interposed therebetween. A positive electrode 21 , a negative electrode 22 , a separator 23 , a positive electrode electrolyte layer 24 , and a negative electrode electrolyte layer 25 are wound around a rotation axis P. Since the positive electrode retaining liquid layer 26 is arranged next to the positive electrode electrolyte layer 24 , it is adjacent to the positive electrode electrolyte layer 24 , and the negative electrode retaining liquid layer 27 is arranged next to the negative electrode electrolyte layer 25 . Therefore, it is adjacent to the negative electrode electrolyte layer 25 . Thus, the positive electrode 21 and the negative electrode 22 are wound while facing each other with the separator 23, the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25 interposed therebetween.
電池素子２０の立体的形状は、特に限定されない。ここでは、電池素子２０は、扁平状であるため、巻回軸Ｐと交差する電池素子２０の断面（ＸＺ面に沿った断面）は、長軸Ｊ１および短軸Ｊ２により規定される扁平形状を有している。この長軸Ｊ１は、Ｘ軸方向に延在すると共に短軸Ｊ２よりも大きい長さを有する仮想軸であると共に、短軸Ｊ２は、Ｘ軸方向と交差するＺ軸方向に延在すると共に長軸Ｊ１よりも小さい長さを有する仮想軸である。ここでは、電池素子２０の立体的形状は、扁平な円筒状であるため、その電池素子２０の断面の形状は、扁平な略楕円形状である。
The three-dimensional shape of the battery element 20 is not particularly limited. Here, since the battery element 20 is flat, the cross section of the battery element 20 intersecting the winding axis P (the cross section along the XZ plane) has a flat shape defined by the long axis J1 and the short axis J2. have. The major axis J1 is a virtual axis that extends in the X-axis direction and has a length greater than that of the minor axis J2. A virtual axis having a length smaller than the axis J1. Here, since the three-dimensional shape of the battery element 20 is a flat cylindrical shape, the cross-sectional shape of the battery element 20 is a flat, substantially elliptical shape.
（正極）
正極２１は、充放電反応を進行させるための電極である。この正極２１は、図２に示したように、正極集電体２１Ａおよび正極活物質層２１Ｂを含んでいる。 (positive electrode)
Thepositive electrode 21 is an electrode for advancing charge/discharge reactions. This positive electrode 21 includes a positive electrode current collector 21A and a positive electrode active material layer 21B, as shown in FIG.
正極２１は、充放電反応を進行させるための電極である。この正極２１は、図２に示したように、正極集電体２１Ａおよび正極活物質層２１Ｂを含んでいる。 (positive electrode)
The
正極集電体２１Ａは、正極活物質層２１Ｂが設けられる一対の面を有している。この正極集電体２１Ａは、金属材料などの導電性材料を含んでおり、その金属材料は、アルミニウムなどである。なお、正極集電体２１Ａの幅は、正極活物質層２１Ｂの幅よりも大きくならないように設定されており、より具体的には、正極活物質層２１Ｂの幅と同じである。正極集電体２１Ａの体積の増加が防止されるため、電池素子２０の体積当たりのエネルギー密度が増加するからである。
The positive electrode current collector 21A has a pair of surfaces on which the positive electrode active material layer 21B is provided. This positive electrode current collector 21A contains a conductive material such as a metal material, and the metal material is aluminum or the like. The width of the positive electrode current collector 21A is set so as not to be larger than the width of the positive electrode active material layer 21B, and more specifically, it is the same as the width of the positive electrode active material layer 21B. This is because an increase in the volume of the positive electrode current collector 21A is prevented, so that the energy density per volume of the battery element 20 increases.
ここでは、正極活物質層２１Ｂは、正極集電体２１Ａの両面に設けられており、リチウムを吸蔵放出可能である正極活物質のうちのいずれか１種類または２種類以上を含んでいる。ただし、正極活物質層２１Ｂは、正極２１が負極２２に対向する側において正極集電体２１Ａの片面だけに設けられていてもよい。また、正極活物質層２１Ｂは、さらに、正極結着剤および正極導電剤などの他の材料のうちのいずれか１種類または２種類以上を含んでいてもよい。正極活物質層２１Ｂの形成方法は、特に限定されないが、具体的には、塗布法などのうちのいずれか１種類または２種類以上である。
Here, the positive electrode active material layer 21B is provided on both sides of the positive electrode current collector 21A, and contains one or more of positive electrode active materials capable of intercalating and deintercalating lithium. However, the positive electrode active material layer 21B may be provided only on one side of the positive electrode current collector 21A on the side where the positive electrode 21 faces the negative electrode 22 . Moreover, the positive electrode active material layer 21B may further contain one or more of other materials such as a positive electrode binder and a positive electrode conductive agent. A method for forming the positive electrode active material layer 21B is not particularly limited, but specifically, one or more of coating methods and the like are used.
正極活物質の種類は、特に限定されないが、具体的には、リチウム含有化合物などである。このリチウム含有化合物は、リチウムと共に１種類または２種類以上の遷移金属元素を構成元素として含む化合物であり、さらに、１種類または２種類以上の他元素を構成元素として含んでいてもよい。他元素の種類は、リチウムおよび遷移金属元素のそれぞれ以外の元素であれば、特に限定されないが、具体的には、長周期型周期表中の２族～１５族に属する元素である。リチウム含有化合物の種類は、特に限定されないが、具体的には、酸化物、リン酸化合物、ケイ酸化合物およびホウ酸化合物などである。酸化物の具体例は、ＬｉＮｉＯ2 、ＬｉＣｏＯ2 、ＬｉＮｉ0.8 Ｃｏ0.15Ａｌ0.05Ｏ2 、ＬｉＮｉ0.33Ｃｏ0.33Ｍｎ0.33Ｏ2 およびＬｉＭｎ2 Ｏ4 などである。リン酸化合物の具体例は、ＬｉＦｅＰＯ4 およびＬｉＭｎＰＯ4 などである。
Although the type of the positive electrode active material is not particularly limited, specific examples thereof include lithium-containing compounds. This lithium-containing compound is a compound containing lithium and one or more transition metal elements as constituent elements, and may further contain one or more other elements as constituent elements. The type of the other element is not particularly limited as long as it is an element other than lithium and transition metal elements, but specifically, it is an element belonging to Groups 2 to 15 in the long period periodic table. The type of lithium-containing compound is not particularly limited, but specific examples include oxides, phosphoric acid compounds, silicic acid compounds and boric acid compounds. Specific examples of oxides include LiNiO2 , LiCoO2 , LiNi0.8Co0.15Al0.05O2 , LiNi0.33Co0.33Mn0.33O2 and LiMn2O4 . Specific examples of phosphoric acid compounds include LiFePO4 and LiMnPO4 .
正極結着剤は、合成ゴムおよび高分子化合物などのうちのいずれか１種類または２種類以上を含んでいる。合成ゴムは、スチレンブタジエン系ゴム、フッ素系ゴムおよびエチレンプロピレンジエンなどである。高分子化合物は、ポリフッ化ビニリデン、ポリイミドおよびカルボキシメチルセルロースなどである。
The positive electrode binder contains one or more of synthetic rubber and polymer compounds. Synthetic rubbers include styrene-butadiene-based rubber, fluorine-based rubber, and ethylene propylene diene. Polymer compounds include polyvinylidene fluoride, polyimide and carboxymethyl cellulose.
正極導電剤は、炭素材料などの導電性材料のうちのいずれか１種類または２種類以上を含んでおり、その炭素材料は、黒鉛、カーボンブラック、アセチレンブラックおよびケッチェンブラックなどである。ただし、導電性材料は、金属材料および高分子化合物などでもよい。
The positive electrode conductive agent contains one or more of conductive materials such as carbon materials, and the carbon materials include graphite, carbon black, acetylene black, and ketjen black. However, the conductive material may be a metal material, a polymer compound, or the like.
（負極）
負極２２は、充放電反応を進行させるための他の電極である。この負極２２は、図２に示したように、負極集電体２２Ａおよび負極活物質層２２Ｂを含んでいる。 (negative electrode)
Thenegative electrode 22 is another electrode for advancing charge/discharge reactions. The negative electrode 22 includes a negative electrode current collector 22A and a negative electrode active material layer 22B, as shown in FIG.
負極２２は、充放電反応を進行させるための他の電極である。この負極２２は、図２に示したように、負極集電体２２Ａおよび負極活物質層２２Ｂを含んでいる。 (negative electrode)
The
負極集電体２２Ａは、負極活物質層２２Ｂが設けられる一対の面を有している。この負極集電体２２Ａは、金属材料などの導電性材料を含んでおり、その金属材料は、銅などである。なお、負極集電体２２Ａの幅は、負極活物質層２２Ｂの幅よりも大きくならないように設定されており、より具体的には、負極活物質層２２Ｂの幅と同じである。負極集電体２２Ａの体積の増加が防止されるため、電池素子２０の体積当たりのエネルギー密度が増加するからである。
The negative electrode current collector 22A has a pair of surfaces on which the negative electrode active material layer 22B is provided. This negative electrode current collector 22A contains a conductive material such as a metal material, and the metal material is copper or the like. The width of the negative electrode current collector 22A is set so as not to be larger than the width of the negative electrode active material layer 22B, and more specifically, it is the same as the width of the negative electrode active material layer 22B. This is because an increase in the volume of the negative electrode current collector 22A is prevented, so that the energy density per volume of the battery element 20 increases.
ここでは、負極活物質層２２Ｂは、負極集電体２２Ａの両面に設けられており、リチウムを吸蔵放出可能である負極活物質のうちのいずれか１種類または２種類以上を含んでいる。ただし、負極活物質層２２Ｂは、負極２２が正極２１に対向する側において負極集電体２２Ａの片面だけに設けられていてもよい。また、負極活物質層２２Ｂは、さらに、負極結着剤および負極導電剤などの他の材料のうちのいずれか１種類または２種類以上を含んでいてもよい。負極活物質層２２Ｂの形成方法は、特に限定されないが、具体的には、塗布法、気相法、液相法、溶射法および焼成法（焼結法）などのうちのいずれか１種類または２種類以上である。
Here, the negative electrode active material layer 22B is provided on both surfaces of the negative electrode current collector 22A, and contains one or more of negative electrode active materials capable of intercalating and deintercalating lithium. However, the negative electrode active material layer 22B may be provided only on one side of the negative electrode current collector 22A on the side where the negative electrode 22 faces the positive electrode 21 . In addition, the negative electrode active material layer 22B may further contain one or more of other materials such as a negative electrode binder and a negative electrode conductor. The method of forming the negative electrode active material layer 22B is not particularly limited, but specifically, any one of a coating method, a vapor phase method, a liquid phase method, a thermal spraying method, a firing method (sintering method), or the like, or Two or more types.
負極活物質の種類は、特に限定されないが、具体的には、炭素材料および金属系材料のうちの一方または双方などである。高いエネルギー密度が得られるからである。炭素材料は、易黒鉛化性炭素、難黒鉛化性炭素および黒鉛（天然黒鉛および人造黒鉛）などである。金属系材料は、リチウムと合金を形成可能である金属元素および半金属元素のうちのいずれか１種類または２種類以上を構成元素として含む材料であり、その金属元素および半金属元素の具体例は、ケイ素およびスズのうちの一方または双方などである。この金属系材料は、単体でもよいし、合金でもよいし、化合物でもよいし、それらの２種類以上の混合物でもよいし、それらの２種類以上の相を含む材料でもよい。金属系材料の具体例は、ＴｉＳｉ2 およびＳｉＯx （０＜ｘ≦２、または０．２＜ｘ＜１．４）などである。
The type of negative electrode active material is not particularly limited, but specifically, one or both of a carbon material and a metal-based material. This is because a high energy density can be obtained. Carbon materials include graphitizable carbon, non-graphitizable carbon and graphite (natural graphite and artificial graphite). A metallic material is a material containing as constituent elements one or more of metallic elements and semi-metallic elements capable of forming an alloy with lithium. , one or both of silicon and tin, and the like. This metallic material may be a single substance, an alloy, a compound, a mixture of two or more of them, or a material containing two or more of these phases. Specific examples of metallic materials include TiSi 2 and SiO x (0<x≦2, or 0.2<x<1.4).
負極結着剤および負極導電剤のそれぞれに関する詳細は、正極結着剤および正極導電剤のそれぞれに関する詳細と同様である。
The details of each of the negative electrode binder and the negative electrode conductive agent are the same as those of the positive electrode binder and the positive electrode conductive agent.
ここでは、負極活物質層２２Ｂの幅は、正極活物質層２１Ｂの幅よりも大きくなっている。正極２１から放出されたリチウムが負極２２において意図せずに析出することを防止するためである。
Here, the width of the negative electrode active material layer 22B is larger than the width of the positive electrode active material layer 21B. This is to prevent lithium released from the positive electrode 21 from unintentionally depositing on the negative electrode 22 .
（セパレータ）
セパレータ２３は、図２に示したように、正極２１と負極２２との間に介在している絶縁性の多孔質膜であり、その正極２１と負極２２との接触（短絡）を防止しながらリチウムイオンを通過させる。このセパレータ２３は、ポリエチレンなどの高分子化合物を含んでいる。 (separator)
Theseparator 23 is an insulating porous film interposed between the positive electrode 21 and the negative electrode 22, as shown in FIG. Allows lithium ions to pass through. This separator 23 contains a polymer compound such as polyethylene.
セパレータ２３は、図２に示したように、正極２１と負極２２との間に介在している絶縁性の多孔質膜であり、その正極２１と負極２２との接触（短絡）を防止しながらリチウムイオンを通過させる。このセパレータ２３は、ポリエチレンなどの高分子化合物を含んでいる。 (separator)
The
（正極電解質層）
正極電解質層２４は、正極２１において吸蔵放出されるリチウムの媒介として機能する第１電解質層であり、図２に示したように、正極２１とセパレータ２３との間に配置されている。すなわち、正極２１およびセパレータ２３は、正極電解質層２４を介して互いに対向している。ここでは、正極電解質層２４は、正極２１とセパレータ２３とにより挟まれており、その正極２１およびセパレータ２３のそれぞれに隣接されている。 (Positive electrode electrolyte layer)
The positiveelectrode electrolyte layer 24 is a first electrolyte layer that functions as an intermediary for lithium that is occluded and released in the positive electrode 21, and is arranged between the positive electrode 21 and the separator 23 as shown in FIG. That is, the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween. Here, the positive electrode electrolyte layer 24 is sandwiched between the positive electrode 21 and the separator 23 and is adjacent to the positive electrode 21 and the separator 23 respectively.
正極電解質層２４は、正極２１において吸蔵放出されるリチウムの媒介として機能する第１電解質層であり、図２に示したように、正極２１とセパレータ２３との間に配置されている。すなわち、正極２１およびセパレータ２３は、正極電解質層２４を介して互いに対向している。ここでは、正極電解質層２４は、正極２１とセパレータ２３とにより挟まれており、その正極２１およびセパレータ２３のそれぞれに隣接されている。 (Positive electrode electrolyte layer)
The positive
具体的には、正極電解質層２４は、電解液および高分子化合物を含んでいるゲル状の電解質であり、その電解液は、高分子化合物により保持されている。このゲル状での電解質である正極電解質層２４を用いることにより、液状の電解質である電解液をそのまま用いる場合とは異なり、その電解液の漏液が防止される。
Specifically, the positive electrode electrolyte layer 24 is a gel electrolyte containing an electrolytic solution and a polymer compound, and the electrolytic solution is held by the polymer compound. By using the positive electrode electrolyte layer 24, which is a gel electrolyte, leakage of the electrolyte is prevented unlike the case where the electrolyte, which is a liquid electrolyte, is used as it is.
ここで説明する電解液は、正極電解質層２４に含まれている第１電解液である。この電解液の種類は、１種類だけでもよいし、２種類以上でもよい。具体的には、電解液は、溶媒および電解質塩を含んでいる。
The electrolytic solution described here is the first electrolytic solution contained in the positive electrode electrolyte layer 24 . The type of the electrolytic solution may be one type, or two or more types. Specifically, the electrolyte contains a solvent and an electrolyte salt.
溶媒は、非水溶媒（有機溶剤）のうちのいずれか１種類または２種類以上を含んでおり、その非水溶媒を含んでいる電解液は、いわゆる非水電解液である。この非水溶媒は、エステル類およびエーテル類などであり、より具体的には、炭酸エステル系化合物、カルボン酸エステル系化合物およびラクトン系化合物などである。炭酸エステル系化合物の具体例は、炭酸エチレン、炭酸プロピレン、炭酸ジメチル、炭酸ジエチルおよび炭酸エチルメチルなどである。カルボン酸エステル系化合物の具体例は、酢酸エチル、プロピオン酸エチルおよびプロピオン酸プロピルなどである。ラクトン系化合物の具体例は、γ－ブチロラクトンおよびγ－バレロラクトンなどである。
The solvent contains one or more of non-aqueous solvents (organic solvents), and the electrolytic solution containing the non-aqueous solvent is the so-called non-aqueous electrolytic solution. The non-aqueous solvents are esters, ethers, and the like, and more specifically, carbonate compounds, carboxylic acid ester compounds, lactone compounds, and the like. Specific examples of carbonate ester compounds include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate. Specific examples of carboxylic acid ester compounds include ethyl acetate, ethyl propionate and propyl propionate. Specific examples of lactone compounds include γ-butyrolactone and γ-valerolactone.
電解質塩は、リチウム塩などの軽金属塩のうちのいずれか１種類または２種類以上を含んでいる。リチウム塩の具体例は、六フッ化リン酸リチウム（ＬｉＰＦ6 ）、四フッ化ホウ酸リチウム（ＬｉＢＦ4 ）、トリフルオロメタンスルホン酸リチウム（ＬｉＣＦ3 ＳＯ3 ）、ビス（フルオロスルホニル）イミドリチウム（ＬｉＮ（ＦＳＯ2 ）2 ）、ビス（トリフルオロメタンスルホニル）イミドリチウム（ＬｉＮ（ＣＦ3 ＳＯ2 ）2 ）、リチウムトリス（トリフルオロメタンスルホニル）メチド（ＬｉＣ（ＣＦ3 ＳＯ2 ）3 ）およびビス（オキサラト）ホウ酸リチウム（ＬｉＢ（Ｃ2 Ｏ4 ）2 ）などである。電解質塩の含有量は、特に限定されないが、具体的には、溶媒に対して０．３ｍｏｌ／ｋｇ～３．０ｍｏｌ／ｋｇである。高いイオン伝導性が得られるからである。
The electrolyte salt contains one or more of light metal salts such as lithium salts. Specific examples of lithium salts include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(fluorosulfonyl)imide (LiN (FSO2) 2 ), lithium bis(trifluoromethanesulfonyl)imide (LiN( CF3SO2 ) 2 ) , lithium tris(trifluoromethanesulfonyl)methide (LiC(CF3SO2)3 ) and bis ( oxalato)boron. Examples include lithium oxide (LiB(C 2 O 4 ) 2 ). The content of the electrolyte salt is not particularly limited, but is specifically 0.3 mol/kg to 3.0 mol/kg with respect to the solvent. This is because high ionic conductivity can be obtained.
