WO2010150397A1 - 正電極板、電池、車両、電池搭載機器、及び、正電極板の製造方法 - Google Patents
正電極板、電池、車両、電池搭載機器、及び、正電極板の製造方法 Download PDFInfo
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- WO2010150397A1 WO2010150397A1 PCT/JP2009/061706 JP2009061706W WO2010150397A1 WO 2010150397 A1 WO2010150397 A1 WO 2010150397A1 JP 2009061706 W JP2009061706 W JP 2009061706W WO 2010150397 A1 WO2010150397 A1 WO 2010150397A1
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- Prior art keywords
- positive electrode
- active material
- battery
- electrode plate
- electrode active
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 claims abstract description 146
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- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 57
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 57
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 15
- 239000011149 active material Substances 0.000 claims description 100
- 239000011230 binding agent Substances 0.000 claims description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 68
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 239000004020 conductor Substances 0.000 claims description 28
- 230000027455 binding Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 152
- 239000011888 foil Substances 0.000 description 36
- 229910052782 aluminium Inorganic materials 0.000 description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 32
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- 230000000052 comparative effect Effects 0.000 description 21
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- 238000012360 testing method Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 238000010248 power generation Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
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- 238000004804 winding Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910015608 LiNi0.82Co0.15Al0.03O2 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- DETKHEZXMOBNHJ-UHFFFAOYSA-N [Co].[Ni].[Li].[Li] Chemical compound [Co].[Ni].[Li].[Li] DETKHEZXMOBNHJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode plate including a base and a positive electrode active material layer formed on the base, a battery using the positive electrode plate, a vehicle equipped with the battery, and a battery-equipped device. Moreover, it is related with the manufacturing method of such a positive electrode plate.
- Patent Document 1 discloses an active material layer (positive electrode active material layer) using only a carboxymethyl cellulose (hereinafter also referred to as CMC) as a binder on a conductive layer (carbon coat layer).
- CMC carboxymethyl cellulose
- a positive electrode a positive electrode plate
- the positive electrode active material layer is formed on the carbon coat layer, there is an advantage that the peel strength of the positive electrode active material layer can be increased.
- the structure of CMC used in the binder changes in the presence of an alkaline substance such as a lithium composite oxide. Thereby, the viscosity of CMC becomes low compared with other binders, such as a polyethylene oxide (henceforth PEO), for example. For this reason, when manufacturing the positive electrode plate described in Patent Document 1, the viscosity of the active material paste in which CMC (binder), positive electrode active material particles, conductive material and solvent are kneaded is reduced.
- Patent Document 1 also exemplifies, for example, polytetrafluoroethylene (hereinafter also referred to as PTFE) in addition to CMC as a binder for the positive electrode active material layer.
- PTFE polytetrafluoroethylene
- the PTFE particles and the conductive material easily form aggregates in the active material paste.
- acetylene black is used as the conductive material, the PTFE particles are not dispersed in the active material paste, and some of them form a relatively large aggregate (particle size: 50 ⁇ m or more) together with acetylene black. End up.
- the peel strength of the positive electrode active material layer is higher when PTFE is not included, and the battery resistance change rate (battery resistance value is the initial battery resistance value of the battery. It has been found that it can also be kept small.
- the present invention has been made in view of such knowledge, and has a positive electrode active material layer with high peel strength and suppressed increase in battery resistance, a battery using this positive electrode plate, and this battery.
- An object is to provide a vehicle equipped with a battery and a battery-equipped device. Moreover, it aims at providing the manufacturing method of the positive electrode plate which can manufacture a positive electrode active material layer appropriately.
- One aspect of the present invention is a positive electrode plate comprising a conductive substrate and a positive electrode active material layer formed on the substrate and including positive electrode active material particles, a conductive material, and a binder,
- the binder is a positive electrode plate made of only polyethylene oxide or made of only polyethylene oxide and carboxymethyl cellulose.
- a battery using a positive electrode plate having a positive electrode active material layer using only PEO as a binder or only PEO and CMC is used as a positive electrode active material layer using PTFE together with PEO and CMC as a binder. It has been found that the peel strength of the positive electrode active material layer is high and the rate of change in battery resistance can be reduced as compared with a battery equipped with a battery. In addition, such a battery has a high peel strength and a low battery resistance change rate even compared to the battery of Patent Document 1, that is, a battery using only CMC as a binder.
- the positive electrode plate described above has a positive electrode active material than a positive electrode active material layer using PTFE as a binder and a positive electrode active material layer using only CMC as a binder.
- the peel strength of the material layer can be improved, and an increase in battery resistance can be suppressed.
- the positive electrode active material layer aggregates derived from PTFE are not formed in the active material paste. That is, in this positive electrode plate, the formation of such aggregates is prevented, and the active material paste is uniformly applied to the substrate. Therefore, the battery characteristics can be stabilized by using this positive electrode plate.
- Examples of the conductive material included in the positive electrode active material layer include the above-described carbon powder and metal powder such as nickel powder.
- Examples of the positive electrode active material particles include lithium transition metal composite oxide particles such as lithium cobaltate, lithium nickelate, and lithium manganate, and iron olivine compounds.
- the positive electrode plate described above may be a positive electrode plate in which a carbon coat layer containing carbon powder is interposed between the base and the positive electrode active material layer.
- the carbon coat layer is interposed between the base and the positive electrode active material layer, the binding force between the base and the positive electrode active material layer can be reliably increased.
- carbon black such as acetylene black, furnace black, and ketjen black, graphite powder, etc. are mentioned, for example.
- the binding material may be a positive electrode plate made of only polyethylene oxide and carboxymethyl cellulose.
- a battery using a positive electrode plate including a positive electrode active material layer containing only PEO and CMC as a binder is more than a battery using a positive electrode plate including a positive electrode active material layer containing only PEO as a binder. It has been found that the battery resistance change rate can be reduced. From this, if the above-mentioned positive electrode plate is used for a battery, it can be set as the battery which suppressed the increase in battery resistance.
- the positive electrode active material layer may be a positive electrode plate containing 1 wt% each of the polyethylene oxide and the carboxymethyl cellulose.
- a battery using a positive electrode plate having a positive electrode active material layer containing 1 wt% of PEO and CMC as a binder includes not only a battery using a positive electrode active material layer containing only CMC but also only PEO. It has been found that the battery resistance change rate can be made smaller than that of a battery using a positive electrode active material layer. This is because the coating amount of the positive electrode active material particles is small with CMC alone, and the surface of the positive electrode active material particles is deteriorated. Conversely, with PEO alone, the coverage of the positive electrode active material particles becomes large, and the area involved in the battery reaction in the surface area of the particles becomes narrow, and the inside of the positive electrode active material particles deteriorates when charging and discharging are repeated as a battery. It is thought that it is easy to do. From this, if the above-mentioned positive electrode plate is used for a battery, it can be set as the battery which suppressed the increase in battery resistance.
