CN110416629A - 全固体电池 - Google Patents
全固体电池 Download PDFInfo
- Publication number
- CN110416629A CN110416629A CN201910308282.4A CN201910308282A CN110416629A CN 110416629 A CN110416629 A CN 110416629A CN 201910308282 A CN201910308282 A CN 201910308282A CN 110416629 A CN110416629 A CN 110416629A
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- CN
- China
- Prior art keywords
- solid
- layer
- state battery
- current collector
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000006183 anode active material Substances 0.000 claims abstract description 67
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 41
- 230000003746 surface roughness Effects 0.000 claims abstract description 38
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 abstract description 5
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 278
- 239000007773 negative electrode material Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910000676 Si alloy Inorganic materials 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000005404 monopole Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002203 sulfidic glass Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 description 2
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910008088 Li-Mn Inorganic materials 0.000 description 1
- 229910006194 Li1+xAlxGe2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006196 Li1+xAlxGe2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 description 1
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 description 1
- 229910006554 Li1+xMn2-x-yMyO4 Inorganic materials 0.000 description 1
- 229910006601 Li1+xMn2−x−yMyO4 Inorganic materials 0.000 description 1
- 229910003405 Li10GeP2S12 Inorganic materials 0.000 description 1
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910009225 Li2S—P2S5—GeS2 Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910011244 Li3xLa2/3-xTiO3 Inorganic materials 0.000 description 1