なお、電解液は、さらに、添加剤のうちのいずれか１種類または２種類以上を含んでいてもよい。具体的には、添加剤は、不飽和環状炭酸エステル、ハロゲン化環状炭酸エステル、スルホン酸エステル、リン酸エステル、酸無水物、ニトリル化合物およびイソシアネート化合物などである。
The electrolytic solution may further contain one or more of additives. Specifically, the additive includes an unsaturated cyclic carbonate, a halogenated cyclic carbonate, a sulfonate, a phosphate, an acid anhydride, a nitrile compound, an isocyanate compound, and the like.
不飽和環状炭酸エステルの具体例は、炭酸ビニレン、炭酸ビニルエチレンおよび炭酸メチレンエチレンなどである。ハロゲン化環状炭酸エステルの具体例は、モノフルオロ炭酸エチレンおよびジフルオロ炭酸エチレンなどである。スルホン酸エステルの具体例は、プロパンスルトンおよびプロペンスルトンなどである。リン酸エステルの具体例は、リン酸トリメチルおよびリン酸トリエチルなどである。酸無水物の具体例は、コハク酸無水物、１，２－エタンジスルホン酸無水物および２－スルホ安息香酸無水物などである。ニトリル化合物の具体例は、スクシノニトリルなどである。イソシアネート化合物の具体例は、ヘキサメチレンジイソシアネートなどである。
Specific examples of unsaturated cyclic carbonates include vinylene carbonate, vinylethylene carbonate and methyleneethylene carbonate. Specific examples of halogenated cyclic carbonates include ethylene monofluorocarbonate and ethylene difluorocarbonate. Specific examples of sulfonate esters include propane sultone and propene sultone. Specific examples of phosphate esters include trimethyl phosphate and triethyl phosphate. Specific examples of acid anhydrides include succinic anhydride, 1,2-ethanedisulfonic anhydride and 2-sulfobenzoic anhydride. Specific examples of nitrile compounds include succinonitrile. Specific examples of isocyanate compounds include hexamethylene diisocyanate.
ここで説明する高分子化合物は、正極電解質層２４に含まれている第１高分子化合物である。この高分子化合物の種類は、１種類だけでもよいし、２種類以上でもよい。
The polymer compound described here is the first polymer compound contained in the positive electrode electrolyte layer 24 . The number of types of the polymer compound may be one, or two or more.
具体的には、高分子化合物は、フッ化ビニリデンの単独重合体およびフッ化ビニリデンの共重合体のうちの一方または双方を含んでいる。正極電解質層２４において優れた物理的強度および優れた電気化学的安定性が得られるからである。フッ化ビニリデンの単独重合体は、いわゆるポリフッ化ビニリデンである。フッ化ビニリデンの共重合体は、フッ化ビニリデンと、１種類または２種類以上の重合成分（単量体）との共重合体であり、その重合成分の種類は、特に限定されない。
Specifically, the polymer compound contains one or both of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer. This is because excellent physical strength and excellent electrochemical stability can be obtained in the positive electrode electrolyte layer 24 . Homopolymers of vinylidene fluoride are so-called polyvinylidene fluoride. The vinylidene fluoride copolymer is a copolymer of vinylidene fluoride and one or more polymerizable components (monomers), and the types of the polymerizable components are not particularly limited.
中でも、フッ化ビニリデンの共重合体は、重合成分としてヘキサフルオロプロピレンを含んでいることが好ましい。すなわち、高分子化合物は、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体であることが好ましい。正極電解質層２４による電解液の保持量が増加するからである。
Above all, the copolymer of vinylidene fluoride preferably contains hexafluoropropylene as a polymerization component. That is, the polymer compound is preferably a copolymer of vinylidene fluoride and hexafluoropropylene. This is because the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 increases.
この場合において、フッ化ビニリデンの共重合体は、さらに、重合性分として不飽和二塩基酸および不飽和二塩基酸モノエステルのうちの一方または双方を含んでいることが好ましい。すなわち、高分子化合物は、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸との共重合体であるか、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸モノエステルとの共重合体であるか、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸と不飽和二塩基酸モノエステルとの共重合体であることが好ましい。正極電解質層２４による電解液の保持量がより増加するからである。
In this case, the vinylidene fluoride copolymer preferably further contains one or both of unsaturated dibasic acid and unsaturated dibasic acid monoester as polymerizable components. That is, the polymer compound is a copolymer of vinylidene fluoride, hexafluoropropylene, and an unsaturated dibasic acid, or a copolymer of vinylidene fluoride, hexafluoropropylene, and an unsaturated dibasic acid monoester. or a copolymer of vinylidene fluoride, hexafluoropropylene, unsaturated dibasic acid, and unsaturated dibasic acid monoester. This is because the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 is further increased.
不飽和二塩基酸の具体例は、マレイン酸、フマル酸、イタコン酸およびシトラコン酸などである。不飽和二塩基酸モノエステルの具体例は、マレイン酸モノメチルエステル、マレイン酸モノエチルエステル、フマル酸モノメチルエステル、フマル酸モノエチルエステル、イタコン酸モノメチルエステル、イタコン酸モノエチルエステル、シトラコン酸モノメチルエステルおよびシトラコン酸モノエチルエステルなどである。
Specific examples of unsaturated dibasic acids include maleic acid, fumaric acid, itaconic acid and citraconic acid. Specific examples of unsaturated dibasic acid monoesters are maleic acid monomethyl ester, maleic acid monoethyl ester, fumaric acid monomethyl ester, fumaric acid monoethyl ester, itaconic acid monomethyl ester, itaconic acid monoethyl ester, citraconic acid monomethyl ester and and citraconic acid monoethyl ester.
なお、正極電解質層２４は、さらに、複数の絶縁性粒子を含んでいることが好ましい。正極電解質層２４による電解液の保持量がより増加するからである。
The positive electrode electrolyte layer 24 preferably further contains a plurality of insulating particles. This is because the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 is further increased.
絶縁性粒子は、無機材料および高分子化合物のうちの一方または双方を含んでいる。無機材料の具体例は、酸化アルミニウム、酸化ジルコニウム、酸化チタンおよび酸化マグネシウムなどである。高分子化合物の具体例は、アクリル樹脂およびスチレン樹脂などである。
The insulating particles contain one or both of an inorganic material and a polymer compound. Specific examples of inorganic materials include aluminum oxide, zirconium oxide, titanium oxide and magnesium oxide. Specific examples of polymer compounds include acrylic resins and styrene resins.
（負極電解質層）
負極電解質層２５は、負極２２において吸蔵放出されるリチウムの媒介として機能する他の第１電解質層であり、図２に示したように、負極２２とセパレータ２３との間に配置されている。すなわち、負極２２およびセパレータ２３は、負極電解質層２５を介して互いに対向している。ここでは、負極電解質層２５は、負極２２とセパレータ２３とにより挟まれており、その負極２２およびセパレータ２３のそれぞれに隣接されている。 (Negative Electrolyte Layer)
The negativeelectrode electrolyte layer 25 is another first electrolyte layer that functions as an intermediary for lithium that is intercalated and deintercalated in the negative electrode 22 , and is arranged between the negative electrode 22 and the separator 23 as shown in FIG. 2 . That is, the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween. Here, the negative electrode electrolyte layer 25 is sandwiched between the negative electrode 22 and the separator 23 and is adjacent to the negative electrode 22 and the separator 23 respectively.
負極電解質層２５は、負極２２において吸蔵放出されるリチウムの媒介として機能する他の第１電解質層であり、図２に示したように、負極２２とセパレータ２３との間に配置されている。すなわち、負極２２およびセパレータ２３は、負極電解質層２５を介して互いに対向している。ここでは、負極電解質層２５は、負極２２とセパレータ２３とにより挟まれており、その負極２２およびセパレータ２３のそれぞれに隣接されている。 (Negative Electrolyte Layer)
The negative
具体的には、負極電解質層２５は、正極電解質層２４の構成と同様の構成を有している。すなわち、負極電解質層２５は、電解液および高分子化合物を含んでいるゲル状の電解質であり、その電解液は、高分子化合物により保持されている。負極電解質層２５を用いることにより、電解液の漏液が防止される。
Specifically, the negative electrode electrolyte layer 25 has the same configuration as the positive electrode electrolyte layer 24 . That is, the negative electrode electrolyte layer 25 is a gel electrolyte containing an electrolytic solution and a polymer compound, and the electrolytic solution is held by the polymer compound. By using the negative electrode electrolyte layer 25, electrolyte leakage is prevented.
ここで説明する電解液は、負極電解質層２５に含まれている他の第１電解液であると共に、ここで説明する高分子化合物は、負極電解質層２５に含まれている他の第１高分子化合物である。負極電解質層２５に含まれている電解液および高分子化合物のそれぞれに関する詳細は、正極電解質層２４に含まれている電解液および高分子化合物のそれぞれに関する詳細と同様である。もちろん、負極電解質層２５は、複数の絶縁性粒子を含んでいてもよい。
The electrolyte solution described here is the other first electrolyte solution contained in the negative electrode electrolyte layer 25, and the polymer compound described here is the other first electrolyte solution contained in the negative electrode electrolyte layer 25. It is a molecular compound. The details of the electrolytic solution and the polymer compound contained in the negative electrode electrolyte layer 25 are the same as the details of the electrolytic solution and the polymer compound contained in the positive electrode electrolyte layer 24 . Of course, the negative electrode electrolyte layer 25 may contain a plurality of insulating particles.
ただし、負極電解質層２５に含まれている電解液の種類と正極電解質層２４に含まれている電解液の種類とは、互いに同じでもよいし、互いに異なってもよい。同様に、負極電解質層２５に含まれている高分子化合物の種類と正極電解質層２４に含まれている高分子化合物の種類とは、互いに同じでもよいし、互いに異なってもよい。
However, the type of electrolytic solution contained in the negative electrode electrolyte layer 25 and the type of electrolytic solution contained in the positive electrode electrolyte layer 24 may be the same or different. Similarly, the type of polymer compound contained in negative electrode electrolyte layer 25 and the type of polymer compound contained in positive electrode electrolyte layer 24 may be the same or different.
（正極保液層）
正極保液層２６は、正極電解質層２４に電解液を供給する第２電解質層であり、図２に示したように、その正極電解質層２４に隣接されている。より具体的には、正極保液層２６は、正極２１およびセパレータ２３が正極電解質層２４を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において、その正極電解質層２４に隣接されている。ここでは、正極保液層２６は、正極２１とセパレータ２３とにより挟まれておらずに、正極電解質層２４の側面に接触している。 (Positive liquid retaining layer)
The positiveelectrode electrolyte layer 26 is a second electrolyte layer that supplies an electrolytic solution to the positive electrode electrolyte layer 24, and is adjacent to the positive electrode electrolyte layer 24 as shown in FIG. More specifically, the positive electrode liquid-retaining layer 26 extends along the direction (Y-axis direction) intersecting the direction (Z-axis direction) in which the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween. 24 are adjacent. Here, the positive electrode liquid retaining layer 26 is not sandwiched between the positive electrode 21 and the separator 23 but is in contact with the side surface of the positive electrode electrolyte layer 24 .
正極保液層２６は、正極電解質層２４に電解液を供給する第２電解質層であり、図２に示したように、その正極電解質層２４に隣接されている。より具体的には、正極保液層２６は、正極２１およびセパレータ２３が正極電解質層２４を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において、その正極電解質層２４に隣接されている。ここでは、正極保液層２６は、正極２１とセパレータ２３とにより挟まれておらずに、正極電解質層２４の側面に接触している。 (Positive liquid retaining layer)
The positive
ここでは、正極保液層２６は、正極電解質層２４の両側に配置されているため、電池素子２０は、２個の正極保液層２６を含んでいる。すなわち、１個目の正極保液層２６は、正極電解質層２４の右側に配置されているため、その正極電解質層２４の右側面に隣接されている。２個目の正極保液層２６は、正極電解質層２４の左側に配置されているため、その正極電解質層２４の左側面に隣接されている。
Here, the positive electrode liquid-retaining layers 26 are arranged on both sides of the positive electrode electrolyte layer 24 , so the battery element 20 includes two positive electrode liquid-retaining layers 26 . That is, the first positive electrode liquid retaining layer 26 is arranged on the right side of the positive electrode electrolyte layer 24 , so it is adjacent to the right side surface of the positive electrode electrolyte layer 24 . The second positive electrode liquid-retaining layer 26 is arranged on the left side of the positive electrode electrolyte layer 24 , so it is adjacent to the left side surface of the positive electrode electrolyte layer 24 .
なお、正極保液層２６は、セパレータ２３の一面に配置されているため、そのセパレータ２３により支持されている。
Note that the positive electrode liquid-retaining layer 26 is arranged on one surface of the separator 23 and thus supported by the separator 23 .
具体的には、正極保液層２６は、正極電解質層２４の構成と同様の構成を有している。すなわち、正極保液層２６は、電解液および高分子化合物を含んでいるゲル状の電解質であり、その電解液は、高分子化合物により保持されている。正極保液層２６が電解液を保持可能になると共に、その正極保液層２６が正極電解質層２４に電解液を供給可能になるからである。
Specifically, the cathode liquid retaining layer 26 has the same configuration as the cathode electrolyte layer 24 . That is, the positive electrode liquid retaining layer 26 is a gel electrolyte containing an electrolytic solution and a polymer compound, and the electrolytic solution is held by the polymer compound. This is because the positive electrode liquid-retaining layer 26 can hold the electrolytic solution and the positive electrode liquid-retaining layer 26 can supply the electrolytic solution to the positive electrode electrolyte layer 24 .
ここで説明する電解液は、正極保液層２６に含まれている第２電解液であると共に、ここで説明する高分子化合物は、正極保液層２６に含まれている第２高分子化合物である。正極保液層２６に含まれている電解液および高分子化合物のそれぞれに関する詳細は、正極電解質層２４に含まれている電解液および高分子化合物のそれぞれに関する詳細と同様である。もちろん、正極保液層２６は、複数の絶縁性粒子を含んでいてもよい。
The electrolyte solution described here is the second electrolyte solution contained in the positive electrode liquid-retaining layer 26, and the polymer compound described here is the second polymer compound contained in the positive electrode liquid-retaining layer 26. is. The details of the electrolytic solution and the polymer compound contained in the positive electrode electrolyte layer 26 are the same as the details of the electrolytic solution and the polymer compound contained in the positive electrode electrolyte layer 24 . Of course, the positive electrode liquid retaining layer 26 may contain a plurality of insulating particles.
ただし、正極保液層２６に含まれている電解液の種類と正極電解質層２４に含まれている電解液の種類とは、互いに同じでもよいし、互いに異なってもよい。同様に、正極保液層２６に含まれている高分子化合物の種類と正極電解質層２４に含まれている高分子化合物の種類とは、互いに同じでもよいし、互いに異なってもよい。
However, the type of electrolytic solution contained in the positive electrode liquid retaining layer 26 and the type of electrolytic solution contained in the positive electrode electrolyte layer 24 may be the same or different. Similarly, the type of polymer compound contained in the positive electrode liquid-retaining layer 26 and the type of polymer compound contained in the positive electrode electrolyte layer 24 may be the same or different.
ここで、正極保液層２６において高分子化合物の重量に対する電解液の重量の比（重量比Ｒ２＝電解液の重量／高分子化合物の重量）は、正極電解質層２４において高分子化合物の重量に対する電解液の重量の比（重量比Ｒ１＝電解液の重量／高分子化合物の重量）よりも大きくなっている。正極保液層２６から正極電解質層２４に十分な量の電解液が供給されるため、充放電繰り返しても放電容量の減少が抑制されるからである。これにより、正極電解質層２４の厚さＴ１が薄くても済むため、電池素子２０の体積当たりのエネルギー密度が増加する。重量比Ｒ１は、正極電解質層２４における電解液の含有率を表すパラメータであると共に、重量比Ｒ２は、正極保液層２６における電解液の含有率を表すパラメータである。
Here, the ratio of the weight of the electrolytic solution to the weight of the polymer compound in the positive electrode electrolyte layer 26 (weight ratio R2=weight of the electrolytic solution/weight of the polymer compound) is It is larger than the weight ratio of the electrolytic solution (weight ratio R1=weight of electrolytic solution/weight of polymer compound). This is because a sufficient amount of the electrolytic solution is supplied from the positive electrode liquid-retaining layer 26 to the positive electrode electrolyte layer 24, so that a decrease in discharge capacity is suppressed even if charging and discharging are repeated. As a result, the thickness T1 of the positive electrode electrolyte layer 24 can be reduced, so that the energy density per volume of the battery element 20 increases. The weight ratio R1 is a parameter that represents the content of the electrolyte in the positive electrode electrolyte layer 24, and the weight ratio R2 is a parameter that represents the content of the electrolyte in the positive electrode liquid-retaining layer .
重量比Ｒ１を求めるためには、二次電池を解体することにより、正極電解質層２４を回収したのち、熱重量示差熱分析法（ＴＧ－ＤＴＡ）を用いて正極電解質層２４を分析する。これにより、電解液の重量および高分子化合物の重量のそれぞれが測定されるため、その測定結果に基づいて重量比Ｒ１を算出可能である。
In order to obtain the weight ratio R1, the positive electrode electrolyte layer 24 is recovered by disassembling the secondary battery, and then the positive electrode electrolyte layer 24 is analyzed using thermogravimetric differential thermal analysis (TG-DTA). As a result, the weight of the electrolytic solution and the weight of the polymer compound are each measured, so the weight ratio R1 can be calculated based on the measurement results.
重量比Ｒ２を求める手順は、正極電解質層２４の代わりに正極保液層２６を回収および分析することを除いて、重量比Ｒ１を求める手順と同様である。
The procedure for obtaining the weight ratio R2 is the same as the procedure for obtaining the weight ratio R1, except that the positive electrode liquid-retaining layer 26 is recovered and analyzed instead of the positive electrode electrolyte layer 24.
正極保液層２６の厚さＴ２は、特に限定されないため、任意に設定可能である。中でも、正極保液層２６の厚さＴ２は、正極電解質層２４の厚さＴ１よりも大きいことが好ましい。正極保液層２６による電解液の保持量が増加するため、その正極保液層２６から正極電解質層２４に供給される電解液の量が増加するからである。
The thickness T2 of the positive electrode liquid-retaining layer 26 is not particularly limited and can be set arbitrarily. Above all, the thickness T2 of the positive electrode liquid retaining layer 26 is preferably larger than the thickness T1 of the positive electrode electrolyte layer 24 . This is because the amount of the electrolytic solution held by the positive electrode liquid-retaining layer 26 increases, and the amount of the electrolytic solution supplied from the positive electrode liquid-retaining layer 26 to the positive electrode electrolyte layer 24 increases.
厚さＴ１を求めるためには、最初に、二次電池を解体することにより、電池素子２０を回収する。続いて、ＹＺ面に沿うように電池素子２０を切断することにより、その電池素子２０の断面を露出させる（図２参照）。この場合には、扁平な立体的形状を有している電池素子２０のうちの平坦部において、その電池素子２０を切断することが好ましい。続いて、走査型電子顕微鏡（ＳＥＭ）などの顕微鏡を用いて電池素子２０の断面を観察することにより、正極電解質層２４の厚さを測定する。この場合には、正極活物質層２１Ｂとセパレータ２３との間の距離を測定することにより、その距離を正極電解質層２４の厚さとする。なお、観察倍率は、任意に設定可能である。最後に、互いに異なる３０箇所において正極電解質層２４の厚さを測定したのち、３０個の厚さの平均値を算出することにより、厚さＴ１とする。
In order to obtain the thickness T1, first, the battery element 20 is collected by disassembling the secondary battery. Subsequently, by cutting the battery element 20 along the YZ plane, the cross section of the battery element 20 is exposed (see FIG. 2). In this case, it is preferable to cut the battery element 20 at the flat portion of the battery element 20 having a flat three-dimensional shape. Subsequently, the thickness of the positive electrode electrolyte layer 24 is measured by observing the cross section of the battery element 20 using a microscope such as a scanning electron microscope (SEM). In this case, the distance between the positive electrode active material layer 21B and the separator 23 is measured, and the distance is taken as the thickness of the positive electrode electrolyte layer 24 . Note that the observation magnification can be arbitrarily set. Finally, after measuring the thickness of the positive electrode electrolyte layer 24 at 30 different locations, the thickness T1 is obtained by calculating the average value of the 30 thicknesses.
