WO2013140942A1 - 全固体リチウム二次電池 - Google Patents
全固体リチウム二次電池 Download PDFInfo
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- WO2013140942A1 WO2013140942A1 PCT/JP2013/054537 JP2013054537W WO2013140942A1 WO 2013140942 A1 WO2013140942 A1 WO 2013140942A1 JP 2013054537 W JP2013054537 W JP 2013054537W WO 2013140942 A1 WO2013140942 A1 WO 2013140942A1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/74—Meshes or woven material; Expanded metal
- H01M4/745—Expanded metal
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- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to an all-solid-state lithium secondary battery using a three-dimensional network metal porous body.
- lithium secondary batteries are actively studied in various fields as batteries capable of obtaining a high energy density because lithium has a small atomic weight and a large ionization energy.
- an electrode using a compound such as lithium metal oxide such as lithium cobaltate, lithium manganate, lithium nickelate, or lithium metal phosphate such as lithium iron phosphate is practical. Have been commercialized or commercialized.
- an electrode or alloy electrode mainly composed of carbon, particularly graphite is used as the negative electrode.
- the electrolyte is generally a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent, but a gel electrolyte or a solid electrolyte is also attracting attention.
- a current collector having a three-dimensional network structure As a current collector of a lithium secondary battery. Since the current collector has a three-dimensional network structure, the contact area with the active material increases. Therefore, according to the said collector, the internal resistance of a lithium secondary battery can be reduced and battery efficiency can be improved. Furthermore, according to the current collector, it is possible to improve the flowability of the electrolytic solution, and it is possible to improve the battery reliability because it is possible to prevent current concentration and Li dendrite formation, which is a conventional problem. Moreover, according to the said collector, heat_generation
- Patent Document 1 discloses a valve metal having an oxide film formed on the surface of any one of aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, an alloy thereof, a stainless alloy, and the like. It is described that it is used as a porous current collector.
- Patent Document 2 primary conductive treatment is performed on a skeleton surface of a synthetic resin having a three-dimensional network structure by electroless plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), metal coating, graphite coating, or the like. It describes that the metal porous body obtained by further performing the metallization process by electroplating after using as a collector.
- CVD chemical vapor deposition
- PVD physical vapor deposition
- metal coating graphite coating, or the like.
- Aluminum is preferred as the material for the current collector of the positive electrode for lithium secondary batteries.
- aluminum has a lower standard electrode potential than hydrogen, water is electrolyzed before being plated in an aqueous solution, so that aluminum plating in an aqueous solution is difficult.
- Patent Document 3 an aluminum porous body obtained by forming an aluminum film on the surface of a polyurethane foam by molten salt plating and then removing the polyurethane foam is used as a current collector for a battery. Is described.
- an organic electrolytic solution is used as an electrolytic solution.
- this organic electrolyte shows a high ionic conductivity, it is a flammable liquid. Therefore, when the organic electrolyte is used as a battery electrolyte, a protection circuit for a lithium ion secondary battery, etc. May need to be installed.
- a metal negative electrode may passivate by reaction with the said organic electrolyte solution, and impedance may increase. As a result, current concentration occurs in a portion with low impedance, dendrite is generated, and this dendrite penetrates the separator existing between the positive and negative electrodes, so that the battery is likely to be short-circuited internally.
- lithium in which a safer inorganic solid electrolyte is used instead of the organic electrolyte.
- Ion secondary batteries have been studied. Further, since inorganic solid electrolytes are generally nonflammable and have high heat resistance, development of an all-solid lithium secondary battery using the inorganic solid electrolyte is desired.
- Patent Document 4 a main component and Li 2 S and P 2 S 5, Li 2 S82.5 ⁇ 92.5 by mol%, the composition of P 2 S 5 7.5 ⁇ 17.5
- Patent Document 4 a main component and Li 2 S and P 2 S 5, Li 2 S82.5 ⁇ 92.5 by mol%, the composition of P 2 S 5 7.5 ⁇ 17.5
- the use of lithium ion conductive sulfide ceramics as an electrolyte for all solid state batteries is described.
- Patent Document 5 discloses the formula M a X-M b Y (wherein M is an alkali metal atom, and X and Y are SO 4 , BO 3 , PO 4 , GeO 4 , WO 4 , MoO 4, respectively). , SiO 4 , NO 3 , BS 3 , PS 4 , SiS 4 and GeS 4 , a is the valence of the X anion, and b is the valence of the Y anion). It is described that a high ion conductive ion glass into which a liquid is introduced is used as a solid electrolyte.
- Patent Document 6 discloses a positive electrode containing a compound selected from the group consisting of transition metal oxides and transition metal sulfides as a positive electrode active material, a lithium ion conductive glass solid electrolyte containing Li 2 S, lithium And a negative electrode containing a metal to be alloyed as an active material, and an all solid lithium secondary battery in which at least one of a positive electrode active material and a negative electrode metal active material contains lithium is described.
- Patent Document 7 the flexibility and mechanical strength of the electrode material layer in the all-solid-state battery are improved, and the loss and cracking of the electrode material and the peeling from the current collector are suppressed.
- an inorganic solid is present in the pores of the porous metal sheet having a three-dimensional network structure as an electrode material used in an all-solid lithium ion secondary battery. It is described that an electrode material sheet formed by inserting an electrolyte is used.
- a three-dimensional network aluminum porous body is used as a positive electrode current collector, and a secondary battery in which a three-dimensional network copper porous body is used as a negative electrode current collector, is repeatedly charged and discharged.
- JP 2005-78991 A Japanese Patent Laid-Open No. 7-22021 International Publication No. 2011/118460 JP 2001-250580 A JP 2006-156083 A JP-A-8-148180 JP 2010-40218 A
- An object of the present invention is to provide an all-solid-state lithium secondary battery that does not increase in internal resistance even after repeated charge and discharge in an all-solid-state lithium secondary battery using a three-dimensional network porous body as a current collector. To do.
- an aluminum alloy is used as a positive electrode current collector.
- the present invention was completed by obtaining the knowledge that the above-mentioned problems can be solved by using a three-dimensional network metal porous body and using a three-dimensional network metal porous body made of a copper alloy as a negative electrode current collector. That is, the present invention relates to an all solid lithium secondary battery as described below.
- An all-solid lithium secondary battery in which the positive electrode and the negative electrode are electrodes in which a three-dimensional network porous body is used as a current collector, and at least an active material is filled in pores of the three-dimensional network porous body,
- the three-dimensional network porous body of the positive electrode is an aluminum alloy having a Young's modulus of 70 GPa or more
- the three-dimensional network porous body of the negative electrode is a copper alloy having a Young's modulus of 120 GPa or more. battery.
- a solid electrolyte filled in pores of the three-dimensional network porous body, and the solid electrolyte forming the solid electrolyte layer is a sulfide solid electrolyte containing lithium, phosphorus and sulfur as constituent elements.