- 229910011245 Li3xLa2/3−xTiO3 Inorganic materials 0.000 description 1
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 1
- 229910011103 Li7−xPS6−xClx Inorganic materials 0.000 description 1
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910010835 LiI-Li2S-P2S5 Inorganic materials 0.000 description 1
- 229910010833 LiI-Li2S-SiS2 Inorganic materials 0.000 description 1
- 229910010842 LiI—Li2S—P2O5 Inorganic materials 0.000 description 1
- 229910010840 LiI—Li2S—P2S5 Inorganic materials 0.000 description 1
- 229910010855 LiI—Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910010847 LiI—Li3PO4-P2S5 Inorganic materials 0.000 description 1
- 229910010864 LiI—Li3PO4—P2S5 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910006327 Li—Mn Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019195 PO4−xNx Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- -1 tin nitride Chemical class 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—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
- H01M10/0562—Solid materials
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- H01M10/0486—Frames for plates or membranes
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
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- B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
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- B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
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- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/048—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of particles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0413—Large-sized flat cells or batteries for motive or stationary systems with plate-like electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/387—Tin or alloys based on tin
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Abstract
本发明提供一种全固体电池,其为由树脂层将全固体电池层叠体的侧面包覆的全固体电池,能够提高全固体电池层叠体与树脂层的粘接性,使结构稳定化。一种全固体电池,具有:全固体电池层叠体,所述全固体电池层叠体具有1个以上全固体单元电池,所述全固体单元电池由正极集电器层、正极活性材料层、固体电解质层、负极活性材料层、和负极集电器层依次层叠而成;和树脂层,所述树脂层将全固体电池层叠体的侧面包覆,正极集电器层和负极集电器层之中至少一层的至少一个面具有层叠部和伸出部,层叠部是与相邻的其它层重叠的部分,伸出部是与该相邻的其它层相比伸出的部分,且伸出部的表面粗糙度大于层叠部的表面粗糙度。
Description
技术领域
本公开内容涉及全固体电池。本公开内容特别涉及具有全固体电池层叠体和将全固体电池层叠体包覆的树脂层的全固体电池。
背景技术
近年来,为了提高安全性,将电解液置换为固体电解质而得的全固体电池特别受到关注。其中,公开了各种与全固体电池层叠体相关的开发。例如在专利文献1中公开了一种具有集电器的双极电池,所述集电器的电极层形成部分与密封构件粘贴部分的表面粗糙度是不同的。另外,在专利文献2中公开了一种全固体电池,其具有如下的结构:相同极性的、表面粗糙化的电极集电器彼此按照面对的方式重叠。
另外,为了提高全固体电池的能量密度,也报告了一种全固体电池,其使用树脂层仅将全固体电池层叠体的侧面包覆来替代外包装体(例如专利文献3)。在专利文献3的全固体电池层叠体中,集电器层、正极混合物层(正极活性材料层)、固体电解质层、和负极混合物层(负极活性材料层)之中至少1层与其它层相比向外侧伸出而成为伸出层,在层叠电池的侧面有多个该伸出层伸出。
现有技术文献
专利文献
专利文献1:日本特开2007-188746号公报
专利文献2:日本特开2017-157271号公报
专利文献3:日本特开2017-220447号公报
发明内容
发明所要解决的课题
在由树脂层将全固体电池层叠体的侧面包覆的全固体电池中,在充放电之时全固体电池层叠体发生体积变化时,全固体电池层叠体与树脂层的粘接部发生剥离,由此,存在全固体电池的结构变得不稳定的可能性。
因此,本公开内容鉴于上述情形而作出,其目的在于提供一种全固体电池,其为由树脂层将全固体电池层叠体的侧面包覆的全固体电池,提高了全固体电池层叠体与树脂层之间的粘接性,由此在结构上稳定。
用于解决课题的手段
本公开内容的本发明人发现,能够利用以下的手段解决上述课题。
<方式1>
一种全固体电池,具有:
全固体电池层叠体,所述全固体电池层叠体具有1个以上全固体单元电池,所述全固体单元电池由正极集电器层、正极活性材料层、固体电解质层、负极活性材料层和负极集电器层依次层叠而成;和
树脂层,所述树脂层将所述全固体电池层叠体的侧面包覆,
所述正极集电器层和所述负极集电器层之中至少一层的至少一个面具有层叠部和伸出部,
所述层叠部是与相邻的其它层重叠的部分,所述伸出部是与所述相邻的其它层相比伸出的部分,且
所述伸出部的表面粗糙度大于所述层叠部的表面粗糙度。
<方式2>
根据方式1所述的全固体电池,其中,全部的所述正极集电器层和全部的所述负极集电器层的至少一个面具有所述层叠部和所述伸出部。
<方式3>
根据方式1或2所述的全固体电池,其中,所述正极集电器层和所述负极集电器层之中至少一层的两个面具有所述层叠部和所述伸出部。
<方式4>
根据方式1至3中任一项所述的全固体电池,其中,所述正极活性材料层与所述负极活性材料层的面积是不同的。
<方式5>
根据方式1至4中任一项所述的全固体电池,其中,所述负极活性材料层的面积大于所述正极活性材料层的面积。
<方式6>
根据方式1至5中任一项所述的全固体电池,其中,所述树脂层的材料是固化性树脂或热塑性树脂。
<方式7>
根据方式1至6中任一项所述的全固体电池,其中,所述全固体电池层叠体在层叠方向被约束。
<方式8>
根据方式1至7中任一项所述的全固体电池,其中,所述全固体电池是全固体锂离子二次电池。
发明效果
根据本公开内容,在由树脂层将全固体电池层叠体的侧面包覆的全固体电池中,利用集电器层的表面粗糙度相对大的伸出部,提高了全固体电池层叠体与树脂层的粘接性,由此,能够使全固体电池在结构上稳定化。
此外,根据本公开内容,通过全固体电池在结构上稳定化,能够促进在电池内部产生的热通过树脂层向电池外部释放。
附图说明
[图1]图1为示出本公开内容的全固体电池的一个例子的示意截面图。
[图2]图2为示出本公开内容的全固体电池的一部分的示意图。
[图3]图3为示出本公开内容的全固体电池的一个例子的示意截面图。
符号说明
1、1a、1b、1c、1d 正极集电器层
2、2a、2b、2c、2d 正极活性材料层
3、3a、3b、3c、3d 固体电解质层
4、4a、4b、4c、4d 负极活性材料层