厚さＴ２を求める手順は、電池素子２０の断面の観察結果に基づいて正極保液層２６の厚さを測定することを除いて、厚さＴ１を求める手順と同様である。
The procedure for obtaining the thickness T2 is the same as the procedure for obtaining the thickness T1, except that the thickness of the positive electrode liquid-retaining layer 26 is measured based on the observation result of the cross section of the battery element 20.
ここでは、上記したように、正極集電体２１Ａの幅は、正極活物質層２１Ｂの幅と同じである。また、正極保液層２６は、図２に示したように、正極電解質層２４の側面に隣接されているだけでなく、正極活物質層２１Ｂの側面の一部にも隣接されている。これにより、正極保液層２６は、正極集電体２１Ａに隣接されておらず、その正極集電体２１Ａから離隔されている。
Here, as described above, the width of the positive electrode current collector 21A is the same as the width of the positive electrode active material layer 21B. Further, as shown in FIG. 2, the positive electrode liquid retaining layer 26 is adjacent not only to the side surface of the positive electrode electrolyte layer 24 but also to a part of the side surface of the positive electrode active material layer 21B. Accordingly, the positive electrode liquid retaining layer 26 is not adjacent to the positive electrode current collector 21A and is separated from the positive electrode current collector 21A.
（負極保液層）
負極保液層２７は、負極電解質層２５に電解液を供給する他の第２電解質層であり、図２に示したように、その負極電解質層２５に隣接されている。より具体的には、負極保液層２７は、負極２２およびセパレータ２３が負極電解質層２５を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において、その負極電解質層２５に隣接されている。ここでは、負極保液層２７は、負極２２とセパレータ２３とにより挟まれておらずに、負極電解質層２５の側面に接触している。 (Negative electrode liquid retaining layer)
The negativeelectrode electrolyte layer 27 is another second electrolyte layer that supplies the electrolyte to the negative electrode electrolyte layer 25, and is adjacent to the negative electrode electrolyte layer 25 as shown in FIG. More specifically, the negative electrode liquid-retaining layer 27 extends along the direction (Y-axis direction) intersecting the direction (Z-axis direction) in which the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween. 25 are adjacent. Here, the negative electrode liquid retaining layer 27 is not sandwiched between the negative electrode 22 and the separator 23 but is in contact with the side surface of the negative electrode electrolyte layer 25 .
負極保液層２７は、負極電解質層２５に電解液を供給する他の第２電解質層であり、図２に示したように、その負極電解質層２５に隣接されている。より具体的には、負極保液層２７は、負極２２およびセパレータ２３が負極電解質層２５を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において、その負極電解質層２５に隣接されている。ここでは、負極保液層２７は、負極２２とセパレータ２３とにより挟まれておらずに、負極電解質層２５の側面に接触している。 (Negative electrode liquid retaining layer)
The negative
ここでは、負極保液層２７は、負極電解質層２５の両側に配置されているため、電池素子２０は、２個の負極保液層２７を含んでいる。すなわち、１個目の負極保液層２７は、負極電解質層２５の右側に配置されているため、その負極電解質層２５の右側面に隣接されている。２個目の負極保液層２７は、負極電解質層２５の左側に配置されているため、その負極電解質層２５の左側面に隣接されている。
Here, since the negative electrode liquid-retaining layers 27 are arranged on both sides of the negative electrode electrolyte layer 25 , the battery element 20 includes two negative electrode liquid-retaining layers 27 . That is, the first negative electrode retaining liquid layer 27 is arranged on the right side of the negative electrode electrolyte layer 25 , so it is adjacent to the right side surface of the negative electrode electrolyte layer 25 . Since the second negative electrode liquid retaining layer 27 is arranged on the left side of the negative electrode electrolyte layer 25 , it is adjacent to the left side surface of the negative electrode electrolyte layer 25 .
なお、負極保液層２７は、セパレータ２３の一面（正極保液層２６が形成されている面とは反対側の面）に配置されているため、そのセパレータ２３により支持されている。
Note that the negative electrode liquid-retaining layer 27 is arranged on one surface of the separator 23 (the surface opposite to the surface on which the positive electrode liquid-retaining layer 26 is formed), and thus is supported by the separator 23 .
具体的には、負極保液層２７は、負極電解質層２５の構成と同様の構成を有している。すなわち、負極保液層２７は、電解液および高分子化合物を含んでいるゲル状の電解質であり、その電解液は、高分子化合物により保持されている。負極保液層２７が電解液を保持可能になると共に、その負極保液層２７が負極電解質層２５に電解液を供給可能になるからである。
Specifically, the negative electrode liquid retaining layer 27 has the same configuration as the negative electrode electrolyte layer 25 . That is, the negative electrode liquid retaining layer 27 is a gel electrolyte containing an electrolyte and a polymer compound, and the electrolyte is retained by the polymer compound. This is because the negative electrode liquid-retaining layer 27 can hold the electrolytic solution and the negative electrode liquid-retaining layer 27 can supply the electrolytic solution to the negative electrode electrolyte layer 25 .
ここで説明する電解液は、負極保液層２７に含まれている他の第２電解液であると共に、ここで説明する高分子化合物は、負極保液層２７に含まれている他の第２高分子化合物である。負極保液層２７に含まれている電解液および高分子化合物のそれぞれに関する詳細は、負極電解質層２５に含まれている電解液および高分子化合物のそれぞれに関する詳細と同様である。もちろん、負極保液層２７は、複数の絶縁性粒子を含んでいてもよい。
The electrolyte solution described here is the other second electrolyte solution contained in the negative electrode liquid-retaining layer 27 , and the polymer compound described here is the other second electrolyte solution contained in the negative electrode liquid-retaining layer 27 . 2 is a polymer compound. The details of the electrolytic solution and the polymer compound contained in the negative electrode electrolyte layer 27 are the same as the details of the electrolytic solution and the polymer compound contained in the negative electrode electrolyte layer 25 . Of course, the negative electrode liquid retaining layer 27 may contain a plurality of insulating particles.
ただし、負極保液層２７に含まれている電解液の種類と負極電解質層２５に含まれている電解液の種類とは、互いに同じでもよいし、互いに異なってもよい。同様に、負極保液層２７に含まれている高分子化合物の種類と負極電解質層２５に含まれている高分子化合物の種類とは、互いに同じでもよいし、互いに異なってもよい。
However, the type of electrolytic solution contained in the negative electrode liquid retaining layer 27 and the type of electrolytic solution contained in the negative electrode electrolyte layer 25 may be the same or different. Similarly, the type of polymer compound contained in the negative electrode liquid-retaining layer 27 and the type of polymer compound contained in the negative electrode electrolyte layer 25 may be the same or different.
ここで、負極保液層２７において高分子化合物の重量に対する電解液の重量の比（重量比Ｒ４＝電解液の重量／高分子化合物の重量）は、負極電解質層２５において高分子化合物の重量に対する電解液の重量の比（重量比Ｒ３＝電解液の重量／高分子化合物の重量）よりも大きくなっている。負極保液層２７から負極電解質層２５に十分な量の電解液が供給されるため、充放電繰り返しても放電容量の減少が抑制されるからである。これにより、負極電解質層２５の厚さＴ３が薄くても済むため、電池素子２０の体積当たりのエネルギー密度が増加する。重量比Ｒ３は、負極電解質層２５における電解液の含有率を表すパラメータであると共に、重量比Ｒ４は、負極保液層２７における電解液の含有率を表すパラメータである。
Here, the ratio of the weight of the electrolyte to the weight of the polymer compound in the anode electrolyte layer 27 (weight ratio R4=weight of the electrolyte solution/weight of the polymer compound) is the weight of the polymer compound in the anode electrolyte layer 25. It is larger than the ratio of the weight of the electrolytic solution (weight ratio R3=weight of electrolytic solution/weight of polymer compound). This is because a sufficient amount of the electrolytic solution is supplied from the negative electrode liquid-holding layer 27 to the negative electrode electrolyte layer 25, so that even if charging and discharging are repeated, a decrease in discharge capacity is suppressed. As a result, the thickness T3 of the negative electrode electrolyte layer 25 can be reduced, so that the energy density per volume of the battery element 20 increases. The weight ratio R3 is a parameter representing the content of the electrolyte in the negative electrode electrolyte layer 25, and the weight ratio R4 is a parameter representing the content of the electrolyte in the negative electrode liquid-retaining layer 27. FIG.
重量比Ｒ３を求める手順は、正極電解質層２４の代わりに負極電解質層２５を回収および分析することを除いて、重量比Ｒ１を求める手順と同様である。重量比Ｒ４を求める手順は、正極電解質層２４の代わりに負極保液層２７を回収および分析することを除いて、重量比Ｒ１を求める手順と同様である。
The procedure for obtaining the weight ratio R3 is the same as the procedure for obtaining the weight ratio R1, except that the negative electrode electrolyte layer 25 is collected and analyzed instead of the positive electrode electrolyte layer 24. The procedure for obtaining the weight ratio R4 is the same as the procedure for obtaining the weight ratio R1, except that the negative electrode liquid-retaining layer 27 is collected and analyzed instead of the positive electrode electrolyte layer 24 .
負極保液層２７の厚さＴ４は、特に限定されないため、任意に設定可能である。中でも、負極保液層２７の厚さＴ４は、負極電解質層２５の厚さＴ３よりも大きいことが好ましい。負極保液層２７による電解液の保持量が増加するため、その負極保液層２７から負極電解質層２５に供給される電解液の量が増加するからである。
The thickness T4 of the negative electrode liquid-retaining layer 27 is not particularly limited and can be set arbitrarily. Among them, the thickness T4 of the negative electrode liquid retaining layer 27 is preferably larger than the thickness T3 of the negative electrode electrolyte layer 25 . This is because the amount of the electrolytic solution held by the negative electrode liquid-retaining layer 27 increases, and the amount of the electrolytic solution supplied from the negative electrode liquid-retaining layer 27 to the negative electrode electrolyte layer 25 increases.
厚さＴ３を求める手順は、電池素子２０の断面の観察結果に基づいて負極電解質層２５の厚さ（負極活物質層２２Ｂとセパレータ２３との間の距離）を測定することを除いて、厚さＴ１を求める手順と同様である。厚さＴ４を求める手順は、電池素子２０の断面の観察結果に基づいて負極保液層２７の厚さを測定することを除いて、厚さＴ１を求める手順と同様である。
The procedure for obtaining the thickness T3 is the thickness T3 except for measuring the thickness of the negative electrode electrolyte layer 25 (the distance between the negative electrode active material layer 22B and the separator 23) based on the observation result of the cross section of the battery element 20. The procedure for determining the thickness T1 is the same. The procedure for determining the thickness T4 is the same as the procedure for determining the thickness T1, except that the thickness of the negative electrode liquid-retaining layer 27 is measured based on the observation result of the cross section of the battery element 20 .
ここでは、上記したように、負極集電体２２Ａの幅は、負極活物質層２２Ｂの幅と同じである。また、負極保液層２７は、図２に示したように、負極電解質層２５の側面に隣接されているだけでなく、負極活物質層２２Ｂの側面の一部にも隣接されている。これにより、負極保液層２７は、負極集電体２２Ａに隣接されておらず、その負極集電体２２Ａから離隔されている。
Here, as described above, the width of the negative electrode current collector 22A is the same as the width of the negative electrode active material layer 22B. Further, as shown in FIG. 2, the negative electrode liquid retaining layer 27 is adjacent not only to the side surface of the negative electrode electrolyte layer 25 but also to a part of the side surface of the negative electrode active material layer 22B. Thus, the negative electrode liquid retaining layer 27 is not adjacent to the negative electrode current collector 22A and is separated from the negative electrode current collector 22A.
［正極リードおよび負極リード］
正極リード３１は、図１に示したように、正極２１に接続された正極端子であり、より具体的には、正極集電体２１Ａに接続されている。この正極リード３１は、外装フィルム１０の内部から外部に導出されており、アルミニウムなどの導電性材料を含んでいる。正極リード３１の形状は、特に限定されないが、具体的には、薄板状および網目状などのうちのいずれかである。 [Positive lead and negative lead]
Thepositive electrode lead 31 is a positive electrode terminal connected to the positive electrode 21, as shown in FIG. 1, and more specifically connected to the positive current collector 21A. The positive electrode lead 31 extends from the inside of the exterior film 10 to the outside, and contains a conductive material such as aluminum. The shape of the positive electrode lead 31 is not particularly limited, but specifically, it is either a thin plate shape, a mesh shape, or the like.
正極リード３１は、図１に示したように、正極２１に接続された正極端子であり、より具体的には、正極集電体２１Ａに接続されている。この正極リード３１は、外装フィルム１０の内部から外部に導出されており、アルミニウムなどの導電性材料を含んでいる。正極リード３１の形状は、特に限定されないが、具体的には、薄板状および網目状などのうちのいずれかである。 [Positive lead and negative lead]
The
負極リード３２は、図１に示したように、負極２２に接続された負極端子であり、より具体的には、負極集電体２２Ａに接続されている。この負極リード３２は、外装フィルム１０の内部から外部に導出されており、銅などの導電性材料を含んでいる。ここでは、負極リード３２の導出方向は、正極リード３１の導出方向と同様である。なお、負極リード３２の形状に関する詳細は、正極リード３１の形状に関する詳細と同様である。
The negative electrode lead 32 is a negative electrode terminal connected to the negative electrode 22, as shown in FIG. 1, and more specifically connected to the negative electrode current collector 22A. The negative electrode lead 32 is led out from the interior of the exterior film 10 and contains a conductive material such as copper. Here, the lead-out direction of the negative lead 32 is the same as the lead-out direction of the positive lead 31 . Details regarding the shape of the negative electrode lead 32 are the same as those regarding the shape of the positive electrode lead 31 .
＜１－２．動作＞
二次電池の充電時には、電池素子２０において、正極２１からリチウムが放出されると共に、そのリチウムが正極電解質層２４および負極電解質層２５を介して負極２２に吸蔵される。一方、二次電池の放電時には、電池素子２０において、負極２２からリチウムが放出されると共に、そのリチウムが正極電解質層２４および負極電解質層２５を介して正極２１に吸蔵される。これらの充電時および放電時には、リチウムがイオン状態で吸蔵および放出される。 <1-2. Operation>
During charging of the secondary battery, in thebattery element 20 , lithium is released from the positive electrode 21 and absorbed into the negative electrode 22 via the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25 . On the other hand, during discharging of the secondary battery, in the battery element 20 , lithium is released from the negative electrode 22 and absorbed into the positive electrode 21 via the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25 . Lithium is intercalated and deintercalated in an ionic state during charging and discharging.
二次電池の充電時には、電池素子２０において、正極２１からリチウムが放出されると共に、そのリチウムが正極電解質層２４および負極電解質層２５を介して負極２２に吸蔵される。一方、二次電池の放電時には、電池素子２０において、負極２２からリチウムが放出されると共に、そのリチウムが正極電解質層２４および負極電解質層２５を介して正極２１に吸蔵される。これらの充電時および放電時には、リチウムがイオン状態で吸蔵および放出される。 <1-2. Operation>
During charging of the secondary battery, in the
二次電池の充放電時には、正極電解質層２４中の電解液が消費されると共に、負極電解質層２５中の電解液が消費されると、正極保液層２６から正極電解質層２４に電解液が供給されると共に、負極保液層２７から負極電解質層２５に電解液が供給される。
During charging and discharging of the secondary battery, when the electrolyte in the positive electrode electrolyte layer 24 is consumed and the electrolyte in the negative electrode electrolyte layer 25 is consumed, the electrolyte is transferred from the positive electrode liquid retaining layer 26 to the positive electrode electrolyte layer 24 . At the same time, the electrolytic solution is supplied from the negative electrode liquid retaining layer 27 to the negative electrode electrolyte layer 25 .
＜１－３．製造方法＞
二次電池を製造する場合には、以下で説明する手順により、正極２１、負極２２、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれを作製したのち、それらを用いて二次電池を作製する。 <1-3. Manufacturing method>
In the case of manufacturing the secondary battery, thepositive electrode 21, the negative electrode 22, the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 are each manufactured by the procedure described below. , to produce a secondary battery using them.
二次電池を製造する場合には、以下で説明する手順により、正極２１、負極２２、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれを作製したのち、それらを用いて二次電池を作製する。 <1-3. Manufacturing method>
In the case of manufacturing the secondary battery, the
［正極の作製］
最初に、正極活物質と、正極結着剤と、正極導電剤とが互いに混合された混合物（正極合剤）を溶媒に投入することにより、ペースト状の正極合剤スラリーを調製する。この溶媒は、水性溶媒でもよいし、有機溶剤でもよい。続いて、正極集電体２１Ａの両面に正極合剤スラリーを塗布することにより、正極活物質層２１Ｂを形成する。こののち、ロールプレス機などを用いて正極活物質層２１Ｂを圧縮成型してもよい。この場合には、正極活物質層２１Ｂを加熱してもよいし、圧縮成型を複数回繰り返してもよい。これにより、正極集電体２１Ａの両面に正極活物質層２１Ｂが形成されるため、正極２１が作製される。 [Preparation of positive electrode]
First, a paste-like positive electrode mixture slurry is prepared by putting a mixture (positive electrode mixture) in which a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent are mixed together into a solvent. This solvent may be an aqueous solvent or an organic solvent. Subsequently, the cathodeactive material layer 21B is formed by applying the cathode mixture slurry to both surfaces of the cathode current collector 21A. After that, the cathode active material layer 21B may be compression-molded using a roll press machine or the like. In this case, the positive electrode active material layer 21B may be heated, or compression molding may be repeated multiple times. As a result, the cathode active material layers 21B are formed on both surfaces of the cathode current collector 21A, so that the cathode 21 is produced.