- another aspect of the present invention is a battery using the positive electrode plate described above.
- the above-described positive electrode plate is used for the battery described above, a battery having high peel strength of the positive electrode active material layer and suppressing an increase in battery resistance can be obtained.
- another aspect of the present invention is a vehicle in which the battery described above is mounted and the electric energy from the battery is used for all or part of the power source.
- the above-mentioned vehicle is equipped with the above-described battery, that is, the battery using the above-mentioned positive electrode plate, it can be a vehicle in which deterioration of driving performance is suppressed.
- the vehicle may be a vehicle that uses electric energy from a battery as a whole or a part of a power source.
- a vehicle that uses electric energy from a battery as a whole or a part of a power source.
- an electric vehicle a hybrid vehicle, a plug-in hybrid vehicle, a hybrid railway vehicle, a forklift, an electric wheelchair, an electric vehicle Examples include assist bicycles and electric scooters.
- the other aspect of this invention is a battery mounting apparatus which mounts the battery mentioned above and uses the electrical energy by this battery as all or one part of an energy source.
- the above-described battery-equipped device is equipped with the above-described battery, that is, a battery using the above-described positive electrode plate, it can be a battery-equipped device in which deterioration of characteristics is suppressed.
- a battery mounting apparatus what is necessary is just an apparatus which mounts a battery and uses this as all or one part of an energy source, for example, a personal computer, a mobile telephone, a battery-powered electric tool, an uninterruptible power supply, etc. And various home appliances driven by batteries, office equipment, and industrial equipment.
- another aspect of the present invention is a positive electrode plate comprising a conductive substrate and a positive electrode active material layer formed on the substrate and including positive electrode active material particles, a conductive material, and a binder.
- the binder is made of polyethylene oxide alone or polyethylene oxide and carboxymethyl cellulose, and the positive electrode active material particles, the conductive material, and the active material paste kneaded with the binder are mixed with the substrate.
- a positive electrode active material in which a positive electrode active material layer is formed by applying an active material paste using only PEO as a binder or using only PEO and CMC to a substrate and drying it. A layer forming step; For this reason, the positive electrode plate which has favorable peel strength and formed the positive electrode active material layer which maintained the appropriate shape in the base
- PEO has higher alkali resistance than CMC.
- CMC carbonate-semiconductor
- the positive electrode plate includes a carbon coat layer containing carbon powder interposed between the base body and the positive electrode active material layer, and the positive electrode active material plate.
- the material layer forming step may be a method for manufacturing a positive electrode plate in which the active material paste is applied on the carbon coat layer formed on the substrate in advance.
- the positive electrode plate manufacturing method described above in the positive electrode active material layer forming step, since the coating is performed on the carbon coat layer formed on the substrate, the binding force between the formed positive electrode active material layer and the substrate is reliably increased. can do.
- the positive electrode plate manufacturing method described above includes a filter passing step of passing the kneaded active material paste through a filter having a collection efficiency of 90% of 50 ⁇ m or less prior to the positive electrode active material layer forming step.
- a method for manufacturing the electrode plate is preferable.
- the above-described positive electrode plate manufacturing method includes the above-described filter passing step, so that foreign matters can be removed by the filter and foreign matters can be efficiently removed without clogging by aggregates.
- the collection efficiency 90% is a thing of 50 micrometers or less, Specifically, the multilayer roll of a nonwoven fabric made from a polypropylene or polyethylene, the single layer pleat of a nonwoven fabric, a thread wound filter etc. are mentioned.
- FIG. 1 is a perspective view of a battery according to Embodiment 1.
- FIG. 3 is a perspective view of a negative electrode plate according to Embodiment 1.
- FIG. 2 is a perspective view of a positive electrode plate according to Embodiment 1.
- FIG. It is an expanded sectional view (A section of Drawing 3) of the positive electrode board of Embodiment 1.
- 2 is a perspective view of a positive electrode plate according to Embodiment 1.
- FIG. 2 is a perspective view of a positive electrode plate according to Embodiment 1.
- FIG. 3 is an explanatory diagram of a positive electrode active material layer forming step of the positive electrode plate according to the first embodiment.
- FIG. 3 is an explanatory diagram of a positive electrode active material layer forming step of the positive electrode plate according to the first embodiment.
- FIG. 3 is an explanatory diagram of a positive electrode active material layer forming step of the positive electrode plate according to the first embodiment.
- FIG. 3 is an explanatory diagram of a positive electrode active material layer forming step of the positive electrode plate according to the first embodiment. It is explanatory drawing of the vehicle concerning Embodiment 2.
- FIG. It is explanatory drawing of the battery mounting apparatus concerning Embodiment 3.
- FIG. 1 shows a perspective view of the battery 1 of the first embodiment.
- the battery 1 is a wound lithium ion secondary battery including a power generating element 20 having a negative electrode plate 40 and a separator 50 in addition to the positive electrode plate 30 and an electrolyte solution (not shown) (see FIG. 1).
- a power generation element 20 and an electrolytic solution are accommodated in a rectangular box-shaped battery case 10.
- the battery case 10 has a battery case body 11 and a sealing lid 12 both made of aluminum. Of these, the battery case main body 11 has a bottomed rectangular box shape, and an insulating film (not shown) made of resin and bent into a box shape is interposed between the battery case 10 and the power generation element 20.
- the sealing lid 12 has a rectangular plate shape, and closes the opening of the battery case body 11 and is welded to the battery case body 11.
- the positive electrode terminal portion 71 ⁇ / b> A and the negative electrode terminal portion 72 ⁇ / b> A located at the distal ends are penetrated through the sealing lid 12. 1 protrudes from the lid surface 12a facing upward.
- An insulating member 75 made of an insulating resin is interposed between the positive terminal 71A and the negative terminal 72A and the sealing lid 12 to insulate each other.
- a rectangular plate-shaped safety valve 77 is also sealed on the sealing lid 12.
- an organic electrolytic solution in which LiPF 6 is added as a solute and a concentration of lithium ions is 1 mol / l.
- the power generating element 20 is formed by winding a strip-shaped negative electrode plate 40 and a positive electrode plate 30 into a flat shape via a strip-shaped separator 50 made of polyethylene (see FIG. 1).
- the positive electrode plate 30 and the negative electrode plate 40 of the power generation element 20 are respectively joined to a plate-like positive current collector 71 or negative current collector 72 bent in a crank shape.
- the negative electrode plate 40 of the power generation element 20 has a strip shape extending in the longitudinal direction DA, a copper foil 48 made of copper, and a first foil main surface 48 a and a second foil main body of the copper foil 48. It has two negative electrode active material layers 41 and 41 laminated on the surface 48b, and a ceramic coat layer 42 formed on the negative electrode active material layers 41 and 41, respectively.