5、5a、5b、5c、5d 负极集电器层
6a、6b、6c、6d 全固体单元电池
7、9 正极活性材料层
8 正极集电器层
10、20 全固体电池层叠体
11、21 树脂层
100、200 全固体电池
具体实施方式
以下,一边参照附图,一边对用于实施本公开内容的方式进行详细说明。需要说明的是,为了方便说明,在各图中对于相同或相当的部分赋予相同的参考符号、并省略重复说明。实施方式的各构成要素并非全都限定为必需物,也存在可省略一部分构成要素的情况。当然,以下的图中所示的方式不过是本公开内容的例示,并不限定本公开内容。
全固体电池
本公开内容的全固体电池具有:
全固体电池层叠体,所述全固体电池层叠体具有1个以上全固体单元电池,所述全固体单元电池由正极集电器层、正极活性材料层、固体电解质层、负极活性材料层和负极集电器层依次层叠而成;和
树脂层,所述树脂层将全固体电池层叠体的侧面包覆,
正极集电器层和负极集电器层之中至少一层的至少一个面具有层叠部和伸出部,
层叠部是与相邻的其它层重叠的部分,伸出部是与该相邻的其它层相比伸出的部分,且
伸出部的表面粗糙度大于层叠部的表面粗糙度。
在本公开内容中,“表面粗糙度”是指基于JIS B0601(1994年)算出的算术平均粗糙度(Ra)。具体地,在从粗糙度曲线沿其中心线的方向选取基准长度L的部分,将该选取部分的中心线设为X轴,将纵向倍率(縦倍率)的方向设为Y轴,并由y=f(x)表示粗糙度曲线时,算术平均粗糙度(Ra)由下式表示:
【数学式1】
需要说明的是,基准长度L可基于JIS B0633(2001)而确定。
图1为示出本公开内容的全固体电池的一个例子的示意截面图。本公开内容的全固体电池100具有:全固体电池层叠体10、和将全固体电池层叠体10的侧面包覆的树脂层11。全固体电池层叠体10具有一个全固体单元电池,所述全固体单元电池由正极集电器层1、正极活性材料层2、固体电解质层3、负极活性材料层4、负极集电器层5依次层叠而成。
在此情况下,例如,正极集电器层1的与正极活性材料层2相邻侧的面具有层叠部和伸出部,该层叠部是与正极活性材料层2重叠的部分,该伸出部是与正极活性材料层2相比伸出的部分。该伸出部的表面粗糙度大于该层叠部的表面粗糙度。
另外,例如,负极集电器层5的与负极活性材料层4相邻侧的面具有层叠部和伸出部,该层叠部是与负极活性材料层4重叠的部分,该伸出部是与负极活性材料层4相比伸出的部分。与上述的正极集电器层1的情况同样地,伸出部的表面粗糙度大于层叠部的表面粗糙度。
需要说明的是,在图1中所示的全固体电池层叠体10中,在正极集电器层1和负极集电器层5两者中分别具有层叠部和伸出部,但实际上,正极集电器层1和负极集电器层5中的仅任一者的层具有层叠部和伸出部的情况也在本公开内容的范围内。
如上所述,由于在充放电之时,产生全固体电池层叠体的体积变化,因此在由树脂层将全固体电池层叠体的侧面包覆的以往的全固体电池中,全固体电池层叠体与树脂层之间的粘接部发生剥离,由此存在全固体电池的结构变得不稳定的可能性。此外,在全固体电池的结构变得不稳定时,也可产生例如如下的课题:在电池内部产生的热变得不易通过树脂层而向电池外部释放。
与此相对,在本公开内容的全固体电池中,正极集电器层和负极集电器层之中至少一层的至少一个面具有层叠部和伸出部,且伸出部的表面粗糙度大于层叠部的表面粗糙度。通过这样地在集电器层中设置表面粗糙度大的伸出部,能够提高集电器层与树脂层的粘接性。
另外,在全固体电池层叠体中,在电池内部产生的热特别容易聚集于集电器层(正极集电器层或负极集电器层),因而在本公开内容的全固体电池中,通过提高集电器层与树脂层的粘接性,使在电池内部产生的热容易通过树脂层而向电池外部释放。
<层叠部和伸出部>
以下,更详细说明本公开内容的全固体电池涉及的层叠部和伸出部。
在本公开内容中,正极集电器层和负极集电器层之中至少一层的至少一个面具有层叠部和伸出部。另外,从更加发挥本公开内容的效果的观点考虑,全部的正极集电器层和全部的负极集电器层的至少一个面优选具有层叠部和伸出部。
层叠部是与相邻的其它层重叠的部分,另外伸出部是与该相邻的其它层相比伸出的部分。即,在正极集电器层的一个面具有层叠部和伸出部的情况下,层叠部是与和正极集电器层的这一个面相邻的其它层例如正极活性材料层重叠的部分。伸出部是与和正极集电器层的该一个面相邻的其它层例如正极活性材料层相比伸出的部分。需要说明的是,在负极集电器层的一个面具有层叠部和伸出部的情况下也同样。