最初に、正極活物質と、正極結着剤と、正極導電剤とが互いに混合された混合物（正極合剤）を溶媒に投入することにより、ペースト状の正極合剤スラリーを調製する。この溶媒は、水性溶媒でもよいし、有機溶剤でもよい。続いて、正極集電体２１Ａの両面に正極合剤スラリーを塗布することにより、正極活物質層２１Ｂを形成する。こののち、ロールプレス機などを用いて正極活物質層２１Ｂを圧縮成型してもよい。この場合には、正極活物質層２１Ｂを加熱してもよいし、圧縮成型を複数回繰り返してもよい。これにより、正極集電体２１Ａの両面に正極活物質層２１Ｂが形成されるため、正極２１が作製される。 [Preparation of positive electrode]
First, a paste-like positive electrode mixture slurry is prepared by putting a mixture (positive electrode mixture) in which a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent are mixed together into a solvent. This solvent may be an aqueous solvent or an organic solvent. Subsequently, the cathode
［負極の作製］
上記した正極２１の作製手順と同様の手順により、負極２２を形成する。具体的には、最初に、負極活物質と、負極結着剤と、負極導電剤とが互いに混合された混合物（負極合剤）を溶媒に投入することにより、ペースト状の負極合剤スラリーを調製する。続いて、負極集電体２２Ａの両面に負極合剤スラリーを塗布することにより、負極活物質層２２Ｂを形成する。こののち、負極活物質層２２Ｂを圧縮成型してもよい。これにより、負極集電体２２Ａの両面に負極活物質層２２Ｂが形成されるため、負極２２が作製される。 [Preparation of negative electrode]
Anegative electrode 22 is formed by the same procedure as that of the positive electrode 21 described above. Specifically, first, a mixture (negative electrode mixture) in which a negative electrode active material, a negative electrode binder, and a negative electrode conductive agent are mixed together is put into a solvent to prepare a pasty negative electrode mixture slurry. Prepare. Subsequently, the anode active material layer 22B is formed by applying the anode mixture slurry to both surfaces of the anode current collector 22A. After that, the negative electrode active material layer 22B may be compression molded. As a result, the negative electrode 22 is manufactured because the negative electrode active material layers 22B are formed on both surfaces of the negative electrode current collector 22A.
上記した正極２１の作製手順と同様の手順により、負極２２を形成する。具体的には、最初に、負極活物質と、負極結着剤と、負極導電剤とが互いに混合された混合物（負極合剤）を溶媒に投入することにより、ペースト状の負極合剤スラリーを調製する。続いて、負極集電体２２Ａの両面に負極合剤スラリーを塗布することにより、負極活物質層２２Ｂを形成する。こののち、負極活物質層２２Ｂを圧縮成型してもよい。これにより、負極集電体２２Ａの両面に負極活物質層２２Ｂが形成されるため、負極２２が作製される。 [Preparation of negative electrode]
A
［正極電解質層の形成および負極電解質層の形成］
最初に、溶媒に電解質塩を投入する。これにより、溶媒中において電解質塩が溶解または分散されるため、電解液が調製される。続いて、電解液と、高分子化合物と、必要に応じて追加の溶媒とを互いに混合させることにより、前駆溶液を調製する。最後に、正極２１の表面に前駆溶液を塗布することにより、正極電解質層２４を形成する。 [Formation of Positive Electrolyte Layer and Negative Electrolyte Layer]
First, the electrolyte salt is added to the solvent. As a result, the electrolyte salt is dissolved or dispersed in the solvent to prepare an electrolytic solution. Subsequently, a precursor solution is prepared by mixing together the electrolytic solution, the polymer compound, and optionally additional solvent. Finally, the positiveelectrode electrolyte layer 24 is formed by applying the precursor solution to the surface of the positive electrode 21 .
最初に、溶媒に電解質塩を投入する。これにより、溶媒中において電解質塩が溶解または分散されるため、電解液が調製される。続いて、電解液と、高分子化合物と、必要に応じて追加の溶媒とを互いに混合させることにより、前駆溶液を調製する。最後に、正極２１の表面に前駆溶液を塗布することにより、正極電解質層２４を形成する。 [Formation of Positive Electrolyte Layer and Negative Electrolyte Layer]
First, the electrolyte salt is added to the solvent. As a result, the electrolyte salt is dissolved or dispersed in the solvent to prepare an electrolytic solution. Subsequently, a precursor solution is prepared by mixing together the electrolytic solution, the polymer compound, and optionally additional solvent. Finally, the positive
上記した正極電解質層２４の形成手順と同様の手順により、負極電解質層２５を形成する。具体的には、電解液を調製すると共に、その電解液および高分子化合物を用いて前駆溶液を調製したのち、負極２２の表面に前駆溶液を塗布することにより、負極電解質層２５を形成する。
The negative electrode electrolyte layer 25 is formed by the same procedure as that for forming the positive electrode electrolyte layer 24 described above. Specifically, an electrolytic solution is prepared, a precursor solution is prepared using the electrolytic solution and a polymer compound, and then the precursor solution is applied to the surface of the negative electrode 22 to form the negative electrode electrolyte layer 25 .
［正極保液層の形成および負極保液層の形成］
最初に、溶媒に電解質塩を投入することにより、電解液を調製する。続いて、電解液と、高分子化合物と、必要に応じて追加の溶媒とを互いに混合させることにより、前駆溶液を調製したのち、セパレータ２３の一面に前駆溶液を塗布することにより、正極保液層２６を形成する。この場合には、ポリプロピレンフィルムなどの高分子フィルムを用いて、セパレータ２３の表面をマスキングしてもよい。 [Formation of positive electrode liquid-retaining layer and formation of negative electrode liquid-retaining layer]
First, an electrolytic solution is prepared by adding an electrolytic salt to a solvent. Subsequently, the electrolytic solution, the polymer compound, and, if necessary, an additional solvent are mixed with each other to prepare a precursor solution. Alayer 26 is formed. In this case, the surface of the separator 23 may be masked with a polymer film such as a polypropylene film.
最初に、溶媒に電解質塩を投入することにより、電解液を調製する。続いて、電解液と、高分子化合物と、必要に応じて追加の溶媒とを互いに混合させることにより、前駆溶液を調製したのち、セパレータ２３の一面に前駆溶液を塗布することにより、正極保液層２６を形成する。この場合には、ポリプロピレンフィルムなどの高分子フィルムを用いて、セパレータ２３の表面をマスキングしてもよい。 [Formation of positive electrode liquid-retaining layer and formation of negative electrode liquid-retaining layer]
First, an electrolytic solution is prepared by adding an electrolytic salt to a solvent. Subsequently, the electrolytic solution, the polymer compound, and, if necessary, an additional solvent are mixed with each other to prepare a precursor solution. A
上記した正極保液層２６の形成手順と同様の手順により、負極保液層２７を形成する。具体的には、電解液を調製すると共に、その電解液および高分子化合物を用いて前駆溶液を調製したのち、セパレータ２３の一面（正極保液層２６が形成されている面とは反対側の面）に前駆溶液を塗布することにより、負極保液層２７を形成する。
The negative electrode liquid-retaining layer 27 is formed by the same procedure as that for forming the positive electrode liquid-retaining layer 26 described above. Specifically, after preparing an electrolytic solution and preparing a precursor solution using the electrolytic solution and a polymer compound, one surface of the separator 23 (the opposite side to the surface on which the positive electrode liquid holding layer 26 is formed) surface), the negative electrode liquid-retaining layer 27 is formed.
［二次電池の組み立て］
最初に、溶接法などを用いて正極２１の正極集電体２１Ａに正極リード３１を接続させると共に、溶接法などを用いて負極２２の負極集電体２２Ａに負極リード３２を接続させる。 [Assembly of secondary battery]
First, thepositive electrode lead 31 is connected to the positive electrode current collector 21A of the positive electrode 21 by welding or the like, and the negative electrode lead 32 is connected to the negative electrode current collector 22A of the negative electrode 22 by welding or the like.
最初に、溶接法などを用いて正極２１の正極集電体２１Ａに正極リード３１を接続させると共に、溶接法などを用いて負極２２の負極集電体２２Ａに負極リード３２を接続させる。 [Assembly of secondary battery]
First, the
続いて、正極保液層２６および負極保液層２７が形成されているセパレータ２３を介して、正極電解質層２４が形成されている正極２１と、負極電解質層２５が形成されている負極２２とを互いに積層させる。これにより、正極保液層２６が正極電解質層２４に隣接されると共に、負極保液層２７が負極電解質層２５に隣接される。続いて、正極２１、負極２２、セパレータ２３、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７を巻回させることにより、電池素子２０を作製する。続いて、プレス機などを用いて電池素子２０をプレスすることにより、その電池素子２０を扁平形状となるように成型する。
Subsequently, the positive electrode 21 formed with the positive electrode electrolyte layer 24 and the negative electrode 22 formed with the negative electrode electrolyte layer 25 are separated through the separator 23 formed with the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27. are stacked on top of each other. As a result, the positive electrode retaining liquid layer 26 is adjacent to the positive electrode electrolyte layer 24 and the negative electrode retaining liquid layer 27 is adjacent to the negative electrode electrolyte layer 25 . Subsequently, the positive electrode 21 , the negative electrode 22 , the separator 23 , the positive electrode electrolyte layer 24 , the negative electrode electrolyte layer 25 , the positive electrode liquid-retaining layer 26 , and the negative electrode liquid-retaining layer 27 are wound to form the battery element 20 . Subsequently, by pressing the battery element 20 using a pressing machine or the like, the battery element 20 is molded into a flat shape.
続いて、窪み部１０Ｕの内部に電池素子２０を収容したのち、外装フィルム１０（融着層／金属層／表面保護層）を折り畳むことにより、その外装フィルム１０同士を互いに対向させる。最後に、熱融着法などを用いて、互いに対向する外装フィルム１０（融着層）のうちの３辺の外周縁部同士を互いに接合させる。この場合には、外装フィルム１０と正極リード３１との間に封止フィルム４１を挿入すると共に、外装フィルム１０と負極リード３２との間に封止フィルム４２を挿入する。これにより、袋状の外装フィルム１０の内部に電池素子２０が封入されるため、二次電池が組み立てられる。
Subsequently, after housing the battery element 20 inside the recess 10U, the exterior films 10 (bonding layer/metal layer/surface protective layer) are folded so that the exterior films 10 face each other. Finally, using a heat-sealing method or the like, the outer peripheral edges of three sides of the exterior films 10 (fusion layers) facing each other are joined together. In this case, a sealing film 41 is inserted between the packaging film 10 and the positive electrode lead 31 and a sealing film 42 is inserted between the packaging film 10 and the negative electrode lead 32 . As a result, the battery element 20 is enclosed inside the bag-shaped exterior film 10, so that the secondary battery is assembled.
［二次電池の安定化］
組み立て後の二次電池を充放電させる。環境温度、充放電回数（サイクル数）および充放電条件などの各種条件は、任意に設定可能である。これにより、正極２１および負極２２のそれぞれの表面に被膜が形成されるため、二次電池の状態が電気化学的に安定化する。よって、外装フィルム１０を用いたラミネートフィルム型の二次電池が完成する。 [Stabilization of secondary battery]
The secondary battery after assembly is charged and discharged. Various conditions such as environmental temperature, number of charge/discharge times (number of cycles), and charge/discharge conditions can be arbitrarily set. As a result, films are formed on the respective surfaces of thepositive electrode 21 and the negative electrode 22, so that the state of the secondary battery is electrochemically stabilized. Thus, a laminated film type secondary battery using the exterior film 10 is completed.
組み立て後の二次電池を充放電させる。環境温度、充放電回数（サイクル数）および充放電条件などの各種条件は、任意に設定可能である。これにより、正極２１および負極２２のそれぞれの表面に被膜が形成されるため、二次電池の状態が電気化学的に安定化する。よって、外装フィルム１０を用いたラミネートフィルム型の二次電池が完成する。 [Stabilization of secondary battery]
The secondary battery after assembly is charged and discharged. Various conditions such as environmental temperature, number of charge/discharge times (number of cycles), and charge/discharge conditions can be arbitrarily set. As a result, films are formed on the respective surfaces of the
＜１－４．作用および効果＞
この二次電池によれば、正極２１およびセパレータ２３が正極電解質層２４を介して互いに対向しており、その正極２１およびセパレータ２３が正極電解質層２４を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において正極電解質層２４に正極保液層２６が隣接されており、その正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きくなっている。 <1-4. Action and effect>
According to this secondary battery, thepositive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween, and the direction in which the positive electrode 21 and the separator 23 face each other with the positive electrode electrolyte layer 24 interposed therebetween (the Z-axis direction). The positive electrode electrolyte layer 24 is adjacent to the positive electrode electrolyte layer 24 in the direction (Y-axis direction) intersecting the , and the weight ratio R2 of the positive electrode electrolyte layer 26 is larger than the weight ratio R1 of the positive electrode electrolyte layer 24. there is
この二次電池によれば、正極２１およびセパレータ２３が正極電解質層２４を介して互いに対向しており、その正極２１およびセパレータ２３が正極電解質層２４を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において正極電解質層２４に正極保液層２６が隣接されており、その正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きくなっている。 <1-4. Action and effect>
According to this secondary battery, the
これにより、上記したように、充放電時において正極電解質層２４中の電解液が消費されると、正極保液層２６から正極電解質層２４に電解液が供給されるため、その正極電解質層２４中の電解液量が減少しにくくなる。この場合には、特に、正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きいため、その正極保液層２６から正極電解質層２４に十分な量の電解液が供給される。よって、充放電繰り返しても放電容量の減少が抑制されるため、優れたサイクル特性を得ることができる。
Accordingly, as described above, when the electrolyte in the positive electrode electrolyte layer 24 is consumed during charging and discharging, the electrolyte is supplied from the positive electrode liquid-retaining layer 26 to the positive electrode electrolyte layer 24, so that the positive electrode electrolyte layer 24 It becomes difficult for the amount of electrolyte inside to decrease. In this case, in particular, since the weight ratio R2 of the positive electrode retaining liquid layer 26 is larger than the weight ratio R1 of the positive electrode electrolyte layer 24, a sufficient amount of electrolyte is supplied from the positive electrode retaining liquid layer 26 to the positive electrode electrolyte layer 24. be done. Therefore, even if charging and discharging are repeated, a decrease in discharge capacity is suppressed, and excellent cycle characteristics can be obtained.
上記した正極電解質層２４および正極保液層２６に基づいて得られる効果は、負極電解質層２５および負極保液層２７に基づいても同様に得られる。すなわち、負極２２およびセパレータ２３が負極電解質層２５を介して互いに対向しており、その負極２２およびセパレータ２３が負極電解質層２５を介して互いに対向する方向（Ｚ軸方向）と交差する方向（Ｙ軸方向）において負極電解質層２５に負極保液層２７が隣接されており、その負極保液層２７の重量比Ｒ４が負極電解質層２５の重量比Ｒ３よりも大きくなっている。これにより、負極保液層２７から負極電解質層２５に十分な量の電解液が供給されるため、その負極電解質層２５中の電解液量が減少しにくくなる。よって、充放電繰り返しても放電容量の減少が抑制されるため、優れたサイクル特性を得ることができる。
The effect obtained based on the positive electrode electrolyte layer 24 and the positive electrode liquid-retaining layer 26 described above can also be similarly obtained based on the negative electrode electrolyte layer 25 and the negative electrode liquid-retaining layer 27 . That is, the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween, and the direction (the Z-axis direction) in which the negative electrode 22 and the separator 23 face each other with the negative electrode electrolyte layer 25 interposed therebetween (the direction Y The negative electrode electrolyte layer 25 is adjacent to the negative electrode electrolyte layer 25 in the axial direction), and the weight ratio R4 of the negative electrode electrolyte layer 27 is larger than the weight ratio R3 of the negative electrode electrolyte layer 25 . As a result, a sufficient amount of electrolytic solution is supplied from the negative electrode liquid retaining layer 27 to the negative electrode electrolyte layer 25, so that the amount of electrolytic solution in the negative electrode electrolyte layer 25 is less likely to decrease. Therefore, even if charging and discharging are repeated, a decrease in discharge capacity is suppressed, and excellent cycle characteristics can be obtained.
特に、正極保液層２６の厚さＴ２が正極電解質層２４の厚さＴ１よりも大きくなっていれば、その正極保液層２６による電解液の保持量が増加する。よって、正極保液層２６から正極電解質層２４に供給される電解液の量が増加するため、より高い効果を得ることができる。
In particular, if the thickness T2 of the positive electrode liquid-retaining layer 26 is greater than the thickness T1 of the positive electrode electrolyte layer 24, the amount of electrolyte retained by the positive electrode liquid-retaining layer 26 increases. Therefore, the amount of the electrolytic solution supplied from the positive electrode liquid retaining layer 26 to the positive electrode electrolyte layer 24 is increased, so that a higher effect can be obtained.
上記した正極電解質層２４の厚さＴ１および正極保液層２６の厚さＴ２に基づいて得られる効果は、負極電解質層２５の厚さＴ３および負極保液層２７の厚さＴ４に基づいても同様に得られる。すなわち、負極保液層２７の厚さＴ４が負極電解質層２５の厚さＴ３よりも大きくなっていれば、その負極保液層２７による電解液の保持量が増加する。よって、負極保液層２７から負極電解質層２５に供給される電解液の量が増加するため、より高い効果を得ることができる。
The effect obtained based on the thickness T1 of the positive electrode electrolyte layer 24 and the thickness T2 of the positive electrode liquid-retaining layer 26 is also based on the thickness T3 of the negative electrode electrolyte layer 25 and the thickness T4 of the negative electrode liquid-retaining layer 27. similarly obtained. That is, if the thickness T4 of the negative electrode liquid-retaining layer 27 is larger than the thickness T3 of the negative electrode electrolyte layer 25, the amount of electrolyte retained by the negative electrode liquid-retaining layer 27 increases. Therefore, the amount of the electrolytic solution supplied from the negative electrode liquid retaining layer 27 to the negative electrode electrolyte layer 25 is increased, so that a higher effect can be obtained.
また、正極電解質層２４に含まれている高分子化合物がフッ化ビニリデンの単独重合体およびフッ化ビニリデンの共重合体のうちの一方または双方を含んでいれば、その正極電解質層２４において優れた物理的強度および優れた電気化学的安定性が得られるため、より高い効果を得ることができる。
Further, if the polymer compound contained in the positive electrode electrolyte layer 24 contains one or both of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer, the positive electrode electrolyte layer 24 is excellent. Higher effect can be obtained due to physical strength and excellent electrochemical stability.
この場合には、フッ化ビニリデンの共重合体が重合成分としてヘキサフルオロプロピレンを含んでいれば、正極電解質層２４による電解液の保持量が増加するため、より高い効果を得ることができる。また、フッ化ビニリデンの共重合体がさらに重合成分として不飽和二塩基酸および不飽和二塩基酸モノエステルのうちの一方または双方を含んでいれば、正極電解質層２４による電解液の保持量がより増加するため、さらに高い効果を得ることができる。
In this case, if the vinylidene fluoride copolymer contains hexafluoropropylene as a polymerization component, the amount of electrolyte retained by the positive electrode electrolyte layer 24 increases, so that a higher effect can be obtained. Further, if the vinylidene fluoride copolymer further contains one or both of unsaturated dibasic acid and unsaturated dibasic acid monoester as polymerization components, the amount of electrolytic solution retained by positive electrode electrolyte layer 24 is increased. Since it increases more, a higher effect can be obtained.
また、正極電解質層２４が複数の絶縁性粒子を含んでいれば、その正極電解質層２４による電解液の保持量が増加するため、より高い効果を得ることができる。
In addition, if the positive electrode electrolyte layer 24 contains a plurality of insulating particles, the amount of electrolyte solution retained by the positive electrode electrolyte layer 24 increases, so that a higher effect can be obtained.
上記した正極電解質層２４の構成（高分子化合物の種類および複数の絶縁性粒子の有無）に基づいて得られる効果は、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれの構成に基づいても同様に得られる。
The effects obtained based on the configuration of the positive electrode electrolyte layer 24 described above (type of polymer compound and presence/absence of a plurality of insulating particles) depend on each of the negative electrode electrolyte layer 25, the positive electrode retaining layer 26, and the negative electrode retaining liquid layer 27. A similar result can be obtained based on the configuration.
