Patent Application
20230103490
The present invention relates to an electrode body, a power storage element, and a power storage module.
Lithium ion secondary batteries are widely used as power sources for mobile devices such as portable telephones and laptop computers, hybrid cars, and the like. With development in these fields, lithium ion secondary batteries are required to have higher performance.
For example, Patent Document 1 discloses a resin current collector. The resin current collector includes a resin layer, and metal layers that are formed on both surfaces thereof. A secondary battery using a resin current collector has a high output density per weight.
Patent Document 1: PCT International Publication No. WO2019/031091
Secondary batteries are produced by laminating or winding a battery sheet. When laminating or winding is performed, if a position of an end surface deviates, a positive electrode and a negative electrode may be short-circuited.
The present disclosure has been made in consideration of the foregoing problems, and an object thereof is to provide an electrode body, a power storage element, and a power storage module using the same, in which a short circuit between a positive electrode and a negative electrode can be curbed.
In order to resolve the foregoing problems, the following features are provided.
(1) An electrode body according to a first aspect includes: a current collector which includes a first layer having a first surface and a second surface facing a side opposite to the first surface and including a resin, a first metal layer on the first surface of the first layer, and a second metal layer on the second surface of the first layer; a first active material layer which is laminated on the first metal layer; a second active material layer which is laminated on the second metal layer; and a separator or a solid electrolyte layer which comes into contact with at least one of the first active material layer and the second active material layer. The first surface of the first layer has a first region in which the first metal layer is laminated, a second region which is exposed from the first metal layer when viewed in a lamination direction of the first metal layer, and a third region which is exposed from the first metal layer and sandwiches the first region with the second region therebetween when viewed in the lamination direction of the first metal layer. A length of the first metal layer in a first direction is shorter than a length of the second metal layer in the first direction.
(2) The electrode body according to the foregoing aspect may further include an insulating layer which is laminated in at least one of the second region and the third region.
(3) In the electrode body according to the foregoing aspect, the insulating layer may include an insulator having a ceramic as a main component.
(4) In the electrode body according to the foregoing aspect, the first layer may be an insulating layer of 1.0×109 Ω·cm or higher.
(5) In the electrode body according to the foregoing aspect, the first layer may include any one selected from the group consisting of polyethylene terephthalate (PET), polyimide (PI), polyamide imide (PAI), polypropylene (PP), and polyethylene (PE).
(6) In the electrode body according to the foregoing aspect, each of the first metal layer and the second metal layer may be any one selected from aluminum, nickel, stainless steel, copper, platinum, and gold.
(7) In the electrode body according to the foregoing aspect, the first metal layer and the second metal layer may include metals or alloys different from each other.
In the electrode body according to the foregoing aspects, a short circuit between a positive electrode and a negative electrode can be curbed.
Hereinafter, preferred examples of the present invention will be described in detail with reference to the accompanying drawings.
Examples of the present invention are provided to those skilled in the art of the technical field so as to describe the present invention in detail. The following Examples may be modified into various other forms, and the scope of the present invention is not limited to the following Examples.
In addition, in the following drawings, the thickness and the size of each layer are presented for the sake of convenience of description and clarity, and the same reference signs in the drawings indicate the same elements. As used in this specification, the term “and/or” includes any one and all combinations of one or more of the enumerated items.
The terms used in this specification are used for describing a particular example and are not intended to limit the present invention. As used in this specification, a singular form can include a plural form unless otherwise designated clearly in its context. In addition, when used in this specification, the term “include” identifies the presence of the shape, the number, the stage, the operation, the member, the element, and/or a group of these which have been mentioned and is not intended to exclude the presence or addition of one or more of other shapes, numbers, operations, members, elements, and/or groups thereof.
Space-related terms such as “lower portion”, “below”, “low”, “upper portion”, “above”, “left”, and “right” may be utilized for easy understanding of one element or characteristic with respect to other elements or characteristics illustrated in the drawings. Such space-related terms are intended to facilitate understanding of the present invention in terms of various states of steps or states of usage of the present invention and are not intended to limit the present invention. For example, if an element or a characteristic in the drawing is turned upside down, “lower portion” or “below” used for describing the element or the characteristic becomes “upper portion” or “above”. Therefore, “lower portion” indicates a concept covering “upper portion” or “below”. In addition, depending on the direction in which an element is viewed in the drawings, “left” and “right” may be reversed.