- the all-solid-state lithium secondary battery of the present invention has an excellent effect that it has a high output and the internal resistance is not increased by repeated charge and discharge. Therefore, the all-solid lithium secondary battery of the present invention exhibits high cycle characteristics and can be manufactured at low cost.
- FIG. 1 is a schematic diagram showing the basic configuration of an all-solid secondary battery.
- an all-solid lithium secondary battery will be described as an example of the secondary battery 10.
- a secondary battery 10 shown in FIG. 1 includes a positive electrode 1, a negative electrode 2, and an ion conductive layer 3 sandwiched between both electrodes 1 and 2.
- the positive electrode 1 is mixed with a conductive powder 6 and a binder resin and loaded on the positive electrode current collector 7 to form a plate shape.
- An electrode is used.
- the negative electrode 2 is a plate-like electrode in which a carbon compound negative electrode active material powder 8 is mixed with a binder resin and supported on a negative electrode current collector 9.
- a solid electrolyte is used as the ion conductive layer 3.
- the positive electrode current collector and the negative electrode current collector are connected to the positive electrode terminal and the negative electrode terminal by lead wires, respectively.
- the positive electrode 1 is a three-dimensional network metal porous body that is a positive electrode current collector 7, a positive electrode active material powder 5 filled in pores of the three-dimensional network metal porous body, and a conductive powder 6. It consists of a conductive aid.
- the negative electrode 2 includes a three-dimensional network metal porous body that is a negative electrode current collector 9 and a negative electrode active material powder 8 filled in pores of the three-dimensional network metal porous body. In some cases, the pores of the three-dimensional network metal porous body can be further filled with a conductive additive.
- FIG. 2 is a schematic diagram illustrating the basic configuration of the all solid state secondary battery.
- an all-solid lithium ion secondary battery will be described as an example of the all-solid secondary battery.
- the all-solid secondary battery 60 shown in FIG. 2 includes a positive electrode 61, a negative electrode 62, and a solid electrolyte layer (SE layer) 63 disposed between the electrodes 61 and 62.
- the positive electrode 61 includes a positive electrode layer (positive electrode body) 64 and a positive electrode current collector 65.
- the negative electrode 62 includes a negative electrode layer 66 and a negative electrode current collector 67.
- the positive electrode 61 includes a three-dimensional network metal porous body that is a positive electrode current collector 65, a positive electrode active material filled in pores of the three-dimensional network metal porous body, and a lithium ion conductive solid electrolyte.
- the negative electrode 62 includes a three-dimensional network metal porous body that is a negative electrode current collector 67, a negative electrode active material filled in pores of the three-dimensional network metal porous body, and a lithium ion conductive solid electrolyte.
- the pores of the three-dimensional network metal porous body can be further filled with a conductive additive.
- a three-dimensional network aluminum alloy porous body made of an aluminum alloy having a Young's modulus of 70 GPa or more is used as a positive electrode current collector, and a three-dimensional network made of a copper alloy having a Young's modulus of 120 GPa or more is used as a negative electrode current collector.
- a copper alloy porous body By using a copper alloy porous body, an increase in internal resistance can be prevented. The details of why the increase in internal resistance can be prevented are unknown, but the following reasons are conceivable.
- the conventional all-solid lithium secondary battery has a gap between the skeleton of the three-dimensional network metal porous body and the active material, and the contact between the three-dimensional network metal porous body and the active material becomes poor. Resistance is thought to increase.
- the all solid lithium secondary battery of the present invention maintains good contact between the skeleton forming the pores of the three-dimensional network metal porous body and the active material filled in the pores. It is thought that the rise of can be prevented. Further, as in the present invention, when a three-dimensional network aluminum alloy porous body and a three-dimensional network copper alloy porous body are used as a current collector of an all-solid lithium secondary battery, the all-solid lithium secondary battery includes a current collector. It is considered that there is an advantage that the contact state between the electric body and the solid electrolyte layer can be maintained well.
- the three-dimensional reticulated aluminum alloy porous body can be produced, for example, by performing the following operation.
- a polyurethane foam having a conductive layer formed on the surface is used as a workpiece.
- the jig is placed in a glove box maintained in an argon atmosphere and a low moisture condition (dew point -30 ° C. or lower), and a molten salt aluminum having a temperature of 40 ° C.
- Immerse in the plating bath connect the jig with the work set to the cathode side of the rectifier, and connect the pure aluminum plate to the anode side.
- molten salt aluminum plating bath for example, a plating bath obtained by adding 1,10-phenanthroline to 33 mol% 1-ethyl-3-methylimidazolium chloride (EMIC) -67 mol% AlCl 3 is used.
- EMIC 1-ethyl-3-methylimidazolium chloride
- an aluminum plating layer is formed on the surface of the polyurethane foam by plating with a direct current having a current density of 3.6 A / dm 2 between the work and the pure aluminum plate to obtain an aluminum-resin composite porous body.
- This plating layer incorporates phenanthroline, which is an organic substance containing carbon.
- heat treatment is performed by heating the aluminum-resin composite porous body to 450 to 630 ° C.
- a copper alloy for example, a copper-nickel alloy
- a copper-nickel alloy can be produced by performing the following operation.
- Polyurethane foam is used as a workpiece.
- the workpiece is immersed in a copper plating bath and plated to form a copper plating layer on the surface of the polyurethane foam.
- the polyurethane foam having a copper plating layer formed on the surface is immersed in a nickel plating bath and plated to form a nickel plating layer on the surface of the copper plating layer.
- the obtained product is heat-treated by heating to about 600 ° C. in an air atmosphere, and after removing the resin, the obtained product is heat-treated by heating to about 1000 ° C. in a hydrogen atmosphere. Thermal diffusion of nickel.
- a copper-nickel alloy can be obtained.
- a nickel plating layer may be formed first, and then a copper plating layer may be formed.
- the Young's modulus of a three-dimensional network metal porous body is measured by embedding the three-dimensional network metal porous body in a resin, cutting it, polishing the cut surface, and pressing a nanoindenter indenter on the skeleton (plating) section. Can do.
- the nanoindenter is a measuring means used for measuring the hardness and Young's modulus of a minute region.
- the three-dimensional network metal porous body is formed on the surface of a porous resin body (porous resin molded body) having continuous pores such as polyurethane foam by using a method such as plating, vapor deposition, sputtering, or thermal spraying. It can be obtained by forming a metal film having a desired thickness and then removing the porous resin body.
- conductive layer is formed on the surface of the resin porous body. Since the conductive layer serves to enable the formation of a metal film (aluminum plating layer, copper plating layer, nickel plating layer, etc.) on the surface of the porous resin body by plating or the like, it has conductivity. If it does, the material and thickness will not be specifically limited.
- the conductive layer is formed on the surface of the resin porous body by various methods that can impart conductivity to the resin porous body.
- an arbitrary method such as an electroless plating method, a vapor deposition method, a sputtering method, or a method of applying a conductive paint containing conductive particles such as carbon particles can be used.