また、二次電池がリチウムイオン二次電池であれば、リチウムの吸蔵放出を利用して十分な電池容量が安定に得られるため、より高い効果を得ることができる。
Also, if the secondary battery is a lithium-ion secondary battery, a sufficient battery capacity can be stably obtained by utilizing the absorption and release of lithium, so a higher effect can be obtained.
＜２．変形例＞
上記した二次電池の構成は、以下で説明するように、適宜、変更可能である。ただし、以下で説明する一連の変形例のうちの任意の２種類以上は、互いに組み合わされてもよい。 <2. Variation>
The configuration of the secondary battery described above can be changed as appropriate, as described below. However, any two or more of the series of modifications described below may be combined with each other.
上記した二次電池の構成は、以下で説明するように、適宜、変更可能である。ただし、以下で説明する一連の変形例のうちの任意の２種類以上は、互いに組み合わされてもよい。 <2. Variation>
The configuration of the secondary battery described above can be changed as appropriate, as described below. However, any two or more of the series of modifications described below may be combined with each other.
［変形例１］
図２では、正極電解質層２４の両側に正極保液層２６が配置されているため、電池素子２０が２個の正極保液層２６を含んでいる。しかしながら、正極電解質層２４の片側だけに正極保液層２６が配置されているため、電池素子２０が１個の正極保液層２６だけを含んでいてもよい。この場合においても、電池素子２０が正極保液層２６を含んでいない場合と比較して、充放電繰り返しても放電容量の減少が抑制されるため、同様の効果を得ることができる。 [Modification 1]
In FIG. 2 , the positive electrode liquid-retaininglayers 26 are arranged on both sides of the positive electrode electrolyte layer 24 , so the battery element 20 includes two positive electrode liquid-retaining layers 26 . However, since the positive electrode liquid-retaining layer 26 is arranged only on one side of the positive electrode electrolyte layer 24 , the battery element 20 may include only one positive electrode liquid-retaining layer 26 . In this case as well, compared with the case where the battery element 20 does not include the positive electrode liquid retaining layer 26, the decrease in discharge capacity is suppressed even after repeated charging and discharging, and the same effect can be obtained.
図２では、正極電解質層２４の両側に正極保液層２６が配置されているため、電池素子２０が２個の正極保液層２６を含んでいる。しかしながら、正極電解質層２４の片側だけに正極保液層２６が配置されているため、電池素子２０が１個の正極保液層２６だけを含んでいてもよい。この場合においても、電池素子２０が正極保液層２６を含んでいない場合と比較して、充放電繰り返しても放電容量の減少が抑制されるため、同様の効果を得ることができる。 [Modification 1]
In FIG. 2 , the positive electrode liquid-retaining
上記した正極保液層２６の配置場所に関する変形は、負極保液層２７の配置場所に関しても同様である。すなわち、負極電解質層２５の両側に負極保液層２７が配置されているため、電池素子２０が２個の負極保液層２７を含んでいるが、その負極電解質層２５の片側だけに負極保液層２７が配置されているため、電池素子２０が１個の負極保液層２７だけを含んでいてもよい。この場合においても、電池素子２０が負極保液層２７を含んでいない場合と比較して、充放電繰り返しても放電容量の減少が抑制されるため、同様の効果を得ることができる。
The above-described modification regarding the placement location of the positive electrode liquid-retaining layer 26 is the same for the placement location of the negative electrode liquid-retaining layer 27 . That is, since the negative electrode liquid-retaining layers 27 are arranged on both sides of the negative electrode electrolyte layer 25, the battery element 20 includes two negative electrode liquid-retaining layers 27. Since the liquid layer 27 is arranged, the battery element 20 may include only one negative electrode liquid-retaining layer 27 . Also in this case, compared with the case where the battery element 20 does not include the negative electrode liquid retaining layer 27, the decrease in the discharge capacity is suppressed even after repeated charging and discharging, so that the same effect can be obtained.
［変形例２］
図２では、正極電解質層２４に正極保液層２６が隣接されていると共に、負極電解質層２５に負極保液層２７が隣接されている。しかしながら、正極電解質層２４に正極保液層２６が隣接されているのに対して、負極電解質層２５に負極保液層２７が隣接されていなくてもよい。または、正極電解質層２４に正極保液層２６が隣接されていないのに対して、負極電解質層２５に負極保液層２７が隣接されていてもよい。この場合においても、正極電解質層２４に正極保液層２６が隣接されていないと共に、負極電解質層２５に負極保液層２７が隣接されていない場合と比較して、充放電繰り返しても放電容量の減少が抑制されるため、同様の効果を得ることができる。 [Modification 2]
In FIG. 2 , the positiveelectrode electrolyte layer 24 is adjacent to the positive electrode liquid-retaining layer 26 , and the negative electrode electrolyte layer 25 is adjacent to the negative electrode liquid-retaining layer 27 . However, while the positive electrode electrolyte layer 24 is adjacent to the positive electrode electrolyte layer 26 , the negative electrode electrolyte layer 25 may not be adjacent to the negative electrode electrolyte layer 27 . Alternatively, while the positive electrode electrolyte layer 24 is not adjacent to the positive electrode electrolyte layer 26 , the negative electrode electrolyte layer 25 may be adjacent to the negative electrode electrolyte layer 27 . Even in this case, compared to the case where the positive electrode electrolyte layer 24 is not adjacent to the positive electrode electrolyte layer 26 and the negative electrode electrolyte layer 25 is not adjacent to the negative electrode electrolyte layer 27, the discharge capacity is lower even after repeated charging and discharging. Since the decrease in is suppressed, a similar effect can be obtained.
図２では、正極電解質層２４に正極保液層２６が隣接されていると共に、負極電解質層２５に負極保液層２７が隣接されている。しかしながら、正極電解質層２４に正極保液層２６が隣接されているのに対して、負極電解質層２５に負極保液層２７が隣接されていなくてもよい。または、正極電解質層２４に正極保液層２６が隣接されていないのに対して、負極電解質層２５に負極保液層２７が隣接されていてもよい。この場合においても、正極電解質層２４に正極保液層２６が隣接されていないと共に、負極電解質層２５に負極保液層２７が隣接されていない場合と比較して、充放電繰り返しても放電容量の減少が抑制されるため、同様の効果を得ることができる。 [Modification 2]
In FIG. 2 , the positive
［変形例３］
図２では、電池素子２０の作製工程において、セパレータ２３の一面に正極保液層２６を形成したのち、その正極保液層２６が形成されたセパレータ２３などを巻回させている。しかしながら、セパレータ２３などを巻回させたのち、そのセパレータ２３の一面に正極保液層２６を形成してもよい。この場合においても、正極保液層２６を含む電池素子２０を作製可能であるため、同様の効果を得ることができる。 [Modification 3]
In FIG. 2, in the manufacturing process of thebattery element 20, the positive electrode liquid-retaining layer 26 is formed on one surface of the separator 23, and then the separator 23 with the positive electrode liquid-retaining layer 26 formed thereon is wound. However, after winding the separator 23 or the like, the positive electrode liquid retaining layer 26 may be formed on one surface of the separator 23 . Even in this case, since the battery element 20 including the positive electrode liquid-retaining layer 26 can be produced, a similar effect can be obtained.
図２では、電池素子２０の作製工程において、セパレータ２３の一面に正極保液層２６を形成したのち、その正極保液層２６が形成されたセパレータ２３などを巻回させている。しかしながら、セパレータ２３などを巻回させたのち、そのセパレータ２３の一面に正極保液層２６を形成してもよい。この場合においても、正極保液層２６を含む電池素子２０を作製可能であるため、同様の効果を得ることができる。 [Modification 3]
In FIG. 2, in the manufacturing process of the
上記した正極保液層２６を含む電池素子２０の作製方法に関する変形は、負極保液層２７を含む電池素子２０の作製方法に関しても同様である。すなわち、セパレータ２３の一面に負極保液層２７を形成したのち、その負極保液層２７が形成されたセパレータ２３などを巻回させているが、セパレータ２３などを巻回させたのち、そのセパレータ２３の一面に負極保液層２７を形成してもよい。この場合においても、負極保液層２７を含む電池素子２０を作製可能であるため、同様の効果を得ることができる。
The modification of the manufacturing method of the battery element 20 including the positive electrode liquid-retaining layer 26 described above also applies to the manufacturing method of the battery element 20 including the negative electrode liquid-retaining layer 27 . That is, after the negative electrode liquid-retaining layer 27 is formed on one surface of the separator 23, the separator 23 having the negative electrode liquid-retaining layer 27 formed thereon is wound. A negative electrode liquid retaining layer 27 may be formed on one surface of 23 . Even in this case, since the battery element 20 including the negative electrode liquid-retaining layer 27 can be produced, a similar effect can be obtained.
［変形例４］
多孔質膜であるセパレータ２３を用いた。しかしながら、ここでは具体的に図示しないが、高分子化合物層を含む積層型のセパレータを用いてもよい。 [Modification 4]
Aseparator 23, which is a porous membrane, was used. However, although not specifically illustrated here, a laminated separator including a polymer compound layer may be used.
多孔質膜であるセパレータ２３を用いた。しかしながら、ここでは具体的に図示しないが、高分子化合物層を含む積層型のセパレータを用いてもよい。 [Modification 4]
A
具体的には、積層型のセパレータは、一対の面を有する多孔質膜と、その多孔質膜の片面または両面に配置された高分子化合物層とを含んでいる。正極２１および負極２２のそれぞれに対するセパレータの密着性が向上するため、電池素子２０の位置ずれ（巻きずれ）が抑制されるからである。これにより、電解液の分解反応などが発生しても、二次電池の膨れが抑制される。高分子化合物層は、ポリフッ化ビニリデンなどの高分子化合物を含んでいる。ポリフッ化ビニリデンなどは、物理的強度に優れていると共に、電気化学的に安定だからである。
Specifically, a laminated separator includes a porous membrane having a pair of surfaces and a polymer compound layer disposed on one or both sides of the porous membrane. This is because the adhesiveness of the separator to each of the positive electrode 21 and the negative electrode 22 is improved, so that positional deviation (winding deviation) of the battery element 20 is suppressed. As a result, swelling of the secondary battery is suppressed even if a decomposition reaction or the like of the electrolytic solution occurs. The polymer compound layer contains a polymer compound such as polyvinylidene fluoride. This is because polyvinylidene fluoride or the like has excellent physical strength and is electrochemically stable.
なお、多孔質膜および高分子化合物層のうちの一方または双方は、複数の絶縁性粒子のうちのいずれか１種類または２種類以上を含んでいてもよい。二次電池の発熱時において複数の絶縁性粒子が放熱するため、その二次電池の安全性（耐熱性）が向上するからである。複数の絶縁性粒子に関する詳細は、上記した通りである。
One or both of the porous film and the polymer compound layer may contain one or more of a plurality of insulating particles. This is because the plurality of insulating particles dissipate heat when the secondary battery generates heat, thereby improving the safety (heat resistance) of the secondary battery. Details regarding the plurality of insulating particles are provided above.
積層型のセパレータを作製する場合には、高分子化合物および溶媒などを含む前駆溶液を調製したのち、多孔質膜の片面または両面に前駆溶液を塗布する。この場合には、必要に応じて、前駆溶液に複数の絶縁性粒子を添加してもよい。
When manufacturing a laminated separator, after preparing a precursor solution containing a polymer compound, a solvent, etc., the precursor solution is applied to one or both sides of the porous membrane. In this case, if necessary, a plurality of insulating particles may be added to the precursor solution.
この積層型のセパレータを用いた場合においても、正極２１と負極２２との間においてリチウムイオンが移動可能になるため、同様の効果を得ることができる。この場合には、特に、上記したように、電池素子２０の巻きずれが抑制されるため、より高い効果を得ることができる。
Even when this laminated separator is used, the same effect can be obtained because lithium ions can move between the positive electrode 21 and the negative electrode 22 . In this case, as described above, the battery element 20 is prevented from being displaced, so that a higher effect can be obtained.
［変形例５］
図１および図２では、巻回電極体である電池素子２０を用いている。しかしながら、図１に対応する図３および図２に対応する図４に示したように、積層電極体である電池素子５０を用いてもよい。以下では、随時、既に説明した図１および図２を参照する。 [Modification 5]
1 and 2, thebattery element 20, which is a wound electrode body, is used. However, as shown in FIG. 3 corresponding to FIG. 1 and FIG. 4 corresponding to FIG. 2, a battery element 50 that is a laminated electrode body may be used. In the following, reference will be made to FIGS. 1 and 2, which have already been described, from time to time.
図１および図２では、巻回電極体である電池素子２０を用いている。しかしながら、図１に対応する図３および図２に対応する図４に示したように、積層電極体である電池素子５０を用いてもよい。以下では、随時、既に説明した図１および図２を参照する。 [Modification 5]
1 and 2, the
図３および図４に示したラミネートフィルム型の二次電池は、電池素子２０（正極２１、負極２２、セパレータ２３、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７）および正極リード３１および負極リード３２の代わりに、電池素子５０（正極５１、負極５２、セパレータ５３、正極電解質層５４、負極電解質層５５、正極保液層５６および負極保液層５７）および正極リード５８および負極リード５９を備えていることを除いて、図１および図２に示したラミネートフィルム型の二次電池の構成とほぼ同様の構成を有している。
The laminated film type secondary battery shown in FIGS. 27) and instead of the positive electrode lead 31 and the negative electrode lead 32, the battery element 50 (the positive electrode 51, the negative electrode 52, the separator 53, the positive electrode electrolyte layer 54, the negative electrode electrolyte layer 55, the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57) and It has substantially the same configuration as the laminated film type secondary battery shown in FIGS.
正極５１、負極５２、セパレータ５３、正極電解質層５４、負極電解質層５５、正極保液層５６、負極保液層５７、正極リード５８および負極リード５９のそれぞれの構成は、以下で説明することを除いて、正極２１、負極２２、セパレータ２３、正極電解質層２４、負極電解質層２５、正極保液層２６、負極保液層２７、正極リード３１および負極リード３２のそれぞれの構成と同様である。
The configurations of the positive electrode 51, the negative electrode 52, the separator 53, the positive electrode electrolyte layer 54, the negative electrode electrolyte layer 55, the positive electrode retaining liquid layer 56, the negative electrode retaining liquid layer 57, the positive electrode lead 58, and the negative electrode lead 59 will be described below. Except for the above, the positive electrode 21 , the negative electrode 22 , the separator 23 , the positive electrode electrolyte layer 24 , the negative electrode electrolyte layer 25 , the positive electrode liquid layer 26 , the negative electrode liquid layer 27 , the positive electrode lead 31 and the negative electrode lead 32 have the same configuration.
すなわち、正極電解質層５４の重量比Ｒ１と正極保液層５６の重量比Ｒ２との関係および負極電解質層５５の重量比Ｒ３と負極保液層５７の重量比Ｒ４との関係は、上記した通りである。また、正極電解質層５４の厚さＴ１と正極保液層５６の厚さＴ２との関係および負極電解質層５５の厚さＴ３と負極保液層５７の厚さＴとの関係は、上記した通りである。
That is, the relationship between the weight ratio R1 of the positive electrode electrolyte layer 54 and the weight ratio R2 of the positive electrode liquid-retaining layer 56 and the relationship between the weight ratio R3 of the negative electrode electrolyte layer 55 and the weight ratio R4 of the negative electrode liquid-retaining layer 57 are as described above. is. Further, the relationship between the thickness T1 of the positive electrode electrolyte layer 54 and the thickness T2 of the positive electrode electrolyte layer 56 and the relationship between the thickness T3 of the negative electrode electrolyte layer 55 and the thickness T of the negative electrode electrolyte layer 57 are as described above. is.
電池素子５０では、正極５１および負極５２がセパレータ５３、正極電解質層５４および負極電解質層５５を介して交互に積層されている。正極保液層５６は、正極電解質層５４に隣接されていると共に、負極保液層５７は、負極電解質層５５に隣接されている。正極５１、負極５２、セパレータ５３、正極電解質層５４および負極電解質層５５のそれぞれの積層数は、特に限定されないため、任意に設定可能である。正極５１は、正極集電体２１Ａおよび正極活物質層２１Ｂに対応する正極集電体５１Ａおよび正極活物質層５１Ｂを含んでいると共に、負極５２は、負極集電体２２Ａおよび負極活物質層２２Ｂに対応する負極集電体５２Ａおよび負極活物質層５２Ｂを含んでいる。
In the battery element 50, positive electrodes 51 and negative electrodes 52 are alternately laminated with separators 53, positive electrode electrolyte layers 54, and negative electrode electrolyte layers 55 interposed therebetween. The positive electrode retaining liquid layer 56 is adjacent to the positive electrode electrolyte layer 54 , and the negative electrode retaining liquid layer 57 is adjacent to the negative electrode electrolyte layer 55 . The number of layers of the positive electrode 51, the negative electrode 52, the separator 53, the positive electrode electrolyte layer 54, and the negative electrode electrolyte layer 55 is not particularly limited, and can be set arbitrarily. The positive electrode 51 includes a positive electrode current collector 51A and a positive electrode active material layer 51B corresponding to the positive electrode current collector 21A and the positive electrode active material layer 21B, and the negative electrode 52 includes the negative electrode current collector 22A and the negative electrode active material layer 22B. and a negative electrode current collector 52A and a negative electrode active material layer 52B corresponding to .
ただし、図３および図４に示したように、正極集電体５１Ａは、正極活物質層５１Ｂが形成されていない突出部５１ＡＴを含んでいると共に、負極集電体５２Ａは、負極活物質層５２Ｂが形成されていない突出部５２ＡＴを含んでいる。この突出部５２ＡＴは、突出部５１ＡＴと重ならない位置に配置されている。複数の突出部５１ＡＴは、互いに接合されているため、１本のリード状の接合部５１Ｚを形成していると共に、複数の突出部５２ＡＴは、互いに接合されているため、１本のリード状の接合部５２Ｚを形成している。正極リード５８は、接合部５１Ｚに接続されていると共に、負極リード５９は、接合部５２Ｚに接続されている。
However, as shown in FIGS. 3 and 4, the positive electrode current collector 51A includes protrusions 51AT on which the positive electrode active material layer 51B is not formed, and the negative electrode current collector 52A includes the negative electrode active material layer. 52B includes projections 52AT that are not formed. The projecting portion 52AT is arranged at a position not overlapping the projecting portion 51AT. Since the plurality of projecting portions 51AT are joined to each other, they form one lead-shaped joint portion 51Z. A joint portion 52Z is formed. The positive lead 58 is connected to the joint 51Z, and the negative lead 59 is connected to the joint 52Z.
図３および図４に示した二次電池の製造方法は、電池素子２０の代わりに電池素子５０を作製すると共に、正極リード３１および負極リード３２の代わりに正極リード５８および負極リード５９を用いて二次電池を組み立てることを除いて、図１および図２に示した二次電池の製造方法と同様である。
3 and 4, the battery element 50 is produced instead of the battery element 20, and the positive electrode lead 58 and the negative electrode lead 59 are used instead of the positive electrode lead 31 and the negative electrode lead 32. The manufacturing method of the secondary battery shown in FIGS. 1 and 2 is the same except that the secondary battery is assembled.