- the ceramic coat layer 42 is made of alumina and polyvinylidene fluoride (PVDF). With this ceramic coat layer 42, even when the separator 50 contracts or breaks due to a short circuit due to a small hole or foreign matter in the separator 50, it is possible to prevent the short circuit point from being widened.
- PVDF polyvinylidene fluoride
- the negative electrode active material layer 41 includes a negative electrode active material (not shown) made of graphite, a binder (not shown) made of carboxymethylcellulose (CMC), and styrene butadiene rubber (SBR, not shown).
- a negative electrode active material made of graphite
- a binder made of carboxymethylcellulose (CMC)
- SBR styrene butadiene rubber
- the positive electrode plate 30 constituting the power generation element 20 will be described with reference to FIGS.
- the positive electrode plate 30 has a strip shape extending in the longitudinal direction DA, an aluminum foil 38 made of aluminum, and main surfaces of the aluminum foil 38 (first foil main surface 38a, second foil).
- Carbon coat layers 37, 37 formed on the main surface 38b) and a positive electrode active material layer 31 formed on the carbon coat layer 37 are provided.
- the carbon coat layer 37 has a thickness of 2 ⁇ m and includes polyvinylidene fluoride (PVDF) (not shown) in addition to the carbon powder CP made of acetylene black.
- PVDF polyvinylidene fluoride
- This carbon coat layer 37 prevents the active material paste 31P (described later) from contacting the aluminum foil 38 and generating corrosion when forming the cathode active material layer 31 (described later). Plays an auxiliary role in physical contact with 31.
- the positive electrode active material layer 31 of the positive electrode plate 30 includes CMC as the first binder 32A and PEO as the second binder 32B, as described below, while polytetrafluoroethylene. (PTFE) is not included. For this reason, there is a concern about a decrease in peel strength of the positive electrode active material layer 31 on the aluminum foil 38.
- PTFE polytetrafluoroethylene.
- the positive electrode active material layer 31 does not include PTFE, and the positive electrode active material particles 36 made of LiNi 0.82 Co 0.15 Al 0.03 O 2 and acetylene black.
- the positive electrode active material layer 31 is kneaded by adding ion-exchanged water AQ to the positive electrode active material particles 36, the first binder 32A, the second binder 32B, and the conductive material 35.
- the active material paste 31P is applied, dried, and further compressed.
- Inventors performed the evaluation test about the characteristic (battery capacity and battery resistance) of the battery 1 mentioned above.
- a new (initial) battery 1 that was just manufactured was tested. Specifically, as a battery capacity evaluation test, for a battery 1 that has been charged with constant current until the voltage between terminals reaches 4.1 V (full charge voltage) at a current value of 1 C, the voltage between terminals at a current value of 1 C Constant current discharge was performed until the voltage reached 2.5 V, and the discharged amount of electricity (battery capacity) was measured.
- the terminal voltage is 3.537 V (the state of charge (SOC) is equivalent to 30% (2.5 to 4.1 V) at a current value of 1 C. (When the battery capacity in the voltage range of 100% is assumed to be 100%)), and then the battery is charged while keeping the voltage constant while gradually decreasing the current value from 1C to 0.02C (constant voltage) charging). After a 30-second pause, constant current discharge was performed at a current value of 30 C, and the voltage value at 10 seconds after the start of discharge was measured. The battery resistance value at this time was calculated according to Ohm's law.
- the battery 1 subjected to the above test was subjected to a cycle test in which constant current charging and constant current discharging (current value is 1C for both) were repeated in a voltage range of 2.5 to 4.1V. Specifically, 2000 cycles were repeated continuously, with one set of charging / discharging as one cycle. Thereafter, the battery resistance value of the battery 1 was measured in the same manner as described above. Then, the battery resistance change rate of the battery 1 after the cycle test was calculated. This battery resistance change rate is obtained by dividing the battery resistance value after the cycle test by the battery resistance value at the time of a new article (initial) before the cycle test.
- the inventors measured the peel strength of the positive electrode active material layer 31 of the positive electrode plate 30 in the battery 1. Specifically, using a tensile tester (not shown), the positive electrode plate 30 is fixed with a double-sided tape having sufficiently higher adhesive strength than the peel strength, and the positive electrode active material layer 31 is placed in a direction perpendicular to the positive electrode plate 30. The strength when pulled was measured.
- the batteries 101 and 201 as other examples and the batteries C1 and C2 as comparative examples are also manufactured, and the evaluation test of these characteristics and the measurement of the peel strength of the positive electrode plate are performed in the same manner as the battery 1. went.
- the battery 101 according to Example 2 is a positive electrode plate having a positive electrode active material layer 131 using only the second binder 32B (PEO) as a binder in addition to the positive electrode active material particles 36 and the conductive material 35. 130 is used (see FIGS. 1 and 5).
- the battery 201 according to Example 3 was replaced with the positive electrode active material particles 36 made of LiCoO 2 instead of the positive electrode active material particles 36 made of LiNi 0.82 Co 0.15 Al 0.03 O 2 used in the battery 1.
- the battery C1 according to Comparative Example 1 includes a positive electrode containing PTFE in addition to the positive electrode active material particles 36, the conductive material 35, the first binder 32A (CMC), and the second binder 32B (PEO).
- a positive electrode plate having an active material layer was used.
- the battery C2 according to Comparative Example 2 includes a positive electrode plate having a positive electrode active material layer using only the first binder 32A (CMC) as a binder in addition to the positive electrode active material particles 36 and the conductive material 35. Using.
- Table 1 shows the test results of these batteries 1, 101, 201 and comparative batteries C1, C2.
- the peel strength of the positive electrode active material layer in the positive electrode plate is a relative value (%) based on the peel strength of the positive electrode active material layer in the positive electrode plate used in the comparative battery C1.
- the battery resistance change rates of the batteries 1, 101 and 201 are all smaller than that of the comparative battery C1. From this, it can be seen that the battery resistance change rate can be reduced in the battery using the positive electrode plate having the positive electrode active material layer not containing PTFE, rather than including PTFE. Furthermore, the peel strengths of the positive electrode active material layers 31, 131, and 231 in the positive electrode plates 30, 130, and 230 used for the batteries 1, 101, and 201, respectively, are relatively higher than those of the comparative battery C1. From this, it can be seen that the positive electrode active material layer not containing PTFE can have higher peel strength than containing PTFE.
- the battery resistance change rates of the batteries 1, 101, 201 are all smaller than the comparative battery C2. Therefore, a positive electrode active material using only PEO (battery 1) or only PEO and CMC (batteries 101 and 201) as a binder rather than using only CMC as a binder (comparative battery C2). It turns out that the battery using the positive electrode plate which has a layer can make the battery resistance change rate small. Further, the peel strengths of the positive electrode active material layers 31, 131, and 231 included in the positive electrode plates 30, 130, and 230 used in the batteries 1, 101, and 201, respectively, are relatively higher than those of the comparative battery C2. From this, it can be seen that the positive electrode active material layer using only PEO or only PEO and CMC can have higher peel strength than using only CMC as the binder.