- the material of the conductive layer is preferably the same material as the metal coating.
- Examples of the electroless plating method include known methods such as a method including cleaning, activation, and plating steps.
- the sputtering method various known sputtering methods such as a magnetron sputtering method can be used.
- aluminum, nickel, chromium, copper, molybdenum, tantalum, gold, aluminum / titanium alloy, nickel / iron alloy, or the like can be used as a material used for forming the conductive layer.
- aluminum, nickel, chromium, copper, and alloys mainly composed of these are suitable in terms of cost and the like.
- the conductive layer may be a layer containing at least one powder selected from the group consisting of graphite, titanium, and stainless steel.
- a conductive layer can be formed by, for example, applying a slurry obtained by mixing a powder of graphite, titanium, stainless steel or the like and a binder to the surface of the resin porous body.
- the said powder may be used independently and may be used in mixture of 2 or more types. Of these powders, graphite powder is preferred.
- the binder for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or the like, which is a fluororesin excellent in electrolytic solution resistance and oxidation resistance, is optimal.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the binder content in the slurry is generally used as a current collector. It may be about 1 ⁇ 2 of the case of using a metal foil, for example, about 0.5% by weight.
- a metal film having a desired thickness is formed by performing plating or the like on the surface of the porous resin body on which the conductive layer is formed. . Thereby, a metal-resin composite porous body is obtained.
- the aluminum alloy film is plated in a molten salt bath containing a component of an aluminum alloy on the surface of a resin porous body whose surface is made conductive according to a method described in International Publication No. 2011/118460. Can be formed. Thereafter, the resin porous body is removed from the metal-resin composite porous body to obtain a three-dimensional network aluminum alloy porous body.
- the copper alloy film can be formed by using a method in which the surface of the resin porous body having a conductive surface is plated in an aqueous plating bath in which a component of the copper alloy is mixed. Thereafter, the resin porous body is removed from the metal-resin composite porous body to obtain a three-dimensional network copper alloy porous body.
- a porous body made of any synthetic resin can be selected.
- the resin porous body include foams of synthetic resins such as polyurethane, melamine resin, polypropylene, and polyethylene.
- the resin porous body only needs to have not only a synthetic resin foam but also continuous pores (continuous ventilation holes), and a resin molded body having any shape (resin porous body) can be used. .
- what has a shape like a nonwoven fabric, for example, entangled with a fibrous synthetic resin can be used instead of the synthetic resin foam.
- the porosity of the resin porous body is preferably 80% to 98%.
- the pore diameter of the porous resin body is preferably 50 ⁇ m to 500 ⁇ m.
- resin porous bodies polyurethane foam and melamine resin foam have high porosity, have pore connectivity and are excellent in thermal decomposability, and can be preferably used as resin porous bodies.
- polyurethane foam is preferable in terms of pore uniformity and availability, and a nonwoven fabric is preferable in that a three-dimensional network metal porous body having a small pore diameter can be obtained.
- the synthetic resin foams often contain residues such as foaming agents and unreacted monomers used in the production process. From the viewpoint of smoothly performing the above step, it is preferable to perform a washing treatment on the synthetic resin foam used in advance.
- the skeleton forms a three-dimensional network to form continuous pores as a whole.
- the skeleton of the polyurethane foam has a substantially triangular shape in a cross section perpendicular to the extending direction.
- the porosity is defined by the following equation.
- Porosity (1 ⁇ (mass of resin porous body [g] / (volume of resin porous body [cm 3 ] ⁇ material density))) ⁇ 100 [%]
- the combination of the metal constituting the positive electrode current collector and the metal constituting the negative electrode current collector and the active material can be variously selected.
- lithium cobalt oxide is used as the positive electrode active material
- examples include a positive electrode using an aluminum alloy porous body as a positive electrode current collector, lithium titanate as a negative electrode active material, and a copper alloy porous body as a negative electrode current collector.
- the active material and the material of the solid electrolyte will be described, and the method of filling the active material into the three-dimensional network metal porous body will be described.
- the positive electrode active material a material capable of inserting or removing lithium ions can be used.
- Examples of other positive electrode active materials include lithium transition metal oxides such as olivine compounds such as lithium iron phosphate (LiFePO 4 ) and LiFe 0.5 Mn 0.5 PO 4 .
- Examples of other materials for the positive electrode active material include lithium metal having a chalcogenide or metal oxide skeleton (that is, a coordination compound containing a lithium atom in the crystal of the chalcogenide or metal oxide).
- Examples of the chalcogenide include TiS 2 , V 2 S 3 , FeS, FeS 2 , LiMS z [M is a transition metal element (eg, Mo, Ti, Cu, Ni, Fe, etc.), Sb, Sn, or Pb. And z represents a number satisfying 1.0 or more and 2.5 or less].
- Examples of the metal oxide include TiO 2 , Cr 3 O 8 , V 2 O 5 , MnO 2 and the like.
- the positive electrode active material can be used in combination with a conductive additive and a binder.
- the material of the positive electrode active material is a compound containing a transition metal atom
- the transition metal atom contained in the material may be partially substituted with another transition metal atom.
- the positive electrode active material may be used alone or in combination of two or more.
- the positive electrode active materials lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), and lithium nickel cobaltate (LiCo x Ni 1-x ) are used from the viewpoint of efficient lithium ion insertion and desorption.
- lithium manganate LiMn 2 O 4
- lithium manganate compound LiM y Mn 2 ⁇ y O 4
- M Cr, Co or Ni, 0 ⁇ y ⁇ 1
- At least one selected from the group is preferred.
- lithium titanate Li 4 Ti 5 O 12
- the negative electrode active material Li 4 Ti 5 O 12
- the negative electrode active material a material capable of inserting or removing lithium ions can be used.
- examples of such a negative electrode active material include graphite and lithium titanate (Li 4 Ti 5 O 12 ).
- An alloy in which at least one kind of the metal is combined with another element and / or compound (that is, an alloy containing at least one kind of the metal) or the like can be used.
- the negative electrode active material may be used alone or in combination of two or more.
- lithium titanate Li 4 Ti 5 O 12
- Li Li, In
- a metal selected from the group consisting of Al, Si, Sn, Mg and Ca, or an alloy containing at least one of the above metals is preferable.
- Solid electrolyte for filling three-dimensional mesh metal porous body It is preferable to use a sulfide solid electrolyte having high lithium ion conductivity as the solid electrolyte for filling the pores of the three-dimensional network metal porous body.
- the sulfide solid electrolyte include a sulfide solid electrolyte containing lithium, phosphorus, and sulfur as constituent elements.
- the sulfide solid electrolyte may further contain elements such as O, Al, B, Si, and Ge as constituent elements.
- Such a sulfide solid electrolyte can be obtained by a known method.
- a sulfide solid electrolyte for example, lithium sulfide (Li 2 S) and diphosphorus pentasulfide (P 2 S 5 ) are used as starting materials, and a molar ratio of Li 2 S and P 2 S 5 (Li 2 S / P 2).