具体的には、最初に、正極集電体５１Ａ（突出部５１ＡＴを除く。）の両面に正極活物質層５１Ｂが形成された正極５１と、負極集電体５２Ａ（突出部５２ＡＴを除く。）の両面に負極活物質層５２Ｂが形成された負極５２とを作製する。続いて、正極５１の表面に正極電解質層５４を形成すると共に、負極５２の表面に負極電解質層５５を形成する。また、セパレータ５３の両面に正極保液層５６および負極保液層５７を形成する。続いて、正極保液層５６および負極保液層５７が形成されているセパレータ５３を介して、正極電解質層５４が形成されている正極５１および負極電解質層５５が形成されている負極５２を交互に積層させることにより、電池素子５０を作製する。
Specifically, first, a positive electrode 51 having positive electrode active material layers 51B formed on both sides of a positive electrode current collector 51A (excluding protrusions 51AT), and a negative electrode current collector 52A (excluding protrusions 52AT). A negative electrode 52 having negative electrode active material layers 52B formed on both surfaces thereof is manufactured. Subsequently, a positive electrode electrolyte layer 54 is formed on the surface of the positive electrode 51 and a negative electrode electrolyte layer 55 is formed on the surface of the negative electrode 52 . Also, a positive electrode liquid-retaining layer 56 and a negative electrode liquid-retaining layer 57 are formed on both surfaces of the separator 53 . Subsequently, the positive electrode 51 formed with the positive electrode electrolyte layer 54 and the negative electrode 52 formed with the negative electrode electrolyte layer 55 are alternately arranged with the separator 53 formed with the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57 interposed therebetween. The battery element 50 is produced by stacking the layers.
続いて、溶接法などを用いて複数の突出部５１ＡＴを互いに接合させることにより、接合部５１Ｚを形成すると共に、溶接法などを用いて複数の突出部５２ＡＴを互いに接合させることにより、接合部５２Ｚを形成する。最後に、溶接法などを用いて突出部５１ＡＴに正極リード５８を接続させると共に、溶接法などを用いて突出部５２ＡＴに負極リード５９を接続させる。
Subsequently, the plurality of projecting portions 51AT are joined to each other using a welding method or the like to form the joining portion 51Z, and the plurality of projecting portions 52AT are joined to each other using a welding method or the like to form the joining portion 52Z. to form Finally, a welding method or the like is used to connect the positive electrode lead 58 to the projecting portion 51AT, and a welding method or the like is used to connect the negative electrode lead 59 to the projecting portion 52AT.
この積層電極体である電池素子５０を用いた場合においても、巻回電極体である電池素子２０を用いた場合と同様に、充放電繰り返しても放電容量の減少が抑制されるため、同様の効果を得ることができる。
Even in the case of using the battery element 50 that is the laminated electrode body, as in the case of using the battery element 20 that is the wound electrode body, the decrease in discharge capacity is suppressed even if charging and discharging are repeated. effect can be obtained.
なお、上記した変形例１～４のそれぞれは、電池素子２０の代わりに電池素子５０に適用されてもよい。
Note that each of Modifications 1 to 4 described above may be applied to the battery element 50 instead of the battery element 20 .
＜３．二次電池の用途＞
二次電池の用途（適用例）は、特に限定されない。電源として用いられる二次電池は、電子機器および電動車両などの主電源でもよいし、補助電源でもよい。主電源とは、他の電源の有無に関係なく、優先的に用いられる電源である。補助電源は、主電源の代わりに用いられる電源、または主電源から切り替えられる電源である。 <3. Use of secondary battery>
The use (application example) of the secondary battery is not particularly limited. A secondary battery used as a power source may be a main power source for electronic devices and electric vehicles, or may be an auxiliary power source. A main power source is a power source that is preferentially used regardless of the presence or absence of other power sources. An auxiliary power supply is a power supply that is used in place of the main power supply or that is switched from the main power supply.
二次電池の用途（適用例）は、特に限定されない。電源として用いられる二次電池は、電子機器および電動車両などの主電源でもよいし、補助電源でもよい。主電源とは、他の電源の有無に関係なく、優先的に用いられる電源である。補助電源は、主電源の代わりに用いられる電源、または主電源から切り替えられる電源である。 <3. Use of secondary battery>
The use (application example) of the secondary battery is not particularly limited. A secondary battery used as a power source may be a main power source for electronic devices and electric vehicles, or may be an auxiliary power source. A main power source is a power source that is preferentially used regardless of the presence or absence of other power sources. An auxiliary power supply is a power supply that is used in place of the main power supply or that is switched from the main power supply.
二次電池の用途の具体例は、以下の通りである。ビデオカメラ、デジタルスチルカメラ、携帯電話機、ノート型パソコン、ヘッドホンステレオ、携帯用ラジオおよび携帯用情報端末などの電子機器である。バックアップ電源およびメモリーカードなどの記憶用装置である。電動ドリルおよび電動鋸などの電動工具である。電子機器などに搭載される電池パックである。ペースメーカおよび補聴器などの医療用電子機器である。電気自動車（ハイブリッド自動車を含む。）などの電動車両である。非常時などに備えて電力を蓄積しておく家庭用または産業用のバッテリシステムなどの電力貯蔵システムである。これらの用途では、１個の二次電池が用いられてもよいし、複数個の二次電池が用いられてもよい。
Specific examples of secondary battery applications are as follows. Electronic devices such as video cameras, digital still cameras, mobile phones, laptop computers, headphone stereos, portable radios and portable information terminals. Backup power and storage devices such as memory cards. Power tools such as power drills and power saws. It is a battery pack mounted on an electronic device. Medical electronic devices such as pacemakers and hearing aids. It is an electric vehicle such as an electric vehicle (including a hybrid vehicle). It is a power storage system such as a home or industrial battery system that stores power in preparation for emergencies. In these uses, one secondary battery may be used, or a plurality of secondary batteries may be used.
電池パックは、単電池を用いてもよいし、組電池を用いてもよい。電動車両は、駆動用電源として二次電池を用いて作動（走行）する車両であり、その二次電池以外の他の駆動源を併せて備えたハイブリッド自動車でもよい。家庭用の電力貯蔵システムでは、電力貯蔵源である二次電池に蓄積された電力を利用して、家庭用の電気製品などを使用可能である。
The battery pack may use a single cell or an assembled battery. An electric vehicle is a vehicle that operates (runs) using a secondary battery as a drive power source, and may be a hybrid vehicle that also includes a drive source other than the secondary battery. In a household electric power storage system, electric power stored in a secondary battery, which is an electric power storage source, can be used to use electric appliances for home use.
ここで、二次電池の適用例の一例に関して具体的に説明する。以下で説明する適用例の構成は、あくまで一例であるため、適宜、変更可能である。
Here, an example of application of the secondary battery will be specifically described. The configuration of the application example described below is merely an example, and can be changed as appropriate.
図５は、電池パックのブロック構成を表している。ここで説明する電池パックは、１個の二次電池を用いた電池パック（いわゆるソフトパック）であり、スマートフォンに代表される電子機器などに搭載される。
Fig. 5 shows the block configuration of the battery pack. The battery pack described here is a battery pack (a so-called soft pack) using one secondary battery, and is mounted in an electronic device such as a smart phone.
この電池パックは、図５に示したように、電源６１と、回路基板６２とを備えている。この回路基板６２は、電源６１に接続されていると共に、正極端子６３、負極端子６４および温度検出端子６５を含んでいる。
This battery pack includes a power supply 61 and a circuit board 62, as shown in FIG. This circuit board 62 is connected to a power supply 61 and includes a positive terminal 63 , a negative terminal 64 and a temperature detection terminal 65 .
電源６１は、１個の二次電池を含んでいる。この二次電池では、正極リードが正極端子６３に接続されていると共に、負極リードが負極端子６４に接続されている。この電源６１は、正極端子６３および負極端子６４を介して外部と接続可能であるため、充放電可能である。回路基板６２は、制御部６６と、スイッチ６７と、熱感抵抗素子（ＰＴＣ素子）６８と、温度検出部６９とを含んでいる。ただし、ＰＴＣ素子６８は省略されてもよい。
The power supply 61 includes one secondary battery. In this secondary battery, the positive lead is connected to the positive terminal 63 and the negative lead is connected to the negative terminal 64 . The power source 61 can be connected to the outside through a positive terminal 63 and a negative terminal 64, and can be charged and discharged. The circuit board 62 includes a control section 66 , a switch 67 , a thermal resistance element (PTC element) 68 and a temperature detection section 69 . However, the PTC element 68 may be omitted.
制御部６６は、中央演算処理装置（ＣＰＵ）およびメモリなどを含んでおり、電池パック全体の動作を制御する。この制御部６６は、必要に応じて電源６１の使用状態の検出および制御を行う。
The control unit 66 includes a central processing unit (CPU), memory, etc., and controls the operation of the entire battery pack. This control unit 66 detects and controls the use state of the power source 61 as necessary.
なお、制御部６６は、電源６１（二次電池）の電圧が過充電検出電圧または過放電検出電圧に到達すると、スイッチ６７を切断することにより、電源６１の電流経路に充電電流が流れないようにする。過充電検出電圧は、特に限定されないが、具体的には、４．２Ｖ±０．０５Ｖであると共に、過放電検出電圧は、特に限定されないが、具体的には、２．４Ｖ±０．１Ｖである。
When the voltage of the power supply 61 (secondary battery) reaches the overcharge detection voltage or the overdischarge detection voltage, the control unit 66 cuts off the switch 67 so that the charging current does not flow through the current path of the power supply 61. to The overcharge detection voltage is not particularly limited, but is specifically 4.2V±0.05V, and the overdischarge detection voltage is not particularly limited, but is specifically 2.4V±0.1V. is.
スイッチ６７は、充電制御スイッチ、放電制御スイッチ、充電用ダイオードおよび放電用ダイオードなどを含んでおり、制御部６６の指示に応じて電源６１と外部機器との接続の有無を切り換える。このスイッチ６７は、金属酸化物半導体を用いた電界効果トランジスタ（ＭＯＳＦＥＴ）などを含んでおり、充放電電流は、スイッチ６７のＯＮ抵抗に基づいて検出される。
The switch 67 includes a charge control switch, a discharge control switch, a charge diode, a discharge diode, and the like, and switches connection/disconnection between the power supply 61 and an external device according to instructions from the control unit 66 . The switch 67 includes a field effect transistor (MOSFET) using a metal oxide semiconductor, etc., and the charge/discharge current is detected based on the ON resistance of the switch 67 .
温度検出部６９は、サーミスタなどの温度検出素子を含んでおり、温度検出端子６５を用いて電源６１の温度を測定すると共に、その温度の測定結果を制御部６６に出力する。温度検出部６９により測定される温度の測定結果は、異常発熱時において制御部６６が充放電制御を行う場合および残容量の算出時において制御部６６が補正処理を行う場合などに用いられる。
The temperature detection unit 69 includes a temperature detection element such as a thermistor, measures the temperature of the power supply 61 using the temperature detection terminal 65 , and outputs the temperature measurement result to the control unit 66 . The measurement result of the temperature measured by the temperature detection unit 69 is used when the control unit 66 performs charging/discharging control at the time of abnormal heat generation and when the control unit 66 performs correction processing when calculating the remaining capacity.
本技術の実施例に関して説明する。
An example of this technology will be explained.
＜実施例１～１１および比較例１～３＞
以下で説明するように、二次電池を作製したのち、その二次電池の電池特性を評価した。 <Examples 1 to 11 and Comparative Examples 1 to 3>
As described below, after the secondary battery was produced, the battery characteristics of the secondary battery were evaluated.
以下で説明するように、二次電池を作製したのち、その二次電池の電池特性を評価した。 <Examples 1 to 11 and Comparative Examples 1 to 3>
As described below, after the secondary battery was produced, the battery characteristics of the secondary battery were evaluated.
［二次電池の作製］
以下の手順により、図１および図２に示した電池素子２０（巻回電極体）を備えたラミネートフィルム型のリチウムイオン二次電池を作製した。 [Production of secondary battery]
A laminated film type lithium ion secondary battery including the battery element 20 (wound electrode body) shown in FIGS. 1 and 2 was produced by the following procedure.
以下の手順により、図１および図２に示した電池素子２０（巻回電極体）を備えたラミネートフィルム型のリチウムイオン二次電池を作製した。 [Production of secondary battery]
A laminated film type lithium ion secondary battery including the battery element 20 (wound electrode body) shown in FIGS. 1 and 2 was produced by the following procedure.
（正極の作製）
最初に、正極活物質（リチウム含有化合物（酸化物）であるＬｉＮｉ0.80Ｃｏ0.15Ａｌ0.05Ｏ2 ）９６質量部と、正極結着剤（ポリフッ化ビニリデン）３質量部と、正極導電剤（カーボンブラック）１質量部とを互いに混合させることにより、正極合剤とした。続いて、溶媒（有機溶剤であるＮ－メチル－２－ピロリドン）に正極合剤を投入したのち、その有機溶剤を撹拌することにより、ペースト状の正極合剤スラリーを調製した。続いて、コーティング装置を用いて正極集電体２１Ａ（厚さ＝１５μｍであるアルミニウム箔）の両面に正極合剤スラリーを塗布したのち、その正極合剤スラリーを乾燥させることにより、正極活物質層２１Ｂを形成した。最後に、ロールプレス機を用いて正極活物質層２１Ｂを圧縮成型したのち、その正極活物質層２１Ｂが形成されている正極集電体２１Ａを帯状（４８ｍｍ×３００ｍｍ）となるように切断した。これにより、正極２１が作製された。 (Preparation of positive electrode)
First, 96 parts by mass of a positive electrode active material (LiNi 0.80 Co 0.15 Al 0.05 O 2 which is a lithium-containing compound (oxide)), 3 parts by mass of a positive electrode binder (polyvinylidene fluoride), and a positive electrode conductor (carbon black ) and 1 part by mass were mixed with each other to obtain a positive electrode mixture. Subsequently, after the positive electrode mixture was put into a solvent (N-methyl-2-pyrrolidone as an organic solvent), the organic solvent was stirred to prepare a pasty positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry is applied to both surfaces of the positive electrodecurrent collector 21A (aluminum foil having a thickness of 15 μm) using a coating device, and then the positive electrode mixture slurry is dried to form a positive electrode active material layer. 21B. Finally, the positive electrode active material layer 21B was compression-molded using a roll press, and then the positive electrode current collector 21A on which the positive electrode active material layer 21B was formed was cut into strips (48 mm×300 mm). Thus, the positive electrode 21 was produced.
最初に、正極活物質（リチウム含有化合物（酸化物）であるＬｉＮｉ0.80Ｃｏ0.15Ａｌ0.05Ｏ2 ）９６質量部と、正極結着剤（ポリフッ化ビニリデン）３質量部と、正極導電剤（カーボンブラック）１質量部とを互いに混合させることにより、正極合剤とした。続いて、溶媒（有機溶剤であるＮ－メチル－２－ピロリドン）に正極合剤を投入したのち、その有機溶剤を撹拌することにより、ペースト状の正極合剤スラリーを調製した。続いて、コーティング装置を用いて正極集電体２１Ａ（厚さ＝１５μｍであるアルミニウム箔）の両面に正極合剤スラリーを塗布したのち、その正極合剤スラリーを乾燥させることにより、正極活物質層２１Ｂを形成した。最後に、ロールプレス機を用いて正極活物質層２１Ｂを圧縮成型したのち、その正極活物質層２１Ｂが形成されている正極集電体２１Ａを帯状（４８ｍｍ×３００ｍｍ）となるように切断した。これにより、正極２１が作製された。 (Preparation of positive electrode)
First, 96 parts by mass of a positive electrode active material (LiNi 0.80 Co 0.15 Al 0.05 O 2 which is a lithium-containing compound (oxide)), 3 parts by mass of a positive electrode binder (polyvinylidene fluoride), and a positive electrode conductor (carbon black ) and 1 part by mass were mixed with each other to obtain a positive electrode mixture. Subsequently, after the positive electrode mixture was put into a solvent (N-methyl-2-pyrrolidone as an organic solvent), the organic solvent was stirred to prepare a pasty positive electrode mixture slurry. Subsequently, the positive electrode mixture slurry is applied to both surfaces of the positive electrode
（負極の作製）
最初に、負極活物質（炭素材料である人造黒鉛）９０質量部と、負極結着剤（ポリフッ化ビニリデン）１０質量部とを互いに混合させることにより、負極合剤とした。続いて、溶媒（有機溶剤であるＮ－メチル－２－ピロリドン）に負極合剤を投入したのち、その有機溶剤を撹拌することにより、ペースト状の負極合剤スラリーを調製した。続いて、コーティング装置を用いて負極集電体２２Ａ（厚さ＝１５μｍである銅箔）の両面に負極合剤スラリーを塗布したのち、その負極合剤スラリーを乾燥させることにより、負極活物質層２２Ｂを形成した。最後に、ロールプレス機を用いて負極活物質層２２Ｂを圧縮成型したのち、その負極活物質層２２Ｂが形成されている負極集電体２２Ａを帯状（５０ｍｍ×３１０ｍｍ）となるように切断した。これにより、負極２２が作製された。 (Preparation of negative electrode)
First, 90 parts by mass of a negative electrode active material (artificial graphite that is a carbon material) and 10 parts by mass of a negative electrode binder (polyvinylidene fluoride) were mixed together to obtain a negative electrode mixture. Subsequently, after the negative electrode mixture was put into a solvent (N-methyl-2-pyrrolidone as an organic solvent), the organic solvent was stirred to prepare a pasty negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry is applied to both surfaces of the negative electrodecurrent collector 22A (copper foil having a thickness of 15 μm) using a coating device, and then the negative electrode mixture slurry is dried to form a negative electrode active material layer. 22B was formed. Finally, the negative electrode active material layer 22B was compression-molded using a roll press, and then the negative electrode current collector 22A on which the negative electrode active material layer 22B was formed was cut into strips (50 mm×310 mm). Thus, the negative electrode 22 was produced.
最初に、負極活物質（炭素材料である人造黒鉛）９０質量部と、負極結着剤（ポリフッ化ビニリデン）１０質量部とを互いに混合させることにより、負極合剤とした。続いて、溶媒（有機溶剤であるＮ－メチル－２－ピロリドン）に負極合剤を投入したのち、その有機溶剤を撹拌することにより、ペースト状の負極合剤スラリーを調製した。続いて、コーティング装置を用いて負極集電体２２Ａ（厚さ＝１５μｍである銅箔）の両面に負極合剤スラリーを塗布したのち、その負極合剤スラリーを乾燥させることにより、負極活物質層２２Ｂを形成した。最後に、ロールプレス機を用いて負極活物質層２２Ｂを圧縮成型したのち、その負極活物質層２２Ｂが形成されている負極集電体２２Ａを帯状（５０ｍｍ×３１０ｍｍ）となるように切断した。これにより、負極２２が作製された。 (Preparation of negative electrode)
First, 90 parts by mass of a negative electrode active material (artificial graphite that is a carbon material) and 10 parts by mass of a negative electrode binder (polyvinylidene fluoride) were mixed together to obtain a negative electrode mixture. Subsequently, after the negative electrode mixture was put into a solvent (N-methyl-2-pyrrolidone as an organic solvent), the organic solvent was stirred to prepare a pasty negative electrode mixture slurry. Subsequently, the negative electrode mixture slurry is applied to both surfaces of the negative electrode
（正極電解質層の形成）
最初に、溶媒（炭酸エステル系化合物である炭酸エチレン（ＥＣ）および炭酸プロピレン（ＰＣ））に電解質塩（リチウム塩であるＬｉＰＦ6 ）を投入したのち、その溶媒を撹拌した。この場合には、溶媒の混合比（重量比）を炭酸エチレン：炭酸プロピレン＝５０：５０、電解質塩の含有量を溶媒に対して１ｍｏｌ／ｋｇとした。 (Formation of positive electrode electrolyte layer)
First, an electrolyte salt (LiPF 6 , which is a lithium salt) was added to a solvent (ethylene carbonate (EC) and propylene carbonate (PC), which are carbonate compounds), and then the solvent was stirred. In this case, the mixing ratio (weight ratio) of the solvent was ethylene carbonate:propylene carbonate=50:50, and the content of the electrolyte salt was 1 mol/kg of the solvent.