- the positive electrode plates 30, 130, and 230 of the batteries 1, 101, and 201 have a comparative battery C 1, that is, a battery having a positive electrode active material layer using PTFE as a binder, and a comparative battery C 2,
- the peel strength of the positive electrode active material layer 31 can be improved and the increase in battery resistance can be suppressed as compared with the case where the positive electrode active material layer using only CMC is used as the binder.
- the positive electrode active material layer 31 including only PEO and CMC as the binder is provided. It can be seen that the battery 1 using the positive electrode plate 30 can have a lower rate of battery resistance change than the battery 101 using the positive electrode plate 130 having the positive electrode active material layer 131 containing only PEO as the binder.
- the battery 201 of Example 3 in which LiCoO 2 was used as the positive electrode active material was also compared with the battery 101 in Example 2 in which the positive electrode active material was LiCoO 2 (details of characteristics are not shown). It has been found that the battery resistance change rate can be reduced. Therefore, it can be seen that it is more preferable to use the positive electrode plates 30 and 230 having the positive electrode active material layer using the binder composed only of PEO and CMC.
- the battery resistance change rate of the battery 1 is smaller than the battery resistance change rate of the battery 101 as well as the comparative batteries C1 and C2. Therefore, it is particularly preferable to use the positive electrode plate 30 having the positive electrode active material layer 31 containing 1 wt% each of the first binder 32A (CMC) and the second binder 32B (PEO) as the binder. I understand that. This is because the coating amount of the positive electrode active material particles is small with CMC alone, and the surface of the positive electrode active material particles is deteriorated.
- the coverage of the positive electrode active material particles becomes large, and the area involved in the battery reaction in the surface area of the particles becomes narrow, and the inside of the positive electrode active material particles deteriorates when charging and discharging are repeated as a battery. It is thought that it is easy to do. Further, the battery 1 using the positive electrode plate 30 having the positive electrode active material layer containing 1 wt% of PEO and CMC, respectively, can further suppress the increase in battery resistance.
- the carbon coat layer 37 is formed on the aluminum foil 38.
- 30 parts by weight of acetylene black forming the carbon powder CP and PVDF / NMP solution having a solid content of 13% obtained by mixing PVDF with n-methylpyrrolidone (NMP) were used.
- NMP n-methylpyrrolidone
- This carbon coat layer paste (not shown) was applied to both surfaces (first foil main surface 38a, second foil main surface 38b) of an aluminum foil 38 having a thickness of 15 ⁇ m with a gravure coater, and then dried.
- a carbon coat layer 37 was formed.
- a kneader 900 including a mixing tank 901 and a stirring blade 902 that stirs the contents stored in the mixing tank 901 while shearing is used.
- the positive electrode active material layer forming step includes a coating step using the coating device 700 shown in FIG. 7 and a pressing step using the press device 800 shown in FIG.
- the coating apparatus 700 includes an unwinding unit 701, a die 710, a heater 730, a winding unit 702, and a plurality of auxiliary rollers 740 (see FIG. 7).
- the die 710 includes a metal paste holding unit 711 that stores therein the active material paste 31P that has passed through the filter 910, and the active material paste 31P that is held in the paste holding unit 711 in the carbon coat layer 37. And a discharge port 712 that continuously discharges toward the end.
- the discharge port 712 is slit-shaped in the width direction of the aluminum foil 38 so as to discharge the active material paste 31P in a band shape onto the carbon coat layers 37, 37 formed on both surfaces of the aluminum foil 38 moving in the longitudinal direction DA. It opens parallel to the depth direction in FIG.
- the heater 730 heats the aluminum foil 38 and the active material paste 31P applied to the aluminum foil 38.
- the drying of the active material paste 31 ⁇ / b> P applied to the carbon coat layer 37 proceeds gradually, and when it has passed through the heater 730, the active material
- the paste 31P is completely dried, that is, the ion-exchanged water AQ in the active material paste 31P is completely evaporated.
- the belt-shaped aluminum foil 38 (thickness: 15 ⁇ m) wound around the unwinding portion 701 is moved in the longitudinal direction DA. Carbon coat layers 37 and 37 are applied in advance on both surfaces of the aluminum foil 38.
- An active material paste 31 ⁇ / b> P is applied to the carbon coat layer 37 on the aluminum foil 38 with a die 710. Thereafter, the active material paste 31P was dried with a heater 730 to form an uncompressed active material layer 31B.
- the single-side supported aluminum foil 38 ⁇ / b> K in which the uncompressed active material layer 31 ⁇ / b> B is supported on the carbon coat layer 37 on one side is temporarily wound around the winding unit 702.
- the active material paste 31P is applied to the carbon coat layer 37 on the side of the single-side supported aluminum foil 38K (aluminum foil 38) on which the uncompressed active material layer 31B is not supported. Apply. Then, the active material paste 31P is completely dried by the heater 730. Thus, an active material laminate 30B before pressing, in which the uncompressed active material layers 31B and 31B are laminated on the carbon coat layers 37 and 37 on both sides of the aluminum foil 38, respectively, is produced.
- the press device 800 includes an unwinding unit 801, a press roller 810, a winding unit 802, and a plurality of auxiliary rollers 820.
- the above-mentioned active material laminated plate 30B before pressing is passed between the two pressing rollers 810 and 810 from the unwinding portion 801 and compressed in the thickness direction DT.
- a positive electrode plate 30 is obtained in which two compressed positive electrode active material layers 31 and 31 are laminated on both sides of the aluminum foil 38 (see FIGS. 3 and 4).
- the inventors investigated the change in the viscosity of the active material paste with the passage of time (standing time) after production.
- the standing time is 0h ( Immediately after production), the respective viscosities at 24 h, 48 h, 72 h and 96 h were measured.
- the active material paste (comparative paste EP) containing only the first binder 32A (CMC) as the binder has a standing time of 0h (immediately after production), 24h, 48h. Each viscosity at the time was also measured.
- the E-type viscosity meter VM shown in FIG. 9 was used for the measurement of the viscosity of each active material paste.
- This E-type viscometer VM has a cone plate VMC having a conical shape on one side (14 mm outer diameter and cone angle of 3 °) that can rotate around an axis AX, and a planar base perpendicular to the axis AX. It is a rotational viscometer having VMB.
- the active material paste 31P immediately after the production was placed on a base VMB of the E-type viscometer VM in a thermostat at 30 ° C. so that the gap was 100 ⁇ m.
- the cone plate VMC was moved from above the active material paste 31P until the tip of the cone plate VMC contacted the base VMB. Thereafter, the cone plate VMC was rotated at a constant speed with a shear rate (rotational speed) of 1 rpm around the axis AX, and the viscosity of the active material paste 31P was measured. Furthermore, the viscosities when the standing time was 24 h, 48 h, 72 h, and 96 h were also measured. For the comparative paste EP of the comparative example, the viscosity at the time when the standing time was 0h, 24h, and 48h was measured in the same manner as the active material paste 31P. These results are shown in FIG.