- S 5 ) is mixed so that it becomes 80/20 to 50/50, and the obtained mixture is melted and quenched (melting quenching method), and the mixture is mechanically milled (mechanical milling method). It is done.
- the sulfide solid electrolyte obtained by the above method is amorphous.
- an amorphous sulfide solid electrolyte may be used as the sulfide solid electrolyte, and a crystalline sulfide solid electrolyte obtained by heating an amorphous sulfide solid electrolyte is used. Also good. Crystallization can be expected to improve lithium ion conductivity.
- Solid electrolyte layer (SE layer)
- the solid electrolyte layer can be obtained by forming the solid electrolyte material into a film shape.
- the thickness of the solid electrolyte layer is preferably 1 ⁇ m to 500 ⁇ m.
- conductive aid in the present invention, known or commercially available conductive assistants can be used.
- the conductive aid is not particularly limited, and examples thereof include carbon black such as acetylene black and ketjen black; activated carbon; graphite and the like.
- graphite when graphite is used as the conductive additive, the shape thereof may be any shape such as a spherical shape, a flake shape, a filament shape, and a fibrous shape such as carbon nanotube (CNT).
- the binder may be any material that is generally used for a positive electrode for a lithium secondary battery.
- the binder material include fluorine resins such as PVDF and PTFE; polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer; thickeners (for example, water-soluble thickener such as carboxymethylcellulose, xanthan gum, and pectin agarose). Agent) and the like.
- the organic solvent used when preparing the slurry is an organic solvent that does not adversely affect the material (that is, the active material, the conductive additive, the binder, and, if necessary, the solid electrolyte) filled in the metal porous body.
- the organic solvent can be appropriately selected.
- examples of such organic solvents include n-hexane, cyclohexane, heptane, toluene, xylene, trimethylbenzene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, vinyl ethylene carbonate.
- the binder may be mixed with a solvent when forming the slurry, but may be dispersed or dissolved in the solvent in advance.
- a solvent when forming the slurry, but may be dispersed or dissolved in the solvent in advance.
- an aqueous dispersion of a fluororesin in which a fluororesin is dispersed in water, an aqueous binder such as an aqueous solution of carboxymethylcellulose; an NMP solution of PVDF ordinarily used when a metal foil is used as a current collector can be used.
- an aqueous solvent can be used, and an expensive organic solvent is used.
- an aqueous binder containing at least one binder selected from the group consisting of a fluororesin, a synthetic rubber, and a thickener, and an aqueous solvent because reuse, consideration for the environment, and the like are not necessary. preferable.
- Content of each component in a slurry is not specifically limited, What is necessary is just to determine suitably according to the binder, solvent, etc. which are used.
- Filling the pores of the three-dimensional network metal porous body with the active material or the like for example, using a known method such as an immersion filling method or a coating method, slurry of the active material or the like in the voids inside the three-dimensional network metal porous body. It can be performed by introducing a slurry of the active material or the like.
- Examples of the coating method include roll coating method, applicator coating method, electrostatic coating method, powder coating method, spray coating method, spray coater coating method, bar coater coating method, roll coater coating method, dip coater coating method, doctor Examples thereof include a blade coating method, a wire bar coating method, a knife coater coating method, a blade coating method, and a screen printing method.
- the amount of the active material to be filled is not particularly limited, but may be, for example, about 20 to 100 mg / cm 2 , preferably about 30 to 60 mg / cm 2 .
- the electrode is preferably pressurized in a state where the current collector is filled with slurry.
- the thickness of the electrode is usually about 100 to 450 ⁇ m.
- the thickness of the electrode is preferably 100 to 250 ⁇ m in the case of an electrode of a high output secondary battery, and preferably 250 to 450 ⁇ m in the case of an electrode of a high capacity secondary battery.
- the pressing step is preferably performed with a roller press. Since the roller press machine is most effective in smoothing the electrode surface, the risk of short-circuiting can be reduced by applying pressure with the roller press machine.
- heat treatment may be performed after the pressurizing step.
- the binder By performing the heat treatment, the binder can be melted to bind the active material and the three-dimensional porous metal porous body more firmly, and the strength of the active material is improved by firing the active material.
- the temperature of the heat treatment is 100 ° C. or higher, preferably 150 to 200 ° C.
- the heat treatment may be performed under normal pressure or under reduced pressure, but is preferably performed under reduced pressure.
- the pressure is, for example, 1000 Pa or less, preferably 1 to 500 Pa.
- the heating time is appropriately determined according to the heating atmosphere, pressure, etc., but is usually 1 to 20 hours, preferably 5 to 15 hours.
- a drying step may be performed according to a conventional method between the filling step and the pressurizing step.
- the electrode material in the conventional lithium ion secondary battery has applied the active material to the surface of metal foil, and in order to improve the battery capacity per unit area, the application
- the three-dimensional network metal porous body in the present embodiment has a high porosity and a large surface area per unit area, so that the active material can be effectively used because the contact area between the current collector and the active material is large. The capacity of the battery can be improved and the mixing amount of the conductive assistant can be reduced.
- the polyurethane foam having a conductive layer formed on the surface was used as a workpiece. After the workpiece is set in a jig having a power feeding function, the jig is put in a glove box maintained in an argon atmosphere and a low moisture condition (dew point -30 ° C. or lower), and a molten salt aluminum having a temperature of 40 ° C. It was immersed in a plating bath.
- the molten salt aluminum plating bath is a plating bath obtained by adding 1,10-phenanthroline to 33 mol% EMIC-67 mol% AlCl 3 at 5 g / L.
- the jig on which the workpiece was set was connected to the cathode side of the rectifier, and a pure aluminum plate was connected to the anode side.
- the surface of the polyurethane foam is plated by applying a direct current of current of 3.6 A / dm 2 for 90 minutes between the work and the pure aluminum plate, thereby plating the surface of the work.
- [Aluminum-resin composite porous body 1] having an aluminum plating layer (aluminum areal weight: 150 g / m 2 ) formed thereon was obtained.
- the aluminum plating layer incorporates phenanthroline, which is an organic substance containing carbon atoms.
- the molten salt aluminum plating bath was stirred using a Teflon (registered trademark) rotor and a stirrer.
- the current density is a value calculated by the apparent area of the polyurethane foam.
- the [aluminum-resin composite porous body 1] is heated in the atmosphere at 450 to 630 ° C. to remove the polyurethane foam, and fine (nanometer order) Al in the crystal grains of the aluminum porous body. 4 C 3 was finely dispersed to obtain [aluminum alloy porous body].
- the Young's modulus of the [aluminum alloy porous body] was 81 GPa.
- Production Example 2 Manufacture of porous aluminum>
- a plating bath composition: 33 mol% EMIC-67 mol% AlCl 3
- the Young's modulus of the [aluminum porous body] was 65 GPa.