例如,作为本公开内容的全固体电池的一部分,由正极活性材料层7、正极集电器层8、和正极活性材料层9依次层叠而成的层叠体的示意图示于图2中。此时,正极集电器层8的与正极活性材料层7相邻侧的面具有层叠部y和伸出部x。该层叠部y是正极集电器层8与相邻于其的正极活性材料层7重叠的部分,该伸出部x是正极集电器层8与相邻于其的正极活性材料层7相比伸出的部分。本公开内容中,伸出部x的表面粗糙度大于层叠部y的表面粗糙度。需要说明的是,为了方便说明,在图2中省略了将全固体电池层叠体的侧面包覆的树脂层和其它部分。
另外,从更加发挥本公开内容的效果的观点考虑,正极集电器层和负极集电器层之中至少一层的两个面优选具有层叠部和伸出部。
例如,在图2中所示的由正极活性材料层7、正极集电器层8、和正极活性材料层9依次层叠而成的层叠体的情况下,正极集电器层8优选的是,在与正极活性材料层7相邻侧的面具有层叠部y和伸出部x的基础上,与正极活性材料层9相邻侧的面也具有层叠部n和伸出部m。该层叠部n是正极集电器层8与相邻于其的正极活性材料层9重叠的部分,该伸出部m是正极集电器层8与相邻于其的正极活性材料层9相比伸出的部分,伸出部m的表面粗糙度大于层叠部n的表面粗糙度。
需要说明的是,正极集电器层和负极集电器层之中至少一层的两个面具有层叠部和伸出部的情况下,只要相同面中的层叠部和伸出部的表面粗糙度的关系满足“伸出部的表面粗糙度大于层叠部的表面粗糙度”的关系即可。例如,在图2中所示的正极集电器8中,满足伸出部x的表面粗糙度大于层叠部y的表面粗糙度的情况、或者是伸出部m的表面粗糙度大于层叠部n的表面粗糙度的情况中的任一者即可。
此处,关于正极集电器层和/或负极集电器层的相同面中层叠部和伸出部的表面粗糙度,只要满足上述的关系,则各自的表面粗糙度没有特别限定。
例如,伸出部的表面粗糙度可以是与其相同的面中的层叠部的表面粗糙度的1.01倍以上、1.02倍以上、1.03倍以上、1.04倍以上、1.05倍以上、1.06倍以上、1.07倍以上、1.08倍以上、1.09倍以上、1.10倍以上、1.50倍以上、1.80倍以上、2.00倍以上、或2.50倍以上。另外,伸出部的表面粗糙度的上限没有特别限定,只要是在制造、加工过程中能够赋予的表面粗糙度的上限值即可。
层叠部的表面粗糙度的范围没有特别限定,可以是利用公知的制造方法获得的正极集电器层和负极集电器层的通常表面粗糙度的范围,也可以是基于正极集电器层和/或负极集电器层与各自相邻的各活性材料层之间的密合性和接触电阻的平衡而合适地施加的表面粗糙度的范围。
另外,正极集电器层和负极集电器层之中至少一层的各面中的层叠部的表面粗糙度彼此可以相同、也可以不同,但是从方便制造方面的观点考虑,优选为相同。同样地,正极集电器层和负极集电器层之中至少一层的各面中的伸出部表面粗糙度彼此可以相同、也可以不同,但是从方便制造方面的观点考虑,优选为相同。例如,在图2中所示的正极集电器8中,层叠部y与层叠部n的表面粗糙度彼此可以相同、也可以不同,从方便制造方面的观点考虑,优选为相同。另外,伸出部x与伸出部m的表面粗糙度彼此可以相同、也可以不同,从方便制造方面的观点考虑,优选为相同。
在本公开内容中,用于在正极集电器层和负极集电器层的至少一个面上获得表面粗糙度不同的层叠部和伸出部的手段没有特别限定。例如,在制造正极集电器层和负极集电器层之时,或者在制造了正极集电器层和负极集电器层之后,利用辊压等之时的压花加工,可分别获得具有所期望的表面粗糙度的层叠部和伸出部。或者在制造正极集电器层和负极集电器层之时,或在制造了正极集电器层和负极集电器层之后,也可通过实施镀敷处理,分别获得具有所期望的表面粗糙度的层叠部和伸出部。
正极集电器层和负极集电器层之中至少一层的各面中的各个层叠部的面积根据与各面相邻的其它层的面积而确定,因而彼此可以相同、也可以不同。出于同样的理由,正极集电器层和负极集电器层之中至少一层的各面中的伸出部各自的面积彼此可以相同、也可以不同。例如,在图2中所示的正极集电器8中,层叠部y的面积与层叠部n的面积可以相同、也可以不同。另外,伸出部x的面积与伸出部m的面积可以相同、也可以不同。
此外,从更发挥本公开内容的效果的观点考虑,更优选的是,位于最外表层的正极集电器层和/或负极集电器层的除最外表面以外的面、以及其它全部的正极集电器层和其它全部的负极集电器层的两个面具有层叠部和伸出部。
例如,图3为示出本公开内容的全固体电池的一个例子的示意截面图。在图3中所示的全固体电池200中,具有全固体电池层叠体20、和将全固体电池层叠体20的侧面包覆的树脂层21。在此情况下,全固体电池层叠体20具有全固体单元电池6a、6b、6c和6d,在各个全固体单元电池6a、6b、6c和6d中,正极集电器层和负极集电器层全都具有层叠部和伸出部,伸出部的表面粗糙度大于层叠部的表面粗糙度。由此,能够提高全固体电池层叠体20与树脂层21的粘接性,使全固体电池200在结构上稳定化。