- the graph in FIG. 10 is a graph showing changes in the viscosity of each active material paste depending on the length of the standing time.
- the standing time is 0 h, that is, when compared immediately after fabrication, the viscosity of the active material paste 31P is higher than the viscosity of the comparative paste EP. From this, it is understood that the viscosity of the active material paste can be improved by using not only CMC but also PEO as the binder of the active material paste.
- the active material paste 31P using PEO and CMC as the binder is applied on the carbon coat layer 37 in the above-described coating process, the active material paste 31P is not dried until it is dried by the heater 730. It is possible to prevent the occurrence of problems such as spreading beyond the range of application or flowing down from the aluminum foil 38. That is, in the manufacturing method of the first embodiment, the positive electrode plate 30 in which the positive electrode active material layer 31 maintaining an appropriate shape is formed on the aluminum foil 38 (carbon coat layer 37) can be manufactured.
- the positive electrode active material layer forming step since it is applied onto the carbon coat layer 37 formed on the aluminum foil 38, the positive electrode active material layer 31 and the aluminum foil 38 are formed by the anchor effect of the carbon coat layer 37. The binding force of can be reliably increased.
- the viscosity of each of the active material paste 31 ⁇ / b> P and the comparative paste EP decreases as the standing time increases. This is because the positive electrode active material particles 36 contained in any paste (active material paste 31P, comparative paste EP) show alkalinity, and accordingly, the viscosity of CMC gradually decreases with time. It is thought that. However, in the active material paste 31P, the rate of viscosity decrease (the viscosity change amount divided by the standing time) is smaller than that of the comparative paste EP. That is, the active material paste 31P has a gradual decrease in viscosity over time. This is presumably because PEO in the active material paste 31P has higher alkali resistance than CMC, and the viscosity of the PEO is maintained in the active material paste 31P.
- the active material paste 31P when used in the above-described coating process, the change in the viscosity of the active material paste 31P with time is small, and even when many positive electrode plates 30 are manufactured, the thickness of the positive electrode active material layer 31 and the like. Thus, the positive electrode plate 30 can be manufactured efficiently.
- a negative electrode plate 40 was manufactured separately from the positive electrode plate 30 described above. Specifically, 98 parts by weight of graphite powder, 81 parts by weight of a 1.23 wt% CMC aqueous solution (that is, 1 part by weight of CMC), and 4 parts by weight of ion-exchanged water were mixed. Further, 70 parts by weight of ion exchange water was added and uniformly kneaded, and then 1 part by weight of styrene butadiene rubber (SBR) was added and stirred to prepare a negative electrode paste (not shown).
- SBR styrene butadiene rubber
- the above-described negative electrode paste was applied to both surfaces of a copper foil 48 having a thickness of 10 ⁇ m with a die coater, then dried, and pressed together with the copper foil 48 to form a negative electrode active material layer 41.
- a ceramic paste was applied onto the negative electrode active material layer 41 using a well-known gravure coater and dried to obtain a ceramic coat layer 42.
- the negative electrode plate 40 is completed (see FIG. 2).
- a power generation element 20 is obtained by winding a 20 ⁇ m separator 50 between the positive electrode plate 30 and the negative electrode plate 40 manufactured as described above. Further, the positive electrode current collecting member 71 and the negative electrode current collecting member 72 are welded to the positive electrode plate 30 (aluminum foil 38) and the negative electrode plate 40 (copper foil 48), respectively, inserted into the battery case body 11, and an electrolyte solution (not shown). Then, the battery case body 11 is sealed by welding with the sealing lid 12. Thus, the battery 1 is completed (see FIG. 1).
- the positive electrode plate 30 In the manufacturing method of the positive electrode plate 30 according to the first embodiment, only the first binder 32A (CMC) and the second binder 32B (PEO) are used as the binder without including PTFE.
- An active material paste 31P is applied to an aluminum foil 38 (on the carbon coat layer 37) and dried to form the positive electrode active material layer 31. For this reason, the positive electrode plate 30 of the battery 1 which has the favorable peel strength and can suppress the increase in the battery resistance can be manufactured.
- the positive electrode plate 30 including the positive electrode active material layer 31 using only the first binder 32A (CMC) and the second binder 32B (PEO) as the binder for the battery 1, there is also an advantage that an increase in the battery resistance can be suppressed (see Table 1 described above). Further, since PTFE is not included in the active material paste 31P, the active material paste 31P can be thinly and uniformly applied without generating aggregates in the active material paste 31P.
- the active material paste 31P does not contain PTFE. For this reason, the aggregate by the electrically conductive material 35 which consists of PTFE particle
- the manufacturing method of the positive electrode plate 130 of the battery 101 according to Example 2 and the manufacturing method of the positive electrode plate 230 of the battery 201 according to Embodiment 3 are the active processes used in the coating process of the positive electrode active material layer forming process. Since the material paste is the same as the above-described method for manufacturing the positive electrode plate 30 of the battery 1 and is otherwise the same, the description thereof is omitted.
- the active material paste 131P is formed using the kneader 900 shown in FIG. Specifically, 87 parts by weight of the positive electrode active material particles 36, 10 parts by weight of the conductive material 35, 1 part by weight of the second binder 32B (PEO), and 85 parts by weight of ion-exchanged water AQ, Each was put into a mixing tank 901 of one kneader 900 and mixed using a stirring blade 902. Thereby, a uniform active material paste 131P is obtained.
- the active material paste 131P produced by the kneader 900 is passed through the filter 910 to remove foreign matters mixed in the active material paste 131P.
- the coating step of the positive electrode active material layer forming step of the positive electrode plate 130 in the battery 101 the carbon coat layer 37 formed on both surfaces of the aluminum foil 38 using the die 710 of the coating apparatus 700 shown in FIG. 37, the active material paste 131P is applied.
- the active material paste 231P is formed using the kneader 900 shown in FIG. Specifically, 87 parts by weight of the positive electrode active material particles 236 made of LiCoO 2 , 10 parts by weight of the conductive material 35, and the first binder 32A (CMC), which are different from the positive electrode active material particles 36 of the battery 1 described above. Then, 1 part by weight of the second binder 32B (PEO) and 85 parts by weight of ion-exchanged water AQ were put into the mixing tank 901 of the first kneader 900, and mixed using the stirring blade 902. Thereby, a uniform active material paste 231P is obtained.
- the active material paste 231P made by the kneader 900 is passed through the filter 910 to remove foreign matters mixed in the active material paste 231P.
- the active material paste 231 ⁇ / b> P is applied to any of 37.
- vehicle 400 is provided with a plurality of the batteries 1 described above.