The power storage element 200 includes the electrode body 100 and the exterior body C. A structure of the electrode body 100 will be described below. The electrode body 100 is accommodated in an accommodation space K of the exterior body C together with an electrolytic solution. The electrode body 100 has tabs t1 and t2 implementing electrical connection to an external device. The tabs t1 and t2 protrude outward from the exterior body C. The tab t1 is connected to a first metal layer 12 which will be described below, and the tab t2 is connected to a second metal layer 13 which will be described below.
The tabs t1 and t2 are constituted to include a metal. For example, a metal is aluminum, copper, nickel, SUS, or the like.
For example, the tabs t1 and t2 have a rectangular shape in a plan view in a z direction which will be described below, but the shapes thereof are not limited to the foregoing shape and diverse shapes can be employed.
The exterior body C is intended to seal the electrode body 100 and the electrolytic solution inside thereof. The exterior body C inhibits leakage of the electrolytic solution to the outside, infiltration of moisture and the like into the electrode body 100 from the outside, and the like.
For example, the exterior body C is a metal laminate film in which a metal foil is coated with polymer films from both sides. For example, the metal foil is an aluminum foil, and for example, the polymer film is made of a resin such as polypropylene. For example, the polymer film on the outward side is made of polyethylene terephthalate (PET), polyamide, or the like, and for example, the polymer film on the inward side is made of polyethylene (PE), polypropylene (PP), or the like. In order to facilitate welding by heat, for example, the polymer film on the inward side has a lower melting point than the polymer film on the outward side.
An adhesive layer including an adhesive substance may be provided between the exterior body C and the electrode body 100. The exterior body C covers the outermost surface of the electrode body 100. An inner surface of the exterior body C faces the outermost surface of the electrode body 100. For example, the adhesive layer is located on a surface of the exterior body C facing the electrode body 100 (inner surface) or a surface of the electrode body 100 facing the exterior body C (the outermost surface of the electrode body). For example, the adhesive layer is a double-sided tape or the like which is resistant to an electrolytic solution. For example, the adhesive layer may be a layer which is obtained by forming an adhesive layer of polyisobutylene rubber on a polypropylene base material, a layer made of a rubber such as a butyl rubber, a layer made of a saturated hydrocarbon resin, or the like. The adhesive layer curbs movement of the electrode body 100 inside the exterior body C. In addition, even when a metal body such as a nail is stuck in the adhesive layer, the adhesive substance is entwined with a metal body such as a nail, and thus occurrence of a short circuit is curbed.
For example, the electrolytic solution is a nonaqueous electrolytic solution including a lithium salt or the like. The electrolytic solution is a solution in which an electrolyte is dissolved in a nonaqueous solvent, and it may contain cyclic carbonates and chain carbonates as nonaqueous solvents.
Cyclic carbonates solvate an electrolyte. For example, the cyclic carbonates are ethylene carbonate, propylene carbonate, butylene carbonate, or the like. Chain carbonates reduce a viscosity of cyclic carbonates. For example, the chain carbonates are diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate. Furthermore, chain carbonates may be used with methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ-butyrolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, or the like mixed thereinto. For example, a proportion of the cyclic carbonates: the chain carbonates is 1:9 to 1:1 in terms of volume ratio.
For example, in the nonaqueous solvent, a portion of hydrogen in the cyclic carbonates or chain carbonates may be substituted with fluorine. For example, the nonaqueous solvent may include fluoroethylene carbonate, difluoroethylene carbonate, or the like.
For example, the electrolyte is a lithium salt such as LiPF6, LiClO4, LiBF4, LiCF3SO3, LiCF3CF2SO3, LiC(CF3SO2)3, LiN(CF3SO2)2, LiN(CF3CF2SO2)2, LiN(CF3SO2)(C4F9SO2), LiN(CF3CF2CO)2, LiBOB, or the like. Regarding these lithium salts, one kind may be used alone, or two or more kinds may be used together. From a viewpoint of the degree of ionization, it is preferable to include LiPF6 as an electrolyte.
When LiPF6 is dissolved in the nonaqueous solvent, for example, the concentration of the electrolyte in the electrolytic solution is adjusted to 0.5 mol/L to 2.0 mol/L. If the concentration of the electrolyte is 0.5 mol/L or higher, the concentration of lithium ions in the nonaqueous electrolytic solution can be sufficiently secured, and a sufficient capacitance at the time of charging and discharging is likely to be obtained. In addition, when the concentration of the electrolyte is regulated to be 2.0 mol/L or lower, increase in coefficient of viscosity of the nonaqueous electrolytic solution can be restricted, mobility of lithium ions can be sufficiently secured, and thus a sufficient capacitance at the time of charging and discharging is likely to be obtained.