最初に、溶媒（炭酸エステル系化合物である炭酸エチレン（ＥＣ）および炭酸プロピレン（ＰＣ））に電解質塩（リチウム塩であるＬｉＰＦ6 ）を投入したのち、その溶媒を撹拌した。この場合には、溶媒の混合比（重量比）を炭酸エチレン：炭酸プロピレン＝５０：５０、電解質塩の含有量を溶媒に対して１ｍｏｌ／ｋｇとした。 (Formation of positive electrode electrolyte layer)
First, an electrolyte salt (LiPF 6 , which is a lithium salt) was added to a solvent (ethylene carbonate (EC) and propylene carbonate (PC), which are carbonate compounds), and then the solvent was stirred. In this case, the mixing ratio (weight ratio) of the solvent was ethylene carbonate:propylene carbonate=50:50, and the content of the electrolyte salt was 1 mol/kg of the solvent.
高分子化合物としては、フッ化ビニリデンの単独重合体であるポリフッ化ビニリデン（ＰＶＤＦ）と、６種類のフッ化ビニリデンの共重合体とを用いた。６種類のフッ化ビニリデンの共重合体としては、フッ化ビニリデンとヘキサフルオロプロピレンとの共重合体（ＶＨ）と、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸（マレイン酸）との共重合体（ＶＨＭＡ）と、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸モノエステル（マレイン酸モノメチルエステル）との共重合体（ＶＨＭＭＭ）と、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸モノエステル（マレイン酸モノエチルエステル）との共重合体（ＶＨＭＭＥ）と、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸モノエステル（シトラコン酸モノメチルエステル）との共重合体（ＶＨＣＭＭ）と、フッ化ビニリデンとヘキサフルオロプロピレンと不飽和二塩基酸モノエステル（シトラコン酸モノエチルエステル）との共重合体（ＶＨＣＭＥ）とを用いた。これにより、電解液が調製された。
As the polymer compound, polyvinylidene fluoride (PVDF), which is a homopolymer of vinylidene fluoride, and six types of copolymers of vinylidene fluoride were used. The six types of vinylidene fluoride copolymers include a copolymer (VH) of vinylidene fluoride and hexafluoropropylene, and a copolymer of vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic acid (maleic acid). Polymer (VHMA), copolymer (VHMMM) of vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic acid monoester (monomethyl maleate), vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic a copolymer (VHMME) with an acid monoester (monoethyl maleate) and a copolymer (VHCMM) with vinylidene fluoride, hexafluoropropylene, and an unsaturated dibasic acid monoester (citraconic acid monomethyl ester); and a copolymer (VHCME) of vinylidene fluoride, hexafluoropropylene, and unsaturated dibasic acid monoester (citraconic acid monoethyl ester). An electrolytic solution was thus prepared.
続いて、電解液と、高分子化合物と、追加の溶媒（炭酸ジメチル）とを互いに混合させることにより、混合溶液を調製した。続いて、ホモジナイザを用いて混合溶液を加熱しながら撹拌することにより（加熱温度＝８０℃，撹拌時間＝３０分間～１時間）、ゾル状の前駆溶液を調整した。最後に、正極２１の表面に前駆溶液を塗布したのち、その前駆溶液を乾燥させることにより、正極電解質層２４を形成した。この正極電解質層２４を形成する場合には、電解液と高分子化合物との混合比を調整することにより、重量比Ｒ１を制御すると共に、前駆溶液の塗布量を調整することにより、厚さＴ１（μｍ）を制御した。重量比Ｒ１および厚さＴ１のそれぞれに関する詳細は、表１に示した通りである。
Subsequently, a mixed solution was prepared by mixing the electrolytic solution, the polymer compound, and an additional solvent (dimethyl carbonate) with each other. Subsequently, the mixed solution was heated and stirred using a homogenizer (heating temperature = 80°C, stirring time = 30 minutes to 1 hour) to prepare a sol precursor solution. Finally, the cathode electrolyte layer 24 was formed by applying the precursor solution to the surface of the positive electrode 21 and then drying the precursor solution. When forming the positive electrode electrolyte layer 24, the weight ratio R1 is controlled by adjusting the mixing ratio of the electrolyte and the polymer compound, and the thickness T1 is adjusted by adjusting the coating amount of the precursor solution. (μm) was controlled. Details of each of the weight ratio R1 and the thickness T1 are shown in Table 1.
（負極電解質層の形成）
負極２２の表面に前駆溶液を塗布したことを除いて、正極電解質層２４の形成手順と同様の手順により、負極電解質層２５を形成した。重量比Ｒ３および厚さＴ３のそれぞれに関する詳細は、表１に示した通りである。 (Formation of negative electrode electrolyte layer)
A negativeelectrode electrolyte layer 25 was formed in the same manner as the positive electrode electrolyte layer 24 except that the precursor solution was applied to the surface of the negative electrode 22 . Details of each of the weight ratio R3 and the thickness T3 are shown in Table 1.
負極２２の表面に前駆溶液を塗布したことを除いて、正極電解質層２４の形成手順と同様の手順により、負極電解質層２５を形成した。重量比Ｒ３および厚さＴ３のそれぞれに関する詳細は、表１に示した通りである。 (Formation of negative electrode electrolyte layer)
A negative
（正極保液層の形成）
セパレータ２３（厚さ＝１１μｍである微孔性ポリプロピレンフィルム）の一面に前駆溶液を塗布したことを除いて、正極電解質層２４の形成手順と同様の手順により、正極保液層２６を形成した。この場合には、電解液と高分子化合物との混合比を調整することにより、正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きくなるようにした。重量比Ｒ２および厚さＴ２のそれぞれに関する詳細は、表１に示した通りである。 (Formation of positive electrode liquid-retaining layer)
A positive electrode liquid-retaininglayer 26 was formed in the same manner as the positive electrode electrolyte layer 24, except that the precursor solution was applied to one surface of the separator 23 (a microporous polypropylene film having a thickness of 11 μm). In this case, the weight ratio R2 of the positive electrode liquid retaining layer 26 was made larger than the weight ratio R1 of the positive electrode electrolyte layer 24 by adjusting the mixing ratio of the electrolytic solution and the polymer compound. Details of each of the weight ratio R2 and thickness T2 are shown in Table 1.
セパレータ２３（厚さ＝１１μｍである微孔性ポリプロピレンフィルム）の一面に前駆溶液を塗布したことを除いて、正極電解質層２４の形成手順と同様の手順により、正極保液層２６を形成した。この場合には、電解液と高分子化合物との混合比を調整することにより、正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きくなるようにした。重量比Ｒ２および厚さＴ２のそれぞれに関する詳細は、表１に示した通りである。 (Formation of positive electrode liquid-retaining layer)
A positive electrode liquid-retaining
（負極保液層の形成）
セパレータ２３の一面（正極保液層２６が形成された面とは反対側の面）に前駆溶液を塗布したことを除いて、正極電解質層２４の形成手順と同様の手順により、負極保液層２７を形成した。この場合には、電解液と高分子化合物との混合比を調整することにより、負極保液層２７の重量比Ｒ４が負極電解質層２５の重量比Ｒ３よりも大きくなるようにした。重量比Ｒ４および厚さＴ４のそれぞれに関する詳細は、表１に示した通りである。 (Formation of negative electrode retaining liquid layer)
A negative electrode liquid-retaining layer was formed by the same procedure as that for forming the positiveelectrode electrolyte layer 24, except that the precursor solution was applied to one surface of the separator 23 (the surface opposite to the surface on which the positive electrode liquid-retaining layer 26 was formed). 27 was formed. In this case, the weight ratio R4 of the negative electrode liquid retaining layer 27 was made larger than the weight ratio R3 of the negative electrode electrolyte layer 25 by adjusting the mixing ratio of the electrolyte and the polymer compound. Details of each of the weight ratio R4 and the thickness T4 are shown in Table 1.
セパレータ２３の一面（正極保液層２６が形成された面とは反対側の面）に前駆溶液を塗布したことを除いて、正極電解質層２４の形成手順と同様の手順により、負極保液層２７を形成した。この場合には、電解液と高分子化合物との混合比を調整することにより、負極保液層２７の重量比Ｒ４が負極電解質層２５の重量比Ｒ３よりも大きくなるようにした。重量比Ｒ４および厚さＴ４のそれぞれに関する詳細は、表１に示した通りである。 (Formation of negative electrode retaining liquid layer)
A negative electrode liquid-retaining layer was formed by the same procedure as that for forming the positive
実施例１～１０および比較例１～３では、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれを形成するために、互いに共通する組成を有する電解液を用いたと共に、互いに共通する種類の高分子化合物を用いた。表１に「高分子化合物」の欄を１個だけ示しているのは、上記したように、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれにおいて互いに共通する種類の高分子化合物を用いたことを表している。
In Examples 1 to 10 and Comparative Examples 1 to 3, in order to form the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27, respectively, electrolytic solutions having compositions common to each other were used. was used, and a common type of polymer compound was used. Table 1 shows only one column of "polymer compound" because, as described above, each of the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 This indicates that a common type of polymer compound was used.
実施例１１では、正極電解質層２４および負極電解質層２５のそれぞれを形成するために用いた高分子化合物の種類と、正極保液層２６および負極保液層２７のそれぞれを形成するために用いた高分子化合物の種類とを互いに異ならせた。具体的には、正極電解質層２４および負極電解質層２５のそれぞれを形成するためにＰＶＤＦを用いたと共に、正極保液層２６および負極保液層２７のそれぞれを形成するためにＶＨＭＭＭを用いた。
In Example 11, the types of polymer compounds used to form the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25, respectively, and the types of polymer compounds used to form the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27, respectively The types of polymer compounds were made different from each other. Specifically, PVDF was used to form each of the positive electrode electrolyte layer 24 and the negative electrode electrolyte layer 25, and VHMMM was used to form each of the positive electrode electrolyte layer 26 and the negative electrode electrolyte layer 27.
なお、比較のために、正極保液層２６および負極保液層２７の双方を形成しなかった。また、比較のために、重量比Ｒ２が重量比Ｒ１以下となるように正極保液層２６を形成したと共に、重量比Ｒ４が重量比Ｒ３以下となるように負極保液層２７を形成した。
For comparison, neither the positive electrode liquid-retaining layer 26 nor the negative electrode liquid-retaining layer 27 was formed. For comparison, the positive electrode liquid-retaining layer 26 was formed such that the weight ratio R2 was equal to or less than the weight ratio R1, and the negative electrode liquid-retaining layer 27 was formed such that the weight ratio R4 was equal to or less than the weight ratio R3.
（二次電池の組み立て）
最初に、正極２１の正極集電体２１Ａにアルミニウム製の正極リード３１を溶接したと共に、負極２２の負極集電体２２Ａに銅製の負極リード３２を溶接した。 (Assembly of secondary battery)
First, thepositive electrode lead 31 made of aluminum was welded to the positive electrode current collector 21A of the positive electrode 21, and the negative electrode lead 32 made of copper was welded to the negative electrode current collector 22A of the negative electrode 22. As shown in FIG.
最初に、正極２１の正極集電体２１Ａにアルミニウム製の正極リード３１を溶接したと共に、負極２２の負極集電体２２Ａに銅製の負極リード３２を溶接した。 (Assembly of secondary battery)
First, the
続いて、正極保液層２６および負極保液層２７が形成されているセパレータ２３を介して、正極電解質層２４が形成されている正極２１と、負極電解質層２５が形成されている負極２２とを互いに積層させた。続いて、正極２１、負極２２、セパレータ２３、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７を巻回させることにより、電池素子２０を作製した。続いて、プレス機を用いて電池素子２０をプレスすることにより、その電池素子２０を扁平形状となるように成型した。
Subsequently, the positive electrode 21 formed with the positive electrode electrolyte layer 24 and the negative electrode 22 formed with the negative electrode electrolyte layer 25 are separated through the separator 23 formed with the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27. were stacked on top of each other. Subsequently, the positive electrode 21, the negative electrode 22, the separator 23, the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 were wound to produce the battery element 20. Subsequently, the battery element 20 was molded into a flat shape by pressing the battery element 20 using a pressing machine.
続いて、窪み部１０Ｕの内部に電池素子２０を収容したのち、外装フィルム１０（融着層／金属層／表面保護層）を折り畳むことにより、その外装フィルム１０同士を互いに対向させた。外装フィルム１０としては、融着層（厚さ＝３０μｍであるポリプロピレンフィルム）と、金属層（厚さ＝４０μｍであるアルミニウム箔）と、表面保護層（厚さ＝２５μｍであるナイロンフィルム）とが内側からこの順に積層されたアルミラミネートフィルムを用いた。
Subsequently, after housing the battery element 20 inside the recess 10U, the exterior films 10 (bonding layer/metal layer/surface protective layer) were folded to face each other. The exterior film 10 includes a fusion layer (polypropylene film with a thickness of 30 μm), a metal layer (aluminum foil with a thickness of 40 μm), and a surface protective layer (nylon film with a thickness of 25 μm). Aluminum laminate films laminated in this order from the inside were used.
最後に、互いに対向する外装フィルム１０（融着層）のうちの３辺の外周縁部同士を互いに熱融着させた。この場合には、外装フィルム１０と正極リード３１との間に封止フィルム４１（厚さ＝５μｍであるポリプロピレンフィルム）を挿入すると共に、外装フィルム１０と負極リード３２との間に封止フィルム４２（厚さ＝５μｍであるポリプロピレンフィルム）を挿入した。これにより、袋状の外装フィルム１０の内部に電池素子２０が封入されたため、二次電池が組み立てられた。
Finally, the outer peripheral edges of three sides of the exterior films 10 (bonding layers) facing each other were heat-bonded to each other. In this case, a sealing film 41 (a polypropylene film having a thickness of 5 μm) is inserted between the exterior film 10 and the positive electrode lead 31, and a sealing film 42 is inserted between the exterior film 10 and the negative electrode lead 32. (polypropylene film with thickness = 5 μm) was inserted. As a result, the battery element 20 was sealed inside the bag-shaped exterior film 10, and thus the secondary battery was assembled.
（二次電池の安定化）
常温環境中（温度＝２３℃）において二次電池を１サイクル充放電させた。充電時には、０．１Ｃの電流で電圧が４．２Ｖに到達するまで定電流充電したのち、その４．２Ｖの電圧で電流が０．０５Ｃに到達するまで定電圧充電した。放電時には、０．１Ｃの電流で電圧が３．０Ｖに到達するまで定電流放電した。０．１Ｃとは、電池容量（理論容量）を１０時間で放電しきる電流値であると共に、０．０５Ｃとは、電池容量を２０時間で放電しきる電流値である。これにより、ラミネートフィルム型の二次電池が完成した。 (Stabilization of secondary battery)
The secondary battery was charged and discharged for one cycle in a normal temperature environment (temperature = 23°C). During charging, constant-current charging was performed at a current of 0.1C until the voltage reached 4.2V, and then constant-voltage charging was performed at the voltage of 4.2V until the current reached 0.05C. During discharge, constant current discharge was performed at a current of 0.1C until the voltage reached 3.0V. 0.1C is a current value that can fully discharge the battery capacity (theoretical capacity) in 10 hours, and 0.05C is a current value that fully discharges the battery capacity in 20 hours. Thus, a laminate film type secondary battery was completed.
常温環境中（温度＝２３℃）において二次電池を１サイクル充放電させた。充電時には、０．１Ｃの電流で電圧が４．２Ｖに到達するまで定電流充電したのち、その４．２Ｖの電圧で電流が０．０５Ｃに到達するまで定電圧充電した。放電時には、０．１Ｃの電流で電圧が３．０Ｖに到達するまで定電流放電した。０．１Ｃとは、電池容量（理論容量）を１０時間で放電しきる電流値であると共に、０．０５Ｃとは、電池容量を２０時間で放電しきる電流値である。これにより、ラミネートフィルム型の二次電池が完成した。 (Stabilization of secondary battery)
The secondary battery was charged and discharged for one cycle in a normal temperature environment (temperature = 23°C). During charging, constant-current charging was performed at a current of 0.1C until the voltage reached 4.2V, and then constant-voltage charging was performed at the voltage of 4.2V until the current reached 0.05C. During discharge, constant current discharge was performed at a current of 0.1C until the voltage reached 3.0V. 0.1C is a current value that can fully discharge the battery capacity (theoretical capacity) in 10 hours, and 0.05C is a current value that fully discharges the battery capacity in 20 hours. Thus, a laminate film type secondary battery was completed.
［電池特性の評価］
二次電池の電池特性（サイクル特性）を評価したところ、表１に示した結果が得られた。 [Evaluation of battery characteristics]
When the battery characteristics (cycle characteristics) of the secondary battery were evaluated, the results shown in Table 1 were obtained.
二次電池の電池特性（サイクル特性）を評価したところ、表１に示した結果が得られた。 [Evaluation of battery characteristics]
When the battery characteristics (cycle characteristics) of the secondary battery were evaluated, the results shown in Table 1 were obtained.
サイクル特性を調べる場合には、最初に、常温環境中（温度＝２３℃）において二次電池を充放電させることにより、放電容量（１サイクル目の放電容量）を測定した。続いて、同環境中においてサイクル数が３００サイクルに到達するまで二次電池を繰り返して充放電させることにより、放電容量（３００サイクル目の放電容量）を測定した。最後に、容量維持率（％）＝（３００サイクル目の放電容量／１サイクル目の放電容量）×１００という計算式に基づいて、サイクル特性を評価するための指標である容量維持率を算出した。
When examining the cycle characteristics, first, the discharge capacity (discharge capacity in the first cycle) was measured by charging and discharging the secondary battery in a normal temperature environment (temperature = 23°C). Subsequently, the secondary battery was repeatedly charged and discharged in the same environment until the number of cycles reached 300 cycles, thereby measuring the discharge capacity (discharge capacity at the 300th cycle). Finally, the capacity retention rate, which is an index for evaluating cycle characteristics, was calculated based on the formula of capacity retention rate (%)=(discharge capacity at 300th cycle/discharge capacity at 1st cycle)×100. .
充放電条件は、充電時の電流および放電時の電流のそれぞれを０．５Ｃに変更したことを除いて、二次電池の安定化時の充放電条件と同様にした。０．５Ｃとは、電池容量を２時間で放電しきる電流値である。
The charge/discharge conditions were the same as the charge/discharge conditions during stabilization of the secondary battery, except that the current during charging and the current during discharging were each changed to 0.5C. 0.5C is a current value that can discharge the battery capacity in 2 hours.