- vehicle 400 is a hybrid vehicle that is driven by using engine 440, front motor 420, and rear motor 430 together.
- the vehicle 400 includes a vehicle body 490, an engine 440, a front motor 420, a rear motor 430, a cable 450, an inverter 460, and an assembled battery 410 having a plurality of batteries 1, 101, 201 therein. is doing.
- the vehicle 400 according to the second embodiment is equipped with the batteries 1, 101, 201 described above, that is, the batteries 1, 101, 201 using the positive electrode plates 30, 130, 230 described above, the driving performance is improved. It can be set as the vehicle 400 which suppressed degradation.
- the hammer drill 500 of the third embodiment is equipped with the battery pack 510 including the batteries 1, 101, 201 described above, and as shown in FIG. 14, a battery-equipped device having the battery pack 510 and the main body 520. It is.
- the battery pack 510 is detachably accommodated in the pack accommodating portion 521 of the main body 520 of the hammer drill 500.
- the hammer drill 500 according to the third embodiment is equipped with the batteries 1, 101, 201 described above, that is, the batteries 1, 101, 201 using the positive electrode plates 30, 130, 230 described above. It can be set as the hammer drill 500 which suppressed deterioration.
- acetylene black is used as the carbon powder included in the carbon coat layer.
- carbon black such as furnace black or ketjen black, graphite powder, or the like other than acetylene black may be used. good.
- the electrically conductive material which consists of acetylene black was used for the positive electrode plate, you may use things other than acetylene black among the carbon powder mentioned above, metal powders, such as nickel powder, etc., for example.
- nickel cobalt lithium lithium was used for the positive electrode active material particles, for example, other lithium transition metal composite oxides such as lithium cobaltate, lithium nickelate, and lithium manganate, and iron olivine compounds may also be used. good.
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Abstract
Description
このような電池に関して、例えば、特許文献1には、導電層(カーボンコート層)の上に、カルボキシメチルセルロース(以下、CMCともいう)のみを結着材とした活物質層(正極活物質層)を備える正極(正電極板)が開示されている。
さらに、活物質ペースト中に存在するCMCの粘度が、時間の経過と共に極端に低下してしまう。このため、正電極板を製造するに当たっては、活物質ペーストを混練後、速やかに塗布しなければならない。また、混練後しばらく時間が経った活物質ペーストは粘度が低下して、塗布の工程に用いることができない。かくして、正電極板を生産(製造)する場合の効率が悪くなる不具合があった。
このような凝集体を含んだ活物質ペーストを塗布して正電極板を製造すると、例えば、凝集体が点在してしまい、この活物質ペーストを基体に薄く一様に塗布できないので、充放電に伴う反応が正極活物質層の部位によってばらつき、正電極板、ひいてはこれを用いた電池の特性が安定しない。また、異物除去のため、この活物質ペーストをフィルタに通すことがあるが、凝集体が生じていると、フィルタが凝集体により目詰まりを起こしやすく、活物質ペーストの通過量を減少させるので、生産性が低下する不具合もある。
また、CMC、PEOと共にPTFEを用いた場合に比して、PTFEを含まない方が正極活物質層の剥離強度が高く、電池抵抗変化率(電池抵抗値を、電池の初期の電池抵抗値で割ったもの)も小さく抑えることができることが判ってきた。
また、そのような電池は、特許文献1の電池、即ち、結着材にCMCのみを用いた電池に比しても、剥離強度を高く、また、電池抵抗変化率を小さくできる。
かくして、上述の正電極板は、結着材にPTFEを用いた正極活物質層を備えたものより、また、結着材にCMCのみを用いた正極活物質層を備えたものより、正極活物質層の剥離強度を向上でき、電池抵抗の増加を抑制できる。
また、正極活物質粒子は、例えば、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム等のリチウム遷移金属複合酸化物粒子や、鉄オリビン化合物が挙げられる。
30,130,230 正電極板
31,131,231 正極活物質層
31P,131P,231P 活物質ペースト
32A 第1結着材(結着材)
32B 第2結着材(結着材)
35 導電材
36,236 正極活物質粒子
37 カーボンコート層
38 アルミ箔(基体)
CP 炭素粉体
400 車両
500 ハンマードリル(電池搭載機器)
910 フィルタ
次に、本発明の実施形態1について、図面を参照しつつ説明する。
まず、本実施形態1にかかる正電極板30を用いてなる電池1(実施例1)について説明する。図1に実施例1の電池1の斜視図を示す。
この電池1は、正電極板30のほかに負電極板40及びセパレータ50を有する発電要素20、及び、図示しない電解液を備える捲回形のリチウムイオン二次電池である(図1参照)。この電池1は、発電要素20及び電解液(図示しない)を矩形箱状の電池ケース10に収容している。この電池ケース10は、共にアルミニウム製の電池ケース本体11及び封口蓋12を有する。このうち電池ケース本体11は有底矩形箱形であり、この電池ケース10と発電要素20との間には、樹脂からなり、箱状に折り曲げた絶縁フィルム(図示しない)が介在させてある。