When LiPF6 is mixed with other electrolytes as well, for example, it is preferable that the concentration of lithium ions in the nonaqueous electrolytic solution be adjusted to 0.5 mol/L to 2.0 mol/L and the concentration of lithium ions from LiPF6 be equal to or higher than 50 mol % thereof.
For example, the nonaqueous solvent may have a room-temperature molten salt. A room-temperature molten salt is a salt which is obtained by a combination of cations and anions and is in a liquid state even if the temperature is lower than 100° C. Since a room-temperature molten salt is a liquid consisting of only ions, it has strong electrostatic interactions and is characterized by being non-volatile and nonflammable.
Regarding cation components of a room-temperature molten salt, there are nitrogen-based cations including nitrogen, phosphorus-based cations including phosphorus, sulfur-based cations including sulfur, and the like. Regarding these cation components, one kind may be included alone or two or more kinds may be included in combination.
Regarding nitrogen-based cations, there are chain or cyclic ammonium cations such as imidazolium cations, pyrrolidinium cations, piperidinium cations, pyridinium cations, and azoniaspiro cations.
Regarding phosphorus-based cations, there are chain or cyclic phosphonium cations.
Examples of sulfur-based cations include chain or cyclic sulfonium cations.
Particularly, as the cation component, N-methyl-N-propyl-pyrrolidinium (P13) that is nitrogen-based cation is preferable since this cation component has high lithium-ion conductivity and has wide resistance to oxidation and reduction when a lithium imide salt is dissolved therein.
Regarding anion components of a room-temperature molten salt, there are AlCl4−, NO2−, NO3−, I−, BF4−, PF6−, AsF6−, SbF6−, NbF6−, TaF6−, F(HF)2.3—, p-CH3PhSO3−, CH3CO2−, CF3CO2−, CH3SO3−, CF3SO3−, (CF3SO2)3C−, C3F7CO2, C4F9SO3−, (FSO2)2N− (bis(fluorosulfonyl)imide: FSI), (CF3SO2)2N− (bis(trifluoromethanesulfonyl)imide: TFSI), (C2F5SO2)2N− (bis(pentafluoroethanesulfonyl)imide), (CF3SO2)(CF3CO)N− ((trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide), (CN)2N− (dicyanoimide), and the like. Regarding these anion components, one kind may be included alone or two or more kinds may be included in combination.
Directions will be defined. A lamination direction of layers of the battery sheet S will be referred to as the z direction. A direction from the second metal layer 13 toward the first metal layer 12 will be referred to as a positive z direction, and a direction opposite to the positive z direction will be referred to as a negative z direction. A direction within a plane where the battery sheet S expands will be referred to as an x direction, and a direction orthogonal to the x direction will be referred to as a y direction.
The battery sheet S includes the current collector 10, a positive electrode active material layer 20, a negative electrode active material layer 30, and the separator 40. The positive electrode active material layer 20 is formed on a first surface 10a side of the current collector 10. The negative electrode active material layer 30 is formed on a second surface 10b side of the current collector 10. The second surface 10b is a surface on a side opposite to the first surface 10a in the current collector 10. The current collector 10 has the first surface 10a, and the second surface 10b facing a side opposite to the first surface 10. The positive electrode active material layer 20 is an example of a first active material layer. The negative electrode active material layer 30 is an example of a second active material layer. The separator 40 comes into contact with the positive electrode active material layer 20 or the negative electrode active material layer 30. The separator 40 is located between the positive electrode active material layer 20 and the negative electrode active material layer 30 in a state in which the electrode body 100 is wound.
The current collector 10 includes the resin layer 11, the first metal layer 12, and the second metal layer 13. The first metal layer 12 is formed on a first surface 11a side of the resin layer 11. The second metal layer 13 is formed on a second surface 11b side of the resin layer 11. The second surface 11b is a surface on a side opposite to the first surface 11a in the resin layer 11. For example, the first metal layer 12 is a positive electrode current collector. For example, the second metal layer 13 is a negative electrode current collector. For example, the positive electrode active material layer 20 is formed on a surface of the first metal layer 12 on a side opposite to the resin layer 11. In this case, the first metal layer 12 and the positive electrode active material layer 20 form the positive electrode Cd. For example, the negative electrode active material layer 30 is formed on a surface of the second metal layer 13 on a side opposite to the resin layer 11. In this case, the second metal layer 13 and the negative electrode active material layer 30 form the negative electrode Ad. The relationship between the first metal layer 12 and the second metal layer 13 may be reversed. The first metal layer 12 may be a negative electrode current collector, and the second metal layer 13 may be a positive electrode current collector. The first metal layer 12 and the second metal layer 13 need only be conductive layers.