- the polyurethane foam having a conductive layer formed on the surface was immersed in a copper plating bath, and a pure copper plate was used as a counter electrode, and copper plating was performed so that the basis weight of copper was 280 g / m 2 .
- the obtained product was immersed in a nickel plating bath, and a pure nickel plate was used as a counter electrode, and nickel plating was performed so that the basis weight of nickel was 120 g / m 2 .
- the obtained product was heat-treated by heating to 600 ° C. in an air atmosphere to remove the resin from the product.
- the obtained product was heat-treated by heating to 1000 ° C. in a hydrogen atmosphere, and nickel was thermally diffused to obtain a [copper alloy porous body].
- the Young's modulus of the [copper alloy porous body] was 160 GPa.
- Production Example 4 In Production Example 3, the same operation as in Production Example 3 was performed, except that copper plating was performed using a copper plating bath so that the weight of copper was 400 g / m 2 and nickel plating was not performed. A [copper porous body] made of pure copper was obtained. The Young's modulus of the [copper porous body] was 115 GPa.
- Table 1 shows the composition of the porous bodies obtained in Production Examples 1 to 4.
- Lithium cobaltate powder positive electrode binder
- Li 2 S—P2S 2 solid electrolyte
- acetylene black conductive aid
- PVDF binder
- the obtained positive electrode mixture slurry is supplied to the surface of the [aluminum alloy porous body] and pressed with a roller under a load of 5 kg / cm ⁇ 2 >, so that the positive electrode is placed in the pores of the [aluminum alloy porous body].
- the [aluminum alloy porous body] filled with the positive electrode mixture was dried at 100 ° C. for 40 minutes to remove the organic solvent, whereby [Positive electrode 1] was obtained.
- the obtained negative electrode mixture slurry is supplied to the surface of the [copper alloy porous body] and pressed with a roller under a load of 5 kg / cm ⁇ 2 >, so that the negative electrode mixture is placed in the pores of the [copper alloy porous body].
- the agent was filled.
- it was made to dry at 100 degreeC for 40 minute (s), and the [negative electrode 1] was obtained by removing an organic solvent.
- Solid electrolyte membrane 1 Li 2 S—P 2 S 2 (solid electrolyte), which is a lithium ion conductive glassy solid electrolyte, is pulverized to 100 mesh or less in a mortar and pressed into a disk shape having a diameter of 10 mm and a thickness of 1.0 mm. [Solid electrolyte membrane 1] was obtained.
- Example 1 [Positive electrode 1] and [Negative electrode 1] were pressed by sandwiching [Solid electrolyte membrane 1] to produce [All solid lithium secondary battery 1].
- Example 1 In Example 1, the same operation as in Example 1 was performed except that [Positive electrode 2] was used instead of [Positive electrode 1] and [Negative electrode 2] was used instead of [Negative electrode 1]. All-solid lithium secondary battery 2] was obtained.
- Example 1 For all the solid lithium secondary batteries obtained in Example 1 and Comparative Example 1, a charge / discharge cycle test was conducted at a current density of 100 ⁇ A / cm 2 to evaluate the 100th discharge capacity retention rate. The results are shown in Table 2.
- the all-solid-state lithium secondary battery of the present invention can be suitably used as a power source for portable electric devices such as mobile phones and smartphones, electric vehicles using a motor as a power source, and hybrid electric vehicles.