このうち、セラミックコート層42は、アルミナ及びポリフッ化ビニリデン(PVDF)からなる。このセラミックコート層42により、セパレータ50の***や異物による短絡に伴い、セパレータ50の収縮や破壊が起きた場合でも、その短絡点を広げないようにすることができる。また、負極活物質層41は、グラファイトからなる負極活物質(図示しない)、カルボキシルメチルセルロース(CMC)からなる結着材(図示しない)、及び、スチレンブタジエンラバー(SBR、図示しない)を含む。なお、スチレンブタジエンラバーは、ペーストに用いるとCMCに比して高い結着作用を呈するので、負極活物質層を形成するにあたり、その形状を適切に保持することができる。
本実施形態1では、負極活物質層41内における、これらの重量比を、負極活物質:結着材:SBR=98:1:1とした。
この正電極板30は、図3,4に示すように、長手方向DAに延びる帯状で、アルミニウムからなるアルミ箔38と、このアルミ箔38の主面(第1箔主面38a,第2箔主面38b)上にそれぞれ形成したカーボンコート層37,37と、このカーボンコート層37上に形成された正極活物質層31とを有している。
このカーボンコート層37は、後述する正極活物質層31の形成の際、後述の活物質ペースト31Pがアルミ箔38に接触して腐食を発生するのを防止し、アルミ箔38と正極活物質層31との物理的接触の補助的役割を果たす。
なお、この正極活物質層31は、後に詳述するが、正極活物質粒子36、第1結着材32A、第2結着材32B及び導電材35に、イオン交換水AQを加えて混練した活物質ペースト31Pを塗布し、乾燥させて、さらにこれを圧縮したものである。
まず、電池1のうち、製造して間もない新品(初期)の電池1について試験を行った。具体的には、電池容量の評価試験として、1Cの電流値で端子間電圧が4.1V(満充電電圧)になるまで定電流充電をした電池1について、1Cの電流値で端子間電圧が2.5Vになるまで定電流放電を行い、放電した電気量(電池容量)を測定した。また、電池抵抗の評価試験では、上述の電池容量の試験の後に、1Cの電流値で、端子間電圧が3.537V(充電状態(SOC)が30%に相当(2.5~4.1Vの電圧範囲における電池容量を100%としたとき))になるまで充電し、その後、その電圧を一定に保ちつつ電流値を1Cから0.02Cまで徐々に小さくしながら充電を行った(定電圧充電)。30秒間の休止の後、30Cの電流値で定電流放電し、放電開始後10秒目の電圧の値を測定した。この時点での電池抵抗値をオームの法則により算出した。
その後、電池1の電池抵抗値を、上述と同様にして測定した。そして、サイクル試験後における電池1の電池抵抗変化率を算出した。この電池抵抗変化率は、サイクル試験後の電池抵抗値を、サイクル試験前の、新品(初期)時の電池抵抗値で割ったものである。
このうち実施例2にかかる電池101は、正極活物質粒子36及び導電材35のほか、結着材として第2結着材32B(PEO)のみを用いた正極活物質層131を有する正電極板130を用いている(図1,5参照)。この正極活物質層131内における、これらの重量比は、正極活物質粒子36:導電材35:第2結着材32B=87:10:2とした。
また、実施例3にかかる電池201は、電池1で用いた、LiNi0.82Co0.15Al0.03O2からなる正極活物質粒子36に代えて、LiCoO2からなる正極活物質粒子236を用いた正極活物質層231を有する正電極板230を用いた(図1,6参照)。この正極活物質層内における、これらの重量比は、正極活物質粒子236:導電材35:第1結着材32A:第2結着材32B=87:10:1:1とした。
また、比較例2にかかる電池C2は、正極活物質粒子36及び導電材35のほか、結着材として第1結着材32A(CMC)のみを用いた正極活物質層を有する正電極板を用いた。この正極活物質層内における、これらの重量比は、正極活物質粒子36:導電材35:第1結着材32A=87:10:2とした。
これら電池1,101,201及び比較電池C1,C2の試験結果を表1に示す。
なお、正電極板における正極活物質層の剥離強度は、比較電池C1に用いた正電極板における正極活物質層の剥離強度を基準として、相対値(%)を示してある。
さらに、電池1,101,201にそれぞれ用いた正電極板30,130,230における正極活物質層31,131,231の剥離強度は、いずれも比較電池C1のそれよりも相対的に高い。このことから、PTFEを含むよりも、このPTFEを含まない正極活物質層の方が、その剥離強度を高くできることが判る。
さらに、電池1,101,201にそれぞれ用いた正電極板30,130,230が有する正極活物質層31,131,231の剥離強度が、いずれも比較電池C2のそれよりも相対的に高い。このことから、結着材にCMCのみを用いるより、PEOのみ、又は、PEO及びCMCのみを用いた正極活物質層の方が、その剥離強度を高くできることが判る。
なお、LiCoO2を正極活物質とした実施例3の電池201についても、実施例2の電池101における、正極活物質をLiCoO2とした電池(特性の詳細は示さない)に比して、その電池抵抗変化率を小さくできることが判っている。
従って、PEO及びCMCのみからなる結着材を用いた正極活物質層を有する正電極板30,230を用いるのがより好ましいことが判る。
また、PEO及びCMCをそれぞれ1wt%ずつ含む正極活物質層を有する正電極板30を用いた電池1は、電池抵抗の増加をより抑制できる。
まず、アルミ箔38にカーボンコート層37を形成する。この工程では、炭素粉体CPをなす30重量部のアセチレンブラックと、PVDFをn-メチルピロリドン(NMP)で混合した、固形分率13%のPVDF/NMP溶液とを用いて、アセチレンブラック及びPVDFの固形分比が30:70になるように均一に混合して、図示しないカーボンコート層用ペーストを作製した。
このカーボンコート層用ペースト(図示しない)を、厚さが15μmのアルミ箔38の両面(第1箔主面38a,第2箔主面38b)にグラビアコータで塗布し、その後に乾燥させて、カーボンコート層37を形成した。
この工程では、混合槽901と、この混合槽901内に収容した収容物を、剪断しつつ攪拌する攪拌羽根902とを備える混練機900を用いる。
このフィルタ通過工程では、混練機900でできた活物質ペースト31Pをフィルタ910に通す。これにより、活物質ペースト31P内に混在している異物を除去する。なお、フィルタ910を通過した活物質ペースト31Pは、ダイ710のペースト保持部711に収容される。
この吐出口712は、スリット状で、長手方向DAに移動するアルミ箔38の両面に形成したカーボンコート層37,37上に、帯状に活物質ペースト31Pを吐出するべく、アルミ箔38の幅方向(図7中、奥行き方向)に平行に開口している。
まず、巻出し部701に捲回した、帯状のアルミ箔38(厚さ:15μm)を長手方向DAに移動させる。なお、このアルミ箔38の両面には、カーボンコート層37,37が予め塗布されている。そのアルミ箔38上のカーボンコート層37に、ダイ710により活物質ペースト31Pを塗布する。
その後、この活物質ペースト31Pをヒータ730で乾燥させ未圧縮活物質層31Bとした。そして、この未圧縮活物質層31Bを片側のカーボンコート層37上に担持した片面担持アルミ箔38Kを、一旦巻取り部702に巻き取る。
プレス装置800は、巻出し部801、プレスローラ810、巻取り部802及び複数の補助ローラ820を備えている。このプレス装置800により、巻出し部801から上述のプレス前の活物質積層板30Bを、2つのプレスローラ810,810の間に通して、厚み方向DTに圧縮する。
かくして、アルミ箔38の両側に、圧縮済みの2つの正極活物質層31、31を積層してなる正電極板30を得る(図3,4参照)。
具体的には、上述の活物質ペースト31P、即ち、結着材として第1結着材32A(CMC)及び第2結着材32B(PEO)を含む活物質ペースト31Pについて、放置時間が0h(製作直後)、24h、48h、72h、96hの時点における各粘度を測定した。
一方、この活物質ペースト31Pの比較として、結着材として第1結着材32A(CMC)のみを含む活物質ペースト(比較ペーストEP)について、放置時間が0h(製作直後)、24h、48hの時点における各粘度についても測定した。
活物質ペースト31Pの粘度の測定では、まず、30℃の恒温槽内で、E型粘度計VMの基盤VMB上に、作製直後の活物質ペースト31Pを、ギャップが100μmとなるように配置した。そして、その活物質ペースト31Pの上方からコーンプレートVMCを、このコーンプレートVMCの先端が基盤VMBに当接するまで移動させた。その後、コーンプレートVMCを、軸芯AXを中心とした1rpmの剪断速度(回転速度)で定速回転させて、活物質ペースト31Pの粘度を測定した。さらに、放置時間が24h,48h,72h,96hの時点での粘度も測定した。