The first surface 11a of the resin layer 11 has a first region A1, a second region A2, and a third region A3. The first region A1 is a region in which the first metal layer 12 is laminated on the first surface 11a and is a region in which the first metal layer 12 and the first surface 11a overlap each other in a view in the z direction. The second region A2 is a region away from the first metal layer 12 on the first surface 11a and is on a lateral side of the first region A1 in the y direction. The third region A3 is a region away from the first metal layer 12 on the first surface 11a and is on a lateral side of the first region A1 in the y direction on a side opposite to the second region A2. The second region A2 and the third region A3 sandwich the first region therebetween in the y direction. For example, there are openings Op on the second region A2 and the third region A3. The first surface 11a is exposed from the first metal layer 12 in the second region A2 and the third region A3.
Lengths of the resin layer 11 and the first metal layer 12 in the x direction may coincide with each other or may differ from each other. Positions of an end side of the resin layer 11 in the x direction and an end side of the first metal layer 12 in the x direction may coincide with each other or may differ from each other. It is preferable that the length of the resin layer 11 in the x direction be longer than the length of the first metal layer 12 in the x direction.
In addition, the length of the first metal layer 12 in the x direction and the length of the second metal layer 13 in the x direction may coincide with each other or may differ from each other. It is preferable that the length of the first metal layer 12 in the x direction be longer than the length of the second metal layer 13 in the x direction.
The first metal layer 12 covers the first surface 11a of the resin layer 11 in the y direction. A length L12 of the first metal layer 12 in the y direction is shorter than a length L11 of the resin layer 11 in the y direction.
The second metal layer 13 covers the entire second surface 11b of the resin layer 11 in the y direction. A length L13 of the second metal layer 13 in the y direction coincides with the length L11 of the resin layer 11 in the y direction. The length L12 of the first metal layer 12 in the y direction is shorter than the length L13 of the second metal layer 13 in the y direction.
The expression that the length L13 of the second metal layer 13 in the y direction coincides with the length L11 of the resin layer 11 in the y direction indicates that the difference between the length L11 of the resin layer 11 in the y direction and the length L13 of the second metal layer 13 in the y direction is within 3%.
The resin layer 11 is constituted to include a material having insulating properties. In this specification, insulating properties denote that a resistance value is 1.0×109 Ω·cm or higher. For example, the resin layer 11 is an insulating layer. The resin layer 11 is an example of a first layer. The resin layer 11 includes any one selected from the group consisting of polyethylene terephthalate (PET), polyimide (PI), polyamide imide (PAI), polypropylene (PP), and polyethylene (PE). For example, the resin layer 11 is a PET film. The resin layer 11 insulates the first metal layer 12 and the second metal layer 13 from each other. For example, a thickness of the resin layer 11 is 3 μm to 9 μm and is preferably 4 μm to 6 μm.
Each of the first metal layer 12 and the second metal layer 13 is any one selected from aluminum, nickel, stainless steel, copper, platinum, and gold. For example, the first metal layer 12 and the second metal layer 13 include metals or alloys different from each other. For example, the first metal layer 12 is aluminum. For example, the second metal layer 13 is copper. The first metal layer 12 and the second metal layer 13 may be formed of the same materials. For example, both the first metal layer 12 and the second metal layer 13 are made of aluminum.
It is preferable that both the first metal layer 12 and the second metal layer 13 be constituted using aluminum or the first metal layer 12 and the second metal layer 13 be constituted such that one of the first metal layer 12 and the second metal layer 13 is made of aluminum and the other is made of copper.
The thicknesses of the first metal layer 12 and the second metal layer 13 may be the same or different from each other. For example, the thicknesses of the first metal layer 12 and the second metal layer 13 are preferably 0.3 μm to 2 μm and are preferably 0.4 μm to 1 μm.
For example, the positive electrode active material layer 20 includes positive electrode active materials, conductive additives, and binders.