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Abstract
Description
前記集電体は、三次元網目構造を有するため、活物質との接触面積が増大する。したがって、前記集電体によれば、リチウム二次電池の内部抵抗を低下させることができ、電池効率を向上させることができる。更に、前記集電体によれば、電解液の流通性を向上させることができ、電流の集中及び従来の問題点であるLiデンドライト形成を防止できることから、電池信頼性を向上させることができる。また、前記集電体によれば、発熱を抑制することができ、電池出力を増大させることができる。更に、前記集電体は、当該集電体の骨格表面に凹凸を有する。したがって、前記集電体によれば、活物質の保持力の向上、活物質の脱落の抑制、大きい比表面積の確保、活物質の利用効率の向上及び電池のさらなる高容量化が可能となる。
すなわち、本発明は、以下に記載する通りの全固体リチウム二次電池に係るものである。
(2)前記正極の活物質が、コバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、ニッケルコバルト酸リチウム(LiCoxNi1-xO2;0<x<1)、マンガン酸リチウム(LiMn2O4)及びリチウムマンガン酸化合物(LiMyMn2-yO4;M=Cr、Co又はNi、0<y<1)からなる群より選択された少なくとも一種であり、前記負極の活物質が黒鉛、チタン酸リチウム(Li4Ti5O12)、又はLi、In、Al、Si、Sn、Mg及びCaからなる群から選ばれる金属、或いは前記金属の少なくとも一種を含む合金であることを特徴とする前記(1)に記載の全固体リチウム二次電池。
(3)前記正極と、前記負極と、前記正極と前記負極とに挟まれた固体電解質層とを備えることを特徴とする前記(1)又は(2)に記載の全固体リチウム二次電池。
(4)前記三次元網状多孔体の気孔中に固体電解質が充填され、該固体電解質及び前記固体電解質層を形成する固体電解質が、リチウムとリンと硫黄とを構成元素として含む硫化物固体電解質であることを特徴とする前記(3)に記載の全固体リチウム二次電池。
また、負極2は、負極集電体9である三次元網状金属多孔体と、この三次元網状金属多孔体の気孔に充填された負極活物質粉末8からなる。
場合によっては、前記三次元網状金属多孔体の気孔には、更に導電助剤を充填することができる。
図2に示される全固体二次電池60は、正極61と、負極62と、両電極61,62間に配置される固体電解質層(SE層)63とを備えている。正極61は、正極層(正極体)64と正極集電体65とからなる。また、負極62は、負極層66と負極集電体67とからなる。
また、負極62は、負極集電体67である三次元網状金属多孔体と、この三次元網状金属多孔体の気孔に充填された負極活物質及びリチウムイオン伝導性の固体電解質とからなる。場合によっては、前記三次元網状金属多孔体の気孔には、更に導電助剤を充填することができる。
正極用集電体としてアルミニウム多孔体及び負極用集電体として三次元網状銅多孔体が用いられた従来の二次電池は、充電-放電を繰り返すと内部抵抗が高まることが分かった。
本発明者らは、正極用集電体として三次元網状アルミニウム合金多孔体を用い、負極用集電体として三次元網状銅合金多孔体を用いることにより上記の問題を解決した。
内部抵抗の上昇を防ぐことができる理由の詳細は不明であるが、次の理由が考えられる。
すなわち、従来の全固体リチウム二次電池のように、集電体として純アルミニウムからなる三次元網状金属多孔体及び純銅からなる三次元網状金属多孔体を用いた場合には、電池の使用初期においては、活物質が膨張した時には活物質を収容する三次元網状金属多孔体の気孔も膨張し、活物質が収縮した時には三次元網状金属多孔体の気孔も収縮することから、三次元網状金属多孔体の骨格と活物質との間の接触は、良好に保たれる。しかしながら、充放電回数が多くなるにつれて、三次元網状金属多孔体の気孔が膨張したまま収縮しにくくなる。したがって、前記従来の全固体リチウム二次電池は、三次元網状金属多孔体の骨格と活物質との間に隙間ができて三次元網状金属多孔体と活物質との接触が悪くなるため、内部抵抗が上昇すると考えられる。
また、本発明のように、三次元網状アルミニウム合金多孔体及び三次元網状銅合金多孔体を全固体リチウム二次電池の集電体として用いた場合、当該全固体リチウム二次電池には、集電体と固体電解質層との接触状態も良好に維持することができるという利点があると考えられる。
表面に導電層が形成されたポリウレタンフォームをワークとして用いる。前記ワークを、給電機能を有する治具にセットした後、当該治具を、アルゴン雰囲気かつ低水分条件(露点-30℃以下)に保たれたグローブボックス内に入れ、温度40℃の溶融塩アルミニウムめっき浴に浸漬させ、ワークをセットした治具を整流器の陰極側に接続し、純アルミニウム板を陽極側に接続する。前記溶融塩アルミニウムめっき浴として、例えば、33mol%1-エチル-3-メチルイミダゾリウムクロリド(EMIC)-67mol%AlCl3に1,10-フェナントロリンを添加することによって得られるめっき浴を用いる。次に、ワークと純アルミニウム板の間に、電流密度3.6A/dm2の直流電流を流してめっきすることにより、ポリウレタンフォーム表面にアルミニウムめっき層を形成させ、アルミニウム-樹脂複合多孔体を得る。このめっき層には、炭素を含む有機物であるフェナントロリンが取り込まれている。次いで、アルミニウム-樹脂複合多孔体を大気中で450~630℃に加熱することによって熱処理を行ない、ポリウレタンフォームを除去するとともに、アルミニウム多孔体の結晶粒内に微細(ナノメートルオーダー)なAl4C3を微分散させる。これにより、ヤング率を向上させた三次元網状アルミニウム合金多孔体を得ることができる。
ポリウレタンフォームをワークとして用いる。前記ワークを銅めっき浴に浸漬させ、めっきを行なうことにより、ポリウレタンフォーム表面に銅めっき層を形成させる。次いで、表面に銅めっき層が形成されたポリウレタンフォームをニッケルめっき浴に浸漬させ、めっきを行なうことにより、前記銅めっき層の表面にニッケルめっき層を形成させる。次に、得られた産物を、大気雰囲気で600℃程度に加熱することによって熱処理を行ない、樹脂を除去した後、得られた産物を、水素雰囲気で1000℃程度に加熱することによって熱処理を行ない、ニッケルを熱拡散させる。これにより、銅-ニッケル合金を得ることができる。なお、ワークとして用いられるポリウレタンフォームには、ニッケルめっき層を先に形成させ、次いで銅めっき層を形成させてもよい。
なお、ナノインデンターは、微小領域の硬さ及びヤング率を測定するために用いられる測定手段である。
樹脂多孔質体の表面に導電層を形成させる方法としては、例えば、めっき法、蒸着法、スパッタ法、溶射法等が挙げられる。これらのなかでは、めっき法が好ましい。この場合、まず、樹脂多孔質体の表面に導電層を形成する。
前記導電層は、めっき法等による樹脂多孔質体の表面における金属皮膜(アルミニウムめっき層、銅めっき層、ニッケルめっき層等)の形成を可能にする役目を果たすものであるため、導電性を有していればその材料及び厚みは、特に限定されるものではない。導電層は、樹脂多孔質体に導電性を付与することができる種々の方法により樹脂多孔質体の表面に形成される。導電性を付与する方法として、例えば、無電解めっき法、蒸着法、スパッタ法、カーボン粒子等の導電性粒子を含有した導電性塗料を塗布する方法等の任意の方法を用いることができる。
導電層の材料は、金属被膜と同じ材料であることが好ましい。
スパッタ法として、公知の種々のスパッタ法、例えば、マグネトロンスパッタ法等を用いることができる。スパッタ法には、導電層の形成に用いられる材料として、アルミニウム、ニッケル、クロム、銅、モリブデン、タンタル、金、アルミニウム・チタン合金、ニッケル・鉄合金等を用いることができる。これらのなかでは、アルミニウム、ニッケル、クロム、銅やこれらを主とする合金がコスト等の点で適当である。