［考察］
表１に示したように、容量維持率は、二次電池の構成に応じて大きく変動した。 [Discussion]
As shown in Table 1, the capacity retention rate varied greatly depending on the configuration of the secondary battery.
表１に示したように、容量維持率は、二次電池の構成に応じて大きく変動した。 [Discussion]
As shown in Table 1, the capacity retention rate varied greatly depending on the configuration of the secondary battery.
具体的には、正極保液層２６および負極保液層２７の双方を用いなかった場合（比較例１）には、容量維持率が著しく減少した。
Specifically, when both the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27 were not used (Comparative Example 1), the capacity retention rate significantly decreased.
これに対して、正極保液層２６および負極保液層２７の双方を用いた場合（実施例１～１１および比較例２，３）には、重量比Ｒ１～Ｒ４に応じて容量維持率に大きな差異が生じた。
On the other hand, when both the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27 are used (Examples 1 to 11 and Comparative Examples 2 and 3), the capacity retention rate varies depending on the weight ratios R1 to R4. It made a big difference.
すなわち、重量比Ｒ２が重量比Ｒ１以下であると共に重量比Ｒ４が重量比Ｒ３以下である場合（比較例２，３）には、正極保液層２６および負極保液層２７の双方を用いなかった場合（比較例１）と比較して、容量維持率がごく僅かに増加した。しかしながら、容量維持率はほぼ維持されたままであるため、依然として著しく減少したままであった。
That is, when the weight ratio R2 is equal to or less than the weight ratio R1 and the weight ratio R4 is equal to or less than the weight ratio R3 (Comparative Examples 2 and 3), neither the positive electrode liquid-retaining layer 26 nor the negative electrode liquid-retaining layer 27 is used. Compared to the case of (Comparative Example 1), the capacity retention rate increased very slightly. However, since the capacity retention rate was almost maintained, it was still significantly reduced.
重量比Ｒ２が重量比Ｒ１よりも大きいと共に重量比Ｒ４が重量比Ｒ３よりも大きい場合（実施例１～１１）には、正極保液層２６および負極保液層２７の双方を用いなかった場合（比較例１）と比較して、容量維持率が著しく増加した。この場合には、容量維持率が２倍以上になったため、その容量維持率が飛躍的に増加した。
When the weight ratio R2 is greater than the weight ratio R1 and the weight ratio R4 is greater than the weight ratio R3 (Examples 1 to 11), both the positive electrode liquid-retaining layer 26 and the negative electrode liquid-retaining layer 27 are not used. Compared to (Comparative Example 1), the capacity retention rate was remarkably increased. In this case, since the capacity retention rate was more than doubled, the capacity retention rate increased dramatically.
特に、重量比Ｒ２が重量比Ｒ１よりも大きいと共に重量比Ｒ４が重量比Ｒ３よりも大きい場合には、以下で説明する一連の傾向が得られた。
In particular, when the weight ratio R2 was greater than the weight ratio R1 and the weight ratio R4 was greater than the weight ratio R3, a series of trends described below were obtained.
第１に、厚さＴ２が厚さＴ１よりも大きいと共に厚さＴ４が厚さＴ３よりも大きいと、容量維持率がより増加した。
First, when the thickness T2 was larger than the thickness T1 and the thickness T4 was larger than the thickness T3, the capacity retention rate was further increased.
第２に、高分子化合物としてフッ化ビニリデンの共重合体を用い、より具体的にはフッ化ビニリデンの共重合体が重合成分としてヘキサフルオロプロピレンを含んでいると、容量維持率がより増加した。この場合には、フッ化ビニリデンの共重合体がさらに重合成分として不飽和二塩基酸および不飽和二塩基酸モノエステルのうちのいずれかを含んでいると、容量維持率がさらに増加した。
Second, when a vinylidene fluoride copolymer was used as the polymer compound, and more specifically, when the vinylidene fluoride copolymer contained hexafluoropropylene as a polymerization component, the capacity retention rate was further increased. . In this case, when the vinylidene fluoride copolymer further contained either an unsaturated dibasic acid or an unsaturated dibasic acid monoester as a polymerization component, the capacity retention rate was further increased.
＜実施例１２～２０＞
表２に示したように、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれに複数の絶縁性粒子を含有させたことを除いて実施例２と同様の手順により、二次電池を作製したと共に電池特性を評価した。 <Examples 12 to 20>
As shown in Table 2, the same as Example 2 except that each of the positiveelectrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 contained a plurality of insulating particles. A secondary battery was produced and the battery characteristics were evaluated by the procedure of .
表２に示したように、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれに複数の絶縁性粒子を含有させたことを除いて実施例２と同様の手順により、二次電池を作製したと共に電池特性を評価した。 <Examples 12 to 20>
As shown in Table 2, the same as Example 2 except that each of the positive
正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれを形成する場合には、電解液、高分子化合物および追加の溶媒（炭酸ジメチル）に複数の絶縁性粒子を添加したことを除いて同様の手順を経た。複数の絶縁性粒子の材質（絶縁性材料）としては、粉末状の無機材料である酸化アルミニウム（Ａｌ2 Ｏ3 ，メジアン径Ｄ５０＝０．４μｍ）および酸化チタン（ＴｉＯ2 ，メジアン径Ｄ５０＝０．４μｍ）と、粉末状の高分子化合物であるアクリル樹脂（メジアン径Ｄ５０＝０．４μｍ）とを用いた。複数の絶縁性粒子の添加量は、電解液の重量と高分子化合物の重量との和に対して２．５重量％とした。
When forming each of the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27, a plurality of insulating particles are added to the electrolyte, the polymer compound, and the additional solvent (dimethyl carbonate). A similar procedure was followed except that . As materials (insulating materials) for the plurality of insulating particles, aluminum oxide (Al 2 O 3 , median diameter D50=0.4 μm) and titanium oxide (TiO 2 , median diameter D50=0), which are powdery inorganic materials, are used. .4 μm) and an acrylic resin (median diameter D50=0.4 μm) which is a powdery polymer compound. The amount of the insulating particles added was 2.5% by weight with respect to the sum of the weight of the electrolytic solution and the weight of the polymer compound.
表２に示したように、正極電解質層２４、負極電解質層２５、正極保液層２６および負極保液層２７のそれぞれが複数の絶縁性粒子を含んでいると（実施例１２～２０）、容量維持率がより増加した。
As shown in Table 2, when each of the positive electrode electrolyte layer 24, the negative electrode electrolyte layer 25, the positive electrode liquid-retaining layer 26, and the negative electrode liquid-retaining layer 27 contains a plurality of insulating particles (Examples 12 to 20), The capacity retention rate has increased.
＜実施例２１～２７および比較例４～６＞
表３に示したように、図１および図２に示した電池素子２０（巻回電極体）を備えたラミネートフィルム型のリチウムイオン二次電池の代わりに、図３および図４に示した電池素子５０（積層電極体）を備えたラミネートフィルム型のリチウムイオン二次電池を作製したこと除いて、実施例１～２０および比較例１～３と同様の手順により、二次電池を作製したと共に電池特性を評価した。 <Examples 21 to 27 and Comparative Examples 4 to 6>
As shown in Table 3, the battery shown in FIGS. 3 and 4 was used instead of the laminated film type lithium ion secondary battery having the battery element 20 (wound electrode body) shown in FIGS. A secondary battery was produced in the same manner as in Examples 1 to 20 and Comparative Examples 1 to 3, except that a laminated film type lithium ion secondary battery including the element 50 (laminated electrode body) was produced. Battery characteristics were evaluated.
表３に示したように、図１および図２に示した電池素子２０（巻回電極体）を備えたラミネートフィルム型のリチウムイオン二次電池の代わりに、図３および図４に示した電池素子５０（積層電極体）を備えたラミネートフィルム型のリチウムイオン二次電池を作製したこと除いて、実施例１～２０および比較例１～３と同様の手順により、二次電池を作製したと共に電池特性を評価した。 <Examples 21 to 27 and Comparative Examples 4 to 6>
As shown in Table 3, the battery shown in FIGS. 3 and 4 was used instead of the laminated film type lithium ion secondary battery having the battery element 20 (wound electrode body) shown in FIGS. A secondary battery was produced in the same manner as in Examples 1 to 20 and Comparative Examples 1 to 3, except that a laminated film type lithium ion secondary battery including the element 50 (laminated electrode body) was produced. Battery characteristics were evaluated.
電池素子５０を備えた二次電池の製造手順は、以下で説明することを除いて、電池素子２０を備えた二次電池の製造手順と同様である。
The manufacturing procedure of the secondary battery having the battery element 50 is the same as the manufacturing procedure of the secondary battery having the battery element 20, except for the following description.
正極保液層５６および負極保液層５７が形成されているセパレータ５３を介して、正極電解質層５４が形成されている正極５１および負極電解質層５５が形成されている負極５２を交互に積層させることにより、電池素子５０を作製した。続いて、複数の突出部５１ＡＴを互いに溶接させることにより、接合部５１Ｚを形成したと共に、複数の突出部５２ＡＴを互いに溶接させることにより、接合部５２Ｚを形成した。続いて、突出部５１ＡＴに正極リード５８を溶接したと共に、突出部５２ＡＴに負極リード５９を溶接した。
The positive electrode 51 formed with the positive electrode electrolyte layer 54 and the negative electrode 52 formed with the negative electrode electrolyte layer 55 are alternately laminated with the separator 53 formed with the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57 interposed therebetween. Thus, a battery element 50 was produced. Subsequently, the plurality of projecting portions 51AT were welded together to form joint portions 51Z, and the plurality of projecting portions 52AT were welded together to form joint portions 52Z. Subsequently, the positive electrode lead 58 was welded to the projecting portion 51AT, and the negative electrode lead 59 was welded to the projecting portion 52AT.
表３に示したように、電池素子５０（積層電極体）を用いた場合（実施例２１～２７および比較例４～６）においても、電池素子２０（巻回電極体）を用いた場合（実施例１～２０および比較例１～３）と同様の結果が得られた。
As shown in Table 3, even when the battery element 50 (laminated electrode body) was used (Examples 21 to 27 and Comparative Examples 4 to 6), when the battery element 20 (wound electrode body) was used ( Results similar to those of Examples 1-20 and Comparative Examples 1-3) were obtained.
すなわち、正極保液層５６および負極保液層５７の双方を用いなかった場合（比較例４）には、容量維持率が著しく減少した。また、正極保液層５６および負極保液層５７のそれぞれを用いても、重量比Ｒ２が重量比Ｒ１以下であると共に重量比Ｒ４が重量比Ｒ３以下である場合（比較例５，６）には、依然として容量維持率が著しく減少したままであった。
That is, when both the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57 were not used (Comparative Example 4), the capacity retention rate significantly decreased. Further, even when each of the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57 is used, when the weight ratio R2 is equal to or less than the weight ratio R1 and the weight ratio R4 is equal to or less than the weight ratio R3 (Comparative Examples 5 and 6) However, the capacity retention rate was still significantly reduced.
これに対して、正極保液層５６および負極保液層５７の双方を用いることにより、重量比Ｒ２が重量比Ｒ１よりも大きいと共に重量比Ｒ４が重量比Ｒ３よりも大きい場合（実施例２１～２７）には、容量維持率が著しく増加した。この他、表１に関して説明した一連の傾向も同様に得られた。
On the other hand, by using both the positive electrode liquid-retaining layer 56 and the negative electrode liquid-retaining layer 57, when the weight ratio R2 is larger than the weight ratio R1 and the weight ratio R4 is larger than the weight ratio R3 (Example 21 to 27), the capacity retention rate was significantly increased. In addition, the set of trends described with respect to Table 1 were obtained as well.
［まとめ］
表１～表３に示した結果から、正極２１とセパレータ２３との間に正極電解質層２４が配置されており、その正極電解質層２４に正極保液層２６が隣接されており、その正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きいと、容量維持率が大幅に改善された。よって、二次電池において優れたサイクル特性が得られた。 [summary]
From the results shown in Tables 1 to 3, the positiveelectrode electrolyte layer 24 is arranged between the positive electrode 21 and the separator 23, the positive electrode electrolyte layer 24 is adjacent to the positive electrode liquid retaining layer 26, and the positive electrode retaining layer 26 is adjacent to the positive electrode electrolyte layer 24. When the weight ratio R2 of the liquid layer 26 was larger than the weight ratio R1 of the positive electrode electrolyte layer 24, the capacity retention rate was significantly improved. Therefore, excellent cycle characteristics were obtained in the secondary battery.
表１～表３に示した結果から、正極２１とセパレータ２３との間に正極電解質層２４が配置されており、その正極電解質層２４に正極保液層２６が隣接されており、その正極保液層２６の重量比Ｒ２が正極電解質層２４の重量比Ｒ１よりも大きいと、容量維持率が大幅に改善された。よって、二次電池において優れたサイクル特性が得られた。 [summary]
From the results shown in Tables 1 to 3, the positive
また、負極２２とセパレータ２３との間に負極電解質層２５が配置されており、その負極電解質層２５に負極保液層２７が隣接されており、その負極保液層２７の重量比Ｒ４が負極電解質層２５の重量比Ｒ３よりも大きい場合においても、容量維持率が大幅に改善されたため、二次電池において優れたサイクル特性が得られた。
A negative electrode electrolyte layer 25 is arranged between the negative electrode 22 and the separator 23, and a negative electrode electrolyte layer 25 is adjacent to the negative electrode electrolyte layer 27. The weight ratio R4 of the negative electrode liquid retaining layer 27 is Even when the weight ratio of the electrolyte layer 25 was greater than R3, the capacity retention rate was significantly improved, and thus the secondary battery had excellent cycle characteristics.
以上、一実施形態および実施例を挙げながら本技術に関して説明したが、その本技術の構成は、一実施形態および実施例において説明された構成に限定されないため、種々に変形可能である。
Although the present technology has been described above while citing one embodiment and example, the configuration of this technology is not limited to the configuration described in the one embodiment and example, and can be variously modified.
二次電池の電池構造がラミネートフィルム型である場合に関して説明したが、その電池構造の種類は、特に限定されない。具体的には、電池構造は、円筒型、角型、コイン型およびボタン型などでもよい。
Although the case where the battery structure of the secondary battery is a laminated film type has been described, the type of battery structure is not particularly limited. Specifically, the battery structure may be cylindrical, rectangular, coin-shaped, button-shaped, and the like.
また、電池素子の構成が巻回型および積層型である場合に関して説明したが、その電池素子の構成は、特に限定されない。具体的には、電池素子の構成は、正極および負極がジグザグに折り畳まれた九十九折り型などでもよい。
In addition, the case where the configuration of the battery element is the wound type and the laminated type has been described, but the configuration of the battery element is not particularly limited. Specifically, the configuration of the battery element may be a ninety-nine fold type in which the positive electrode and the negative electrode are folded in a zigzag pattern.
さらに、電極反応物質がリチウムである場合に関して説明したが、その電極反応物質の種類は、特に限定されない。具体的には、電極反応物質は、上記したように、ナトリウムおよびカリウムなどの他のアルカリ金属でもよいし、ベリリウム、マグネシウムおよびカルシウムなどのアルカリ土類金属でもよい。この他、電極反応物質は、アルミニウムなどの他の軽金属でもよい。
Furthermore, although the case where the electrode reactant is lithium has been described, the type of the electrode reactant is not particularly limited. Specifically, the electrode reactants may be other alkali metals such as sodium and potassium, or alkaline earth metals such as beryllium, magnesium and calcium, as described above. Alternatively, the electrode reactant may be other light metals such as aluminum.
本明細書中に記載された効果は、あくまで例示であるため、本技術の効果は、本明細書中に記載された効果に限定されない。よって、本技術に関して、他の効果が得られてもよい。
Since the effects described in this specification are merely examples, the effects of the present technology are not limited to the effects described in this specification. Accordingly, other advantages may be obtained with respect to the present technology.
Claims (7)
- 第１電解液および第１高分子化合物を含む第１電解質層と、
前記第１電解質層を介して互いに対向する電極およびセパレータと、
前記電極および前記セパレータが前記第１電解質層を介して互いに対向する方向と交差する方向において前記第１電解質層に隣接され、第２電解液および第２高分子化合物を含む第２電解質層と
を備え、
前記第２高分子化合物の重量に対する前記第２電解液の重量の比は、前記第１高分子化合物の重量に対する前記第１電解液の重量の比よりも大きい、
二次電池。 a first electrolyte layer containing a first electrolytic solution and a first polymer compound;
an electrode and a separator facing each other across the first electrolyte layer;
a second electrolyte layer that is adjacent to the first electrolyte layer in a direction that intersects the direction in which the electrode and the separator face each other through the first electrolyte layer, and contains a second electrolyte solution and a second polymer compound; prepared,
the ratio of the weight of the second electrolytic solution to the weight of the second polymer compound is greater than the ratio of the weight of the first electrolytic solution to the weight of the first polymer compound;
secondary battery. - 前記第２電解質層の厚さは、前記第１電解質層の厚さよりも大きい、
請求項１記載の二次電池。 the thickness of the second electrolyte layer is greater than the thickness of the first electrolyte layer;
The secondary battery according to claim 1. - 前記第１高分子化合物および前記第２高分子化合物のうちの少なくとも一方は、フッ化ビニリデンの単独重合体およびフッ化ビニリデンの共重合体のうちの少なくとも一方を含む、
請求項１または請求項２に記載の二次電池。 At least one of the first polymer compound and the second polymer compound contains at least one of a vinylidene fluoride homopolymer and a vinylidene fluoride copolymer,
The secondary battery according to claim 1 or 2. - 前記フッ化ビニリデンの共重合体は、重合成分としてヘキサフルオロプロピレンを含む、
請求項３記載の二次電池。 The vinylidene fluoride copolymer contains hexafluoropropylene as a polymerization component,
The secondary battery according to claim 3. - 前記フッ化ビニリデンの共重合体は、さらに、重合成分として不飽和二塩基酸および不飽和二塩基酸モノエステルのうちの少なくとも一方を含む、
請求項４記載の二次電池。 The vinylidene fluoride copolymer further contains at least one of an unsaturated dibasic acid and an unsaturated dibasic acid monoester as a polymerization component.
The secondary battery according to claim 4. - 前記第１電解質層および前記第２電解質層のうちの少なくとも一方は、さらに、複数の絶縁性粒子を含む、
請求項１ないし請求項５のいずれか１項に記載の二次電池。 at least one of the first electrolyte layer and the second electrolyte layer further comprising a plurality of insulating particles;
The secondary battery according to any one of claims 1 to 5. - リチウムイオン二次電池である、
請求項１ないし請求項６のいずれか１項に記載の二次電池。 A lithium ion secondary battery,
The secondary battery according to any one of claims 1 to 6.
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| JP2014056695A (en) * | 2012-09-12 | 2014-03-27 | Sony Corp | Secondary battery, battery pack and electric vehicle |
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| JP2007207461A (en) * | 2006-01-31 | 2007-08-16 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2012074367A (en) * | 2010-08-30 | 2012-04-12 | Sony Corp | Nonaqueous electrolyte battery and manufacturing method thereof, insulation material and manufacturing method thereof, and battery pack, electronic apparatus, electric vehicle, power storage device and electric power system |
| JP2014056695A (en) * | 2012-09-12 | 2014-03-27 | Sony Corp | Secondary battery, battery pack and electric vehicle |
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