The positive electrode active materials can reversibly proceed absorbing and desorbing of lithium ions, separation and intercalation of lithium ions, or doping and de-doping of lithium ions and counter anions.
For example, the positive electrode active materials are lithium cobaltate (LiCoO2), lithium nickelate (LiNiO2), lithium manganate (LiMnO2), lithium manganese spinel (LiMn2O4), complex metal oxide expressed by general formula: LiNixCoyMnzMaO2 (x+y+z+a=1, 0≤x<1, 0≤y<1, 0≤z<1, 0≤a<1, and M is one or more kinds of elements selected from Al, Mg, Nb, Ti, Cu, Zn, and Cr), a lithium vanadium compound (LiV2O5), olivine-type LiMPO4 (M indicates one or more kinds of elements selected from Co, Ni, Mn, Fe, Mg, Nb, Ti, Al, and Zr, or VO), lithium titanate (Li4Ti5O12), complex metal oxide such as LiNixCoyAlzO2 (0.9<x+y+z<1.1), polyacetylene, polyaniline, polypyrrole, polythiophene, polyacene, or the like. In addition, the positive electrode active materials may be mixtures of these.
The conductive additives are dotted inside the positive electrode active material layer. The conductive additives enhance the conductivity between the positive electrode active materials in the positive electrode active material layer. For example, the conductive additives are carbon powder such as carbon blacks, carbon nanotubes, carbon materials, fine powder of a metal such as copper, nickel, stainless steel, or iron, a mixture of a carbon material and a metal fine powder, or conductive oxide such as ITO. It is preferable that the conductive additives be carbon materials such as carbon black. When sufficient conductivity can be secured with active materials, the positive electrode active material layer 20 may not include conductive additives.
The binders bind the positive electrode active materials to each other in the positive electrode active material layer. Known binders can be used as the binders. For example, the binders are fluororesins. For example, fluororesins are polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), an ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), an ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), or the like.
In addition to the above-described materials, for example, the binders may be vinylidene fluoride-based fluororubber such as vinylidene fluoride-hexafluoropropylene-based fluororubber (VDF-HFP-based fluororubber), vinylidene fluoride-hexafluoropropyl ene-tetrafluoroethylene-based fluororubber (VDF-HFP-TFE-based fluororubber), vinylidene fluoride-pentafluoropropylene-based fluororubber (VDF-PFP-based fluororubber), vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene-based fluororubber (VDF-PFP-TFE-based fluororubber), vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene-based fluororubber (VDF-PFMVE-TFE-based fluororubber), and vinylidene fluoride-chlorotrifluoroethylene-based fluororubber (VDF-CTFE-based fluororubber).
The negative electrode active material layer 30 includes negative electrode active materials. In addition, as necessary, it may include conductive additives, binders, and solid electrolytes.
The negative electrode active materials need only be compounds capable of absorbing and desorbing ions, and negative electrode active materials used in known lithium ion secondary batteries can be used. For example, the negative electrode active materials are metal lithium; lithium alloys; carbon materials such as graphite capable of absorbing and desorbing ions (natural graphite or artificial graphite), carbon nanotubes, hardly graphitizable carbon, easily graphitizable carbon, and low-temperature baked carbon; a metalloid or a metal such as aluminum, silicon, tin, or germanium which can be chemically combined with a metal such as lithium; amorphous compounds mainly including oxide such as SiOx (0<x<2) or tin dioxide; or particles including lithium titanate (Li4Ti5O12) or the like.
As described above, for example, the negative electrode active material layer 30 may include silicon, tin, or germanium. Silicon, tin, or germanium may be present as a single element or may be present as a compound. For example, a compound is an alloy and oxide. As an example, when the negative electrode active materials are silicon, the negative electrode may be referred to as a Si negative electrode. For example, the negative electrode active materials may be a mixed system of a simple substance or a compound of silicon, tin, and germanium and a carbon material. For example, a carbon material is natural graphite. In addition, for example, the negative electrode active materials may be a simple substance or a compound of silicon, tin, and germanium of which a surface is covered with carbon. A carbon material and covered carbon enhance the conductivity between the negative electrode active materials and a conductive additive. If the negative electrode active material layer includes silicon, tin, or germanium, the capacitance of the power storage element 200 increases.