前記方法によって樹脂多孔質体の表面に薄く導電層を形成させた後、導電層が形成された樹脂多孔質体の表面にめっき処理等を施すことにより、所望の厚さの金属被膜を形成させる。これにより、金属-樹脂複合多孔体が得られる。
樹脂多孔質体の素材として、任意の合成樹脂からなる多孔質体を選択できる。前記樹脂多孔質体としては、例えば、ポリウレタン、メラミン樹脂、ポリプロピレン、ポリエチレン等の合成樹脂の発泡体等が挙げられる。なお、樹脂多孔質体は、合成樹脂の発泡体のみならず、連続した気孔(連通気孔)を有するものであればよく、任意の形状の樹脂成形体(樹脂多孔質体)を用いることができる。また、合成樹脂の発泡体の代わりに、例えば繊維状の合成樹脂を絡めて不織布のような形状を有するものも使用可能である。樹脂多孔質体の気孔率は、80%~98%が好ましい。また、樹脂多孔質体の気孔径は、50μm~500μmが好ましい。樹脂多孔質体のなかでも、ポリウレタンフォーム及びメラミン樹脂発泡体は、高い気孔率を有し、また気孔の連通性があるとともに熱分解性にも優れているため、樹脂多孔質体として好ましく使用できる。
特に、ポリウレタンフォームは、気孔の均一性や入手の容易さ等の点で好ましく、不織布は気孔径の小さな三次元網状金属多孔体が得られる点で好ましい。
気孔率=(1-(樹脂多孔質体の質量[g]/(樹脂多孔質体の体積[cm3]×素材密度)))×100[%]
また、気孔径は、樹脂多孔質体表面を顕微鏡写真等で拡大し、1インチ(25.4mm)あたりの気孔数を計数して、平均気孔径=25.4mm/気孔数として平均的な値を求める。
以下では、リチウム二次電池の場合を例にとって、活物質及び固体電解質の材料について述べ、また、三次元網状金属多孔体への活物質の充填法について述べる。
正極活物質として、リチウムイオンの挿入又は脱離が可能な物質を用いることができる。
このような正極活物質の材料としては、例えば、コバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、ニッケルコバルト酸リチウム(LiCoxNi1-xO2;0<x<1)、マンガン酸リチウム(LiMn2O4)、リチウムマンガン酸化合物(LiMyMn2-yO4;M=Cr、Co又はNi、0<y<1)等が挙げられる。他の正極活物質の材料としては、リチウムリン酸鉄(LiFePO4)、LiFe0.5Mn0.5PO4等のオリビン型化合物等のリチウム遷移金属酸化物等が挙げられる。
負極活物質として、リチウムイオンの挿入又は脱離が可能な物質を用いることができる。このような負極活物質としては、例えば、黒鉛、チタン酸リチウム(Li4Ti5O12)等が挙げられる。
また、他の負極活物質として、金属リチウム(Li)、金属インジウム(In)、金属アルミニウム(Al)、金属ケイ素(Si)、金属スズ(Sn)、金属マグネシウム(Mn)、金属カルシウム(Ca)等の金属;前記金属の少なくとも1種と他の元素及び/又は化合物とを組み合せた合金(すなわち、前記金属の少なくとも1種を含む合金)等を用いることができる。
前記負極活物質は、単独で用いてもよく、2種類以上を混合して用いてもよい。前記負極活物質のなかでは、効率の良いリチウムイオンの挿入及び脱離並びに効率の良いリチウムとの合金形成を行なう観点から、黒鉛、チタン酸リチウム(Li4Ti5O12)、又はLi、In、Al、Si、Sn、Mg及びCaからなる群より選ばれた金属、或いは前記金属の少なくとも1種を含む合金が好ましい。
三次元網状金属多孔体の気孔に充填するための固体電解質として、リチウムイオン伝導度の高い硫化物固体電解質を使用することが好ましい。前記硫化物固体電解質としては、リチウムとリンと硫黄とを構成元素として含む硫化物固体電解質が挙げられる。硫化物固体電解質は、さらに、O、Al、B、Si、Ge等の元素を構成元素として含んでいてもよい。
固体電解質層は、前記固体電解質材料を膜状に形成させることによって得ることができる。
この固体電解質層の層厚は、1μm~500μmであることが好ましい。
本発明においては、導電助剤として、公知又は市販のものを用いることができる。前記導電助剤としては、特に限定されるものではなく、例えば、アセチレンブラック、ケッチェンブラック等のカーボンブラック;活性炭;黒鉛等が挙げられる。導電助剤として黒鉛を用いる場合、その形状は、球状、フレーク状、フィラメント状、カーボンナノチューブ(CNT)などの繊維状等のいずれの形状であってもよい。
活物質及び固体電解質(「活物質等」ともいう)に必要に応じて導電助剤やバインダを加え、得られた混合物に有機溶剤、水等を混合してスラリーを作製する。
バインダは、リチウム二次電池用正極で一般的に用いられるものであればよい。バインダの材料としては、例えば、PVDF、PTFE等のフッ素樹脂;ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体等のポリオレフィン樹脂;増粘剤(例えば、カルボキシメチルセルロース、キサンタンガム、ペクチンアガロース等の水溶性増粘剤等)等が挙げられる。
スラリー中の各成分の含有量は特に限定されるものではなく、用いられるバインダ、溶媒等に応じて適宜決定すればよい。
三次元網状金属多孔体の気孔への活物質等の充填は、例えば、活物質等のスラリーを、浸漬充填法や塗工法などの公知の方法を用い、三次元網状金属多孔体内部の空隙に前記活物質等のスラリーを入り込ませることによって行なうことができる。塗工法としては、例えば、ロール塗工法、アプリケーター塗工法、静電塗工法、粉体塗工法、スプレー塗工法、スプレーコーター塗工法、バーコーター塗工法、ロールコーター塗工法、ディップコーター塗工法、ドクターブレード塗工法、ワイヤーバー塗工法、ナイフコーター塗工法、ブレード塗工法、及びスクリーン印刷法などが挙げられる。
充填させる活物質の量は、特に限定されないが、例えば、20~100mg/cm2、好ましくは30~60mg/cm2程度であればよい。
この加圧により、電極の厚みを、通常、100~450μm程度にする。前記電極の厚みは、高出力用二次電池の電極の場合、好ましくは100~250μmであり、高容量用二次電池の電極の場合、好ましくは250~450μmである。加圧工程は、ローラプレス機で行なうことが好ましい。ローラプレス機は、電極面の平滑化に最も効果があるので、当該ローラプレス機で加圧することにより、短絡のおそれを少なくすることができる。
加熱処理の温度は、100℃以上であり、好ましくは150~200℃である。
加熱処理は、常圧下で行なってもよく、減圧下で行なってもよいが、減圧下で行なうことが好ましい。減圧下で加熱処理を行なう場合、圧力は、例えば、1000Pa以下、好ましくは1~500Paである。
加熱時間は、加熱雰囲気、圧力等に応じて適宜決定されるが、通常1~20時間、好ましくは5~15時間とすればよい。
さらに必要に応じて、充填工程と加圧工程との間に、常法に従って乾燥工程を行なってもよい。
<アルミニウム合金多孔体1の製造>
(導電層の形成)
樹脂多孔質体として、ポリウレタンフォーム(気孔率:95%、厚さ:1mm、1インチ当たりの気孔数:30個(気孔径847μm))を用いた。前記ポリウレタンフォームの表面に、スパッタ法によってアルミニウムの目付量が10g/m2となるように成膜して導電層を形成させた。
表面に導電層が形成された前記ポリウレタンフォームをワークとして用いた。前記ワークを、給電機能を有する治具にセットした後、当該治具を、アルゴン雰囲気及び低水分条件(露点-30℃以下)に保たれたグローブボックス内に入れ、温度40℃の溶融塩アルミニウムめっき浴に浸漬した。なお、溶融塩アルミニウムめっき浴は、33mol%EMIC-67mol%AlCl3に、1,10-フェナントロリンを5g/Lとなるように添加することによって得られためっき浴である。ワークがセットされた治具を整流器の陰極側に接続し、純アルミニウム板を陽極側に接続した。次に、溶融塩アルミニウムめっき浴を撹拌しながら、ワークと純アルミニウム板との間に電流密度3.6A/dm2の直流電流を90分間流してワークの表面をめっきすることにより、ポリウレタンフォーム表面にアルミニウムめっき層(アルミニウムの目付量:150g/m2)が形成された[アルミニウム-樹脂複合多孔体1]を得た。前記アルミニウムめっき層には炭素原子を含む有機物であるフェナントロリンが取り込まれている。なお、前記溶融塩アルミニウムめっき浴の攪拌は、テフロン(登録商標)製の回転子とスターラーとを用いて行なった。ここで、電流密度は、ポリウレタンフォームの見かけの面積で計算した値である。