比較例の比較ペーストEPについても、活物質ペースト31Pと同様にして、放置時間が0h,24h,48hの時点での粘度を測定した。これらの結果について、図10に示す。
まず、放置時間が0h、即ち、作製直後について比較すると、活物質ペースト31Pの粘度は、比較ペーストEPの粘度よりも高い。このことから、活物質ペーストの結着材として、CMCのみならず、PEOをも用いることで、活物質ペーストの粘度を向上させうることが判る。
但し、活物質ペースト31Pにおいては、粘度の低下速度(粘度の変化量を放置時間で除したもの)が、比較ペーストEPのそれよりも小さい。即ち、活物質ペースト31Pは、粘度の経時的な低下が緩やかである。これは、活物質ペースト31P中のPEOが、CMCに比して高い耐アルカリ性を有しており、活物質ペースト31P中でPEOの粘度が維持されるためであると考えられる。
この正電極板30の製造方法では、上述のフィルタ通過工程を備えるので、フィルタ910による異物の除去が可能な上、上述の凝集体による目詰まりがなく、効率的に異物を除去できる。
電池101における正電極板130の正極活物質層形成工程のうちの塗工工程では、図11に示す塗工装置700のダイ710を用いて、アルミ箔38の両面に形成したカーボンコート層37,37のいずれかに、活物質ペースト131Pを塗布する。
電池201における正電極板230の正極活物質層形成工程のうちの塗工工程では、図12に示す塗工装置700のダイ710を用いて、アルミ箔38の両面に形成したカーボンコート層37,37のいずれかに、活物質ペースト231Pを塗布する。
本実施形態2にかかる車両400は、前述した電池1を複数搭載したものである。具体的には、図13に示すように、車両400は、エンジン440、フロントモータ420及びリアモータ430を併用して駆動するハイブリッド自動車である。この車両400は、車体490、エンジン440、これに取り付けられたフロントモータ420、リアモータ430、ケーブル450、インバータ460、及び、複数の電池1,101,201を自身の内部に有する組電池410を有している。
また、本実施形態3のハンマードリル500は、前述した電池1,101,201を含むバッテリパック510を搭載したものであり、図14に示すように、バッテリパック510、本体520を有する電池搭載機器である。なお、バッテリパック510はハンマードリル500の本体520のうちパック収容部521に脱着可能に収容されている。
例えば、実施形態1では、カーボンコート層に含む炭素粉体として、アセチレンブラックを用いたが、例えば、アセチレンブラック以外の、ファーネスブラック、ケッチェンブラック等のカーボンブラックや、グラファイト粉末等を用いても良い。また、正電極板にアセチレンブラックからなる導電材を用いたが、例えば、上述した炭素粉体のうち、アセチレンブラック以外のものや、ニッケル粉末等の金属粉末などを用いても良い。
また、正極活物質粒子にニッケルコバルト酸リチウムを用いたが、例えば、このほかの、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム等のリチウム遷移金属複合酸化物や、鉄オリビン化合物を用いても良い。
Claims (10)
- 導電性を有する基体と、
上記基体に形成してなり、正極活物質粒子、導電材及び結着材を含む正極活物質層と、を備える
正電極板であって、
上記結着材は、ポリエチレンオキサイドのみ、又は、ポリエチレンオキサイド及びカルボキシメチルセルロースのみからなる
正電極板。 - 請求項1に記載の正電極板であって、
前記基体と前記正極活物質層との間に、炭素粉体を含むカーボンコート層を介在させてなる
正電極板。 - 請求項1又は請求項2に記載の正電極板であって、
前記結着材は、ポリエチレンオキサイド及びカルボキシメチルセルロースのみからなる
正電極板。 - 請求項3に記載の正電極板であって、
前記正極活物質層は、前記ポリエチレンオキサイド及び前記カルボキシメチルセルロースをそれぞれ1wt%ずつ含む
正電極板。 - 請求項1~請求項4のいずれか一項に記載の正電極板を用いた電池。
- 請求項5に記載の電池を搭載し、この電池による電気エネルギを動力源の全部又は一部に使用する車両。
- 請求項5に記載の電池を搭載し、この電池による電気エネルギをエネルギ源の全部又は一部として使用する電池搭載機器。
- 導電性を有する基体と、
上記基体に形成してなり、正極活物質粒子、導電材及び結着材を含む正極活物質層と、を備える
正電極板の製造方法であって、
上記結着材は、ポリエチレンオキサイドのみ、又は、ポリエチレンオキサイド及びカルボキシメチルセルロースのみからなり、
上記正極活物質粒子、上記導電材及び上記結着材を混練した活物質ペーストを上記基体に塗布し乾燥させて、上記正極活物質層を形成する正極活物質層形成工程、を備える
正電極板の製造方法。 - 請求項8に記載の正電極板の製造方法であって、
上記正電極板は、
前記基体と前記正極活物質層との間に、炭素粉体を含むカーボンコート層を介在させてなり、
前記正極活物質層形成工程は、
前記活物質ペーストを、予め上記基体に形成した上記カーボンコート層上に塗布する
正電極板の製造方法。 - 請求項8又は請求項9に記載の正電極板の製造方法であって、
前記正極活物質層形成工程に先立ち、
混練後の活物質ペーストを、捕集効率90%が50μm以下のフィルタに通すフィルタ通過工程を備える
正電極板の製造方法。
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- 2009-06-26 US US13/379,108 patent/US20120107685A1/en not_active Abandoned
- 2009-06-26 KR KR1020117030667A patent/KR101390548B1/ko active IP Right Grant
Patent Citations (4)
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JPH1055798A (ja) * | 1996-08-08 | 1998-02-24 | Fuji Elelctrochem Co Ltd | シート状電極 |
JPH10340740A (ja) * | 1997-06-09 | 1998-12-22 | Yuasa Corp | リチウム電池 |
JPH11162446A (ja) * | 1997-11-26 | 1999-06-18 | Yuasa Corp | 単位電池とこれを用いた蓄電池装置 |
JP2001266890A (ja) * | 2000-03-16 | 2001-09-28 | Matsushita Electric Ind Co Ltd | 非水電解液二次電池及びその製造法 |
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JP2012009423A (ja) * | 2010-05-28 | 2012-01-12 | Semiconductor Energy Lab Co Ltd | 蓄電装置及びその作製方法 |
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Publication number | Publication date |
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KR101390548B1 (ko) | 2014-04-30 |
KR20120020184A (ko) | 2012-03-07 |
JPWO2010150397A1 (ja) | 2012-12-06 |
JP5375959B2 (ja) | 2013-12-25 |
US20120107685A1 (en) | 2012-05-03 |
CN102460779A (zh) | 2012-05-16 |
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