As described above, for example, the negative electrode active material layer 30 may include lithium. Lithium may be metal lithium or a lithium alloy. The negative electrode active material layer 30 may be made of metal lithium or a lithium alloy. For example, a lithium alloy is an alloy of one or more kinds of elements selected from the group consisting of Si, Sn, C, Pt, Ir, Ni, Cu, Ti, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Sb, Pb, In, Zn, Ba, Ra, Ge, and Al, and lithium. As an example, when the negative electrode active materials are metal lithium, the negative electrode may be referred to as a Li negative electrode. The negative electrode active material layer 30 may be a lithium sheet.
The negative electrode may consist of a negative electrode current collector (second metal layer 13) without having the negative electrode active material layer 30 at the time of production. If the power storage element 200 is charged, metal lithium is precipitated on a surface of the negative electrode current collector. Metal lithium is lithium of a simple substance in which lithium ions are precipitated, and metal lithium functions as a negative electrode active material layer.
Regarding the conductive additives and the binders, materials similar to those of the positive electrode active material layer 20 can be used. In addition to those exemplified in the positive electrode active material layer 20, for example, the binders in the negative electrode active material layer 30 may be cellulose, styrene butadiene rubber, ethylene propylene rubber, a polyimide resin, a polyamide imide resin, an acrylic resin, or the like. For example, cellulose may be carboxymethyl cellulose (CMC).
For example, the separator 40 has an electrically insulating porous structure. Examples of the separator 40 include a single layer body of a film consisting of polyolefin such as polyethylene or polypropylene; a stretched film of a laminate and a mixture of the foregoing resins; and fibrous nonwoven fabric made of at least one kind of constituent materials selected from the group consisting of cellulose, polyester, polyacrylonitrile, polyamide, polyethylene, and polypropylene.
In place of the separator 40, a solid electrolyte layer may be provided. When a solid electrolyte layer is used, an electrolytic solution is no longer necessary. A solid electrolyte layer and the separator 40 may be used together.
For example, the solid electrolyte is an ion conductive layer of which the ion conductivity is 1.0×10−8 S/cm or higher and 1.0×10−2 S/cm or lower. For example, the solid electrolyte is a polymer solid electrolyte, an oxide-based solid electrolyte, or a sulfide-based solid electrolyte. For example, the polymer solid electrolyte is an electrolyte in which an alkali metal salt is dissolved in a polyethylene oxide-based polymer. For example, the oxide-based solid electrolyte is Li1.3Al0.3Ti1.7(PO4)3 (NASICON type), Li1.07Al0.69Ti1.46(PO4)3 (glass ceramics), Li0.34La0.51TiO2.94 (Perovskite type), Li7La3Zr2O12 (garnet type), Li2.9PO3.3N0.46 (amorphous, LIPON), 50Li4SiO4.50Li2BO3 (glass), or 90Li3BO3.10Li2SO4 (glass ceramics). For example, the sulfide-based solid electrolyte is Li3.25Ge0.25P0.75S4 (crystal), Li10GeP2S12 (crystal, LGPS), Li6PS5Cl (crystal, argyrodite type), Li9.54Si1.74P1.44S11.7Cl0.3 (crystal), Li3.25P0.95S4 (glass ceramics), Li7P3S11 (glass ceramics), 70Li2S.30P2S5 (glass), 30Li2S.26B2S3.44LiI (glass), 50Li2S.17P2S5.33LiBH4 (glass), 63Li2S.36SiS2.Li3PO4 (glass), or 57Li2S.38SiS2.5Li4SiO4 (glass).
Next, a method for manufacturing a power storage element will be described. First, the first metal layer 12 and the second metal layer 13 are formed on both surfaces of a commercially available resin film. For example, the first metal layer 12 and the second metal layer 13 can be formed by a sputtering method, a chemical vapor deposition method (CVD method), or the like. In the first metal layer 12, for example, film formation is performed utilizing a mask or the like except for both end portions of the resin film in the y direction. After the first metal layer 12 is laminated on one surface of the resin film, both the end portions may be removed by etching or the like.
Next, a surface of the first metal layer 12 is coated with positive electrode slurry. The positive electrode slurry is obtained by mixing positive electrode active materials, binders, and a solvent and making the mixture into a paste. For example, the positive electrode slurry can be coated by a slit die coating method, a doctor blade method, or the like.
A solvent in the positive electrode slurry after coating is removed. A removal method is not particularly limited. For example, the current collector 10 coated with the positive electrode slurry is dried at a temperature of 80° C. to 150° C. in an atmosphere. Next, the obtained coated film is pressed so as to increase the density of the positive electrode active material layer 20. For example, regarding the pressing device, a roll press machine, an isostatic pressing machine, or the like can be used.