前記[アルミニウム-樹脂複合多孔体1]を大気中で450~630℃に加熱することによって熱処理を行ない、ポリウレタンフォームを除去するとともに、アルミニウム多孔体の結晶粒内に微細(ナノメートルオーダー)なAl4C3を微分散させ、[アルミニウム合金多孔体]を得た。
[アルミニウム合金多孔体]のヤング率は、81GPaであった。
<アルミニウム多孔体の製造>
製造例1において、溶融塩アルミニウムめっき浴として、めっき浴(組成:33mol%EMIC-67mol%AlCl3)を用いたことを除き、製造例1と同様の操作を行ない、[アルミニウム多孔体]を得た。
[アルミニウム多孔体]のヤング率は、65GPaであった。
<銅合金多孔体1の製造>
製造例1で用いられたポリウレタンフォームの表面に、スパッタ法によって銅の目付量が10g/m2となるように成膜して導電層を形成させた。
[銅合金多孔体]のヤング率は、160GPaであった。
製造例3において、銅めっき浴を用いて銅の目付量が400g/m2となるように銅めっきを行なったこと及びニッケルめっきを行なわなかったことを除き、製造例3と同様の操作を行ない、純銅からなる[銅多孔体]を得た。
[銅多孔体]のヤング率は、115GPaであった。
<正極1の製造>
正極活物質として、コバルト酸リチウム粉末(平均粒子径:5μm)を用いた。コバルト酸リチウム粉末(正極括物質)と、Li2S-P2S2(固体電解質)と、アセチレンブラック(導電助剤)と、PVDF(バインダ)とを、質量比(正極活物質/固体電解質/導電助剤/バインダ)が55/35/5/5となるように混合した。得られた混合物にN-メチル-2-ピロリドン(有機溶剤)を滴下して混合し、ペースト状の正極合剤スラリーを得た。次に、得られた正極合剤スラリーを、[アルミニウム合金多孔体]の表面に供給し、ローラで5kg/cm2の負荷をかけて押圧することにより、[アルミニウム合金多孔体]の気孔に正極合剤を充填した、その後、正極合剤が充填された[アルミニウム合金多孔体]を100℃で40分間乾燥させて有機溶剤を除去することにより、[正極1]を得た。
<正極2の製造>
製造例5において、[アルミニウム合金多孔体]に代えて[アルミニウム多孔体]を用いたことを除き、製造例5と同様の操作を行ない、[正極2]を得た。
<負極1の製造>
負極活物質として、チタン酸リチウム粉末(平均粒子径が2μm)を用いた。チタン酸リチウム粉末(負極活物質)と、Li2S-P2S2(固体電解質)と、アセチレンブラック(導電助剤)と、PVDF(バインダ)とを、質量比(負極活物質/固体電解質/導電助剤/バインダ)が50/40/5/5となるように混合した。得られた混合物にN-メチル-2-ピロリドン(有機溶剤)を滴下して混合し、ペースト状の負極合剤スラリーを得た。次に、得られた負極合剤スラリーを[銅合金多孔体]の表面に供給し、ローラで5kg/cm2の負荷をかけて押圧することにより、[銅合金多孔体]の気孔に負極合剤を充填した。その後、100℃で40分間乾燥させて有機溶剤を除去することにより、[負極1]を得た。
<負極2の製造>
製造例7において、[銅合金多孔体]に代えて[銅多孔体]を用いたことを除き、製造例7と同様の操作を行ない、[負極2]を得た。
<固体電解質膜1の製造>
リチウムイオン導電性ガラス状固体電解質であるLi2S-P2S2(固体電解質)を乳鉢で100メッシュ以下に粉砕し、直径10mm、厚さ1.0mmのディスク状に加圧成形して、[固体電解質膜1]を得た。
[正極1]と[負極1]とで[固体電解質膜1]を挟んで圧接し、[全固体リチウム二次電池1]を作製した。
実施例1において、[正極1]に代えて[正極2]を用いたこと及び[負極1]に代えて[負極2]を用いたことを除き、実施例1と同様の操作を行ない、[全固体リチウム二次電池2]を得た。
実施例1及び比較例1で得られた各全個体リチウム二次電池について、電流密度100μA/cm2で充放電サイクル試験を行ない100回目の放電容量維持率を評価した。その結果を表2に示す。
2 負極
3 イオン伝導層
4 電極積層体
5 正極活物質粉末
6 導電性粉末
7 正極集電体
8 負極活物質粉末
9 負極集電体
10 全固体二次電池
60 全固体二次電池
61 正極
62 負極
63 固体電解質層(SE層)
64 正極層(正極体)
65 正極集電体
66 負極層
67 負極集電体
Claims (4)
- 正極及び負極が三次元網状多孔体を集電体とし、該三次元網状多孔体の気孔中に少なくとも活物質が充填されてなる電極である全固体リチウム二次電池であって、
前記正極の三次元網状多孔体が、ヤング率が70GPa以上のアルミニウム合金であり、 前記負極の三次元網状多孔体が、ヤング率が120GPa以上の銅合金である
ことを特徴とする全固体リチウム二次電池。 - 前記正極の活物質が、コバルト酸リチウム(LiCoO2)、ニッケル酸リチウム(LiNiO2)、ニッケルコバルト酸リチウム(LiCoxNi1-xO2;0<x<1)、マンガン酸リチウム(LiMn2O4)及びリチウムマンガン酸化合物(LiMyMn2-yO4;M=Cr、Co又はNi、0<y<1)からなる群より選択された少なくとも一種であり、
前記負極の活物質が黒鉛、チタン酸リチウム(Li4Ti5O12)、又はLi、In、Al、Si、Sn、Mg及びCaからなる群から選ばれる金属、或いは前記金属の少なくとも一種を含む合金であることを特徴とする請求項1に記載の全固体リチウム二次電池。 - 前記正極と、前記負極と、前記正極と前記負極とに挟まれた固体電解質層とを備えることを特徴とする請求項1又は2に記載の全固体リチウム二次電池。
- 前記三次元網状多孔体の気孔中に固体電解質が充填され、該固体電解質及び前記固体電解質層を形成する固体電解質が、リチウムとリンと硫黄とを構成元素として含む硫化物固体電解質であることを特徴とする請求項3に記載の全固体リチウム二次電池。
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JP7239551B2 (ja) | 2020-12-28 | 2023-03-14 | 本田技研工業株式会社 | リチウムイオン二次電池用電極 |
JP2022108360A (ja) * | 2021-01-13 | 2022-07-26 | 本田技研工業株式会社 | 電極及びそれを用いた二次電池 |
JP7170759B2 (ja) | 2021-01-13 | 2022-11-14 | 本田技研工業株式会社 | 電極及びそれを用いた二次電池 |
JP7190516B2 (ja) | 2021-01-19 | 2022-12-15 | 本田技研工業株式会社 | 円筒形固体電池及びその製造方法 |
JP2022110670A (ja) * | 2021-01-19 | 2022-07-29 | 本田技研工業株式会社 | 円筒形固体電池及びその製造方法 |
WO2024029466A1 (ja) * | 2022-08-02 | 2024-02-08 | マクセル株式会社 | 全固体電池 |
Also Published As
Publication number | Publication date |
---|---|
KR20140137371A (ko) | 2014-12-02 |
US20150017549A1 (en) | 2015-01-15 |
DE112013001595T5 (de) | 2015-01-08 |
JPWO2013140942A1 (ja) | 2015-08-03 |
CN104205467A (zh) | 2014-12-10 |
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