Next, a surface of the second metal layer 13 on a side opposite to the surface coated with the positive electrode slurry is coated with negative electrode slurry. The negative electrode slurry is obtained by mixing negative electrode active materials, binders, and a solvent and making the mixture into a paste. The negative electrode slurry can be coated by a method similar to that of the positive electrode slurry. A solvent in the negative electrode slurry after coating is removed by drying; and thereby, the negative electrode active material layer 30 is obtained. When the negative electrode active materials are metal lithium, a lithium foil may be adhered to the second metal layer 13.
Next, portions of the positive electrode active material layer 20 and the negative electrode active material layer 30 are removed, the tab t1 is bonded to the first metal layer 12, and the tab t2 is bonded to the second metal layer 13. For example, the tabs t1 and t2 are welded to the metal layers by ultrasonic waves. The tabs t1 and t2 may be bonded to the metal layers, may be screwed thereto, or may be welded thereto by heat or the like.
Next, the separator 40 is provided at a position where it comes into contact with the positive electrode active material layer 20 or the negative electrode active material layer 30, and the resultant laminate is wound around one end side as an axis. Thereafter, the electrode body 100 together with an electrolytic solution are sealed inside the exterior body C. Sealing is performed while decompression and heating are performed so that the electrolytic solution is impregnated into the electrode body 100. After the exterior body C is sealed by heat or the like, the power storage element 200 is obtained.
The electrode body 100 according to the first embodiment has the openings Op in both end portions on the first surface 11a of the resin layer 11. In the electrode body 100, the first metal layer 12 and the positive electrode active material layer 20 are on the inward side of the second metal layer 13 and the negative electrode active material layer 30 in the winding axis direction (the y direction in the developed body) by the amounts of the openings Op. For this reason, for example, even when deviation occurs at a position of the end portion of the wound battery sheet S due to a cause such as occurrence of winding deviation during winding of the electrode body 100, a short circuit between the positive electrode Cd and the negative electrode Ad can be curbed.
The current collector 10A according to the second embodiment differs from the current collector 10 according to the first embodiment in that the current collector 10A has an insulating layer 14. In the power storage element according to the second embodiment, regarding constitutions similar to those of the power storage element 200 according to the first embodiment, description thereof will be omitted.
The insulating layer 14 covers at least one of the second region A2 and the third region A3. For example, the insulating layer 14 is on the second region A2 and the third region A3. The second region A2 and the third region A3 illustrated in
The electrode body according to the second embodiment includes the insulating layer 14 in both end portions on the first surface 11a of the resin layer 11. In the electrode body, the first metal layer 12 and the positive electrode active material layer 20 are on the inward side of the second metal layer 13 and the negative electrode active material layer 30 in the winding axis direction (the y direction in the developed body) by the amount of the insulating layer 14, and the side surface of the first metal layer 12 is covered with the insulating layer 14. For this reason, for example, even when deviation occurs at a position of the end portion of the wound battery sheet due to a cause such as occurrence of winding deviation during winding of the electrode body, a short circuit between the positive electrode Cd and the negative electrode Ad can be curbed.
In the first embodiment and the second embodiment, a case in which widths of the second region A2 and the third region A3 in the y direction are the same as each other has been described as an example, but the widths of the second region A2 and the third region A3 in the y direction may be different from each other.
In the electrode body 110, a plurality of battery sheets S2 are laminated. Each of the battery sheets S2 includes the separator 40, the negative electrode active material layer 30, the current collector 10, and the positive electrode active material layer 20. The constitutions of the separator 40, the negative electrode active material layer 30, the current collector 10, and the positive electrode active material layer 20 are similar to those in the battery sheet S according to the first embodiment.
For example, the first metal layer 12 covers the first surface of the resin layer 11. The lengths of the first metal layer 12 in the x direction and the y direction are shorter than the lengths of the resin layer 11 in the x direction and the y direction.
For example, the second metal layer 13 covers the entire second surface of the resin layer 11 in the x direction and the y direction. The lengths of the second metal layer 13 in the x direction and the y direction coincide with the lengths of the resin layer 11 in the x direction and the y direction. For this reason, the lengths of the first metal layer 12 in the x direction and the y direction are shorter than the lengths of the second metal layer 13 in the x direction and the y direction.
The electrode body 110 according to the third embodiment has the openings Op in a surrounding portion on the first surface 11a of the resin layer 11. In the electrode body 110, the first metal layer 12 and the positive electrode active material layer 20 are on the inward side of the second metal layer 13 and the negative electrode active material layer 30 in the x direction toward a center layer C. For this reason, for example, even when deviation occurs at a position of each layer in the x direction during lamination of the electrode body 110, a short circuit between the positive electrode Cd and the negative electrode Ad can be curbed.
Hereinafter, embodiments of the present invention have been described in detail with reference to the drawings, but the constituents, combinations thereof, and the like in each of the embodiments are examples, and addition, omission, replacement, and other changes of the constituents can be made within a range not departing from the features of the present invention.
(Production of Current Collector)
First, as a resin layer, a PET film having a thickness of 6.0 μm was cut to have a length of 100 mm and a width of 10 mm. Next, aluminum having a thickness of 1.0 μm was laminated as a first metal layer on the first surface of the resin layer. Aluminum was not laminated in ranges from both ends of the resin layer to 20 mm away from both ends of the resin layer in the y direction. Next, copper having a thickness of 1.0 μm was laminated as a second metal layer on the second surface of the resin layer. The second metal layer was laminated on the entire second surface of the resin layer.
(Production of Positive Electrode Active Material Layer)
Lithium cobaltate (LiCoO2) was used as a positive electrode active material. A slurry was prepared by dispersing 1.90 parts by mass of this positive electrode active material, 5 parts by mass of acetylene black, and 5 parts by mass of polyvinylidene fluoride (PVDF) into N-methyl-2-pyrrolidone (NMP). The obtained slurry was coated on a part in which the aluminum was laminated on the PET film. Thereafter, it was dried at a temperature of 140° C. for 30 minutes. Thereafter, it was pressed using a roll press apparatus to obtain a positive electrode active material layer.
(Production of Negative Electrode Active Material Layer)
A slurry was prepared by dispersing 90 parts by mass of natural graphite powder (negative electrode active material) and 10 parts by mass of PVDF into NMP. The obtained slurry was coated on a part in which copper was laminated on the PET film. Thereafter, it was dried under reduced pressure at a temperature of 140° C. for 30 minutes. Thereafter, it was pressed using a roll press apparatus to obtain a negative electrode active material layer.
(Preparation of Separator)
A polyethylene microporous film (porosity: 40%, shutdown temperature: 134° C.) having a film thickness of 20 μm was prepared.
(Production of Electrode Body)
Portions of the positive electrode active material layer and the negative electrode active material layer were scraped off with a cotton swab soaked in methyl ethyl ketone (MEK), and tabs were connected thereto. Next, the separator was put on one surface of the battery sheet and the resultant laminate was wound around the first end of the resin layer as an axis; and thereby, an electrode body was produced.
(Electrolytic Solution)
As an electrolyte, a nonaqueous electrolyte solution was prepared by dissolving LiPF6 at 1.0 mol/L in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC). The volume ratio between the EC and the DEC in the mixed solvent was EC:DEC=30:70.
(Production of Battery)
A battery cell of Example 1 was produced by sealing the electrode body together with a nonaqueous electrolytic solution in an aluminum laminate.
Ten samples were produced under the same conditions, and it was checked whether the positive electrode and the negative electrode were short-circuited. None of the ten samples in the power storage element according to Example 1 was short-circuited.
Example 2 differed from Example 1 in that aluminum was not laminated in ranges from both ends of the resin layer to 1.0 mm away from both ends of the resin layer in the y direction and ceramic layers were provided in these parts. A main component of the ceramic layers was alumina (Al2O3).
In Example 2 as well, similar to Example 1, ten samples were produced under the same conditions, and it was checked whether the positive electrode and the negative electrode were short-circuited. None of the ten samples in the power storage element according to Example 2 was short-circuited.
In Comparative Example 1, aluminum was also laminated in ranges from both ends of the resin layer to 20 mm away from both ends of the resin layer in the y direction, and the first metal layer was laminated on the entire second surface of the resin layer. In Comparative Example 1 as well, similar to Example 1, ten samples were produced under the same conditions, and it was checked whether the positive electrode and the negative electrode were short-circuited. Six samples among the ten samples of the power storage elements according to Comparative Example 1 were short-circuited.
No short circuit occurred in Examples 1 and 2 having openings or insulating layers in both end portions on the first surface of the resin layer, whereas some samples were short-circuited in Comparative Example 1.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2020/014191 | 3/27/2020 | WO |