<全固体电池层叠体>
在本公开内容中,全固体电池层叠体可具有1个以上的全固体单元电池。另外,全固体单元电池由正极集电器层、正极活性材料层、固体电解质层、负极活性材料层、和负极集电器层依次层叠而成。
例如,图3中所示的全固体电池层叠体20具有4个全固体单元电池6a、6b、6c和6d。另外,全固体单元电池6a由正极集电器层1a、正极活性材料层2a、固体电解质层3a、负极活性材料层4a、和负极集电器层5a(5b)依次层叠而成。全固体单元电池6b由负极集电器层5a(5b)、负极活性材料层4b、固体电解质层3b、正极活性材料层2b、和正极集电器层1b(1c)依次层叠而成。全固体单元电池6c由正极集电器层1b(1c)、正极活性材料层2c、固体电解质层3c、负极活性材料层4c、和负极集电器层5c(5d)依次层叠而成。全固体单元电池6由负极集电器层5c(5d)、负极活性材料层4d、固体电解质层3d、正极活性材料层2d、正极集电器层1d依次层叠而成。
另外,全固体电池层叠体具有2个以上的全固体单元电池的情况下,可以是单极型的全固体电池层叠体,也可以是双极型的全固体电池层叠体。
在单极型的全固体电池层叠体的情况下,在层叠方向相邻的2个全固体单元电池可以是共有正极集电器层或负极集电器层的单极型的构成。例如如图3中所示的那样,相邻的全固体单元电池6a和6b共有负极集电器层5a(5b),相邻的全固体单元电池6b和6c共有正极集电器层1b(1c),另外相邻的全固体单元电池6c和6d共有负极集电器层5c(5d),将这些全固体单元电池6a、6b、6c和6d组合而构成了单极型的全固体电池层叠体20。
在双极型的全固体电池层叠体的情况下,在层叠方向相邻的2个全固体单元电池可以是,将用作正极集电器层和负极集电器层两者的正极/负极集电器层共有的双极型的构成。因此,例如全固体电池层叠体可以是,将用作正极集电器层和负极集电器层两者的正极/负极集电器层共有的3个全固体单元电池的层叠体,具体地,可依次具有正极集电器层、正极活性材料层、固体电解质层、负极活性材料层、正极/负极集电器层、正极活性材料层、固体电解质层、负极活性材料层、正极/负极集电器层、正极活性材料层、固体电解质层、负极活性材料层、和负极集电器层(未图示)。另外,在此情况下,“正极/负极集电器层”用作正极集电器层和负极集电器层两者,因而对本公开内容所说的“正极集电器层”或“负极集电器层”中的任一者均适用。即,“正极/负极集电器层”之中至少一层的至少一个面可具有上述的层叠部和伸出部。
在本公开内容中,正极活性材料层和负极活性材料层的面积优选为不同。特别是,负极活性材料层的面积优选大于正极活性材料层的面积。由此,在充电之时,可使锂离子从正极活性材料层可靠地移动到负极活性材料层。
另外,本公开内容的全固体电池可具有电连接至正极集电器层的正极集电极耳,且可具有电连接至负极集电器层的负极集电极耳。在此情况下,这些集电极耳可从树脂层突出。根据该构成,可经由集电极耳,将由全固体电池层叠体产生的电力取出至外部。
正极集电器层可具有向面方向突出的正极集电器突出部,正极集电极耳可电连接至该正极集电器突出部。同样地,负极集电器层可具有负极集电器突出部,负极集电极耳可电连接至该负极集电器突出部。
另外,在本公开内容的全固体电池中,全固体电池层叠体优选在层叠方向被约束。由此,在充放电之时,可改良在全固体电池层叠体的各层的内部和各层之间离子和电子的传导性,可进一步促进电池反应。
以下,对全固体电池层叠体涉及的各构件进行详细说明。需要说明的是,为了容易地理解本公开内容,以全固体锂离子二次电池的全固体电池层叠体涉及的各构件为例进行说明,但是本公开内容的全固体电池不限定于锂离子二次电池,并可广泛地应用。
(正极集电器层)
正极集电器层中使用的导电材料没有特别限定,可合适地采用在全固体电池中能够使用的导电材料。例如,正极集电器层中使用的导电材料可以是SUS、铝、铜、镍、铁、钛或碳等,但是不限定于它们。
作为正极集电器层的形状,没有特别限定,例如可列举箔状、板状、网眼状等。它们之中,优选为箔状。
(正极活性材料层)
正极活性材料层至少包含正极活性材料,优选还包含后述的固体电解质。此外,可根据使用用途、使用目的等,包含例如导电助剂或粘合剂等在全固体电池的正极活性材料层中使用的添加剂。
作为正极活性材料的材料,没有特别限定。例如,正极活性材料可以是钴酸锂(LiCoO2)、镍酸锂(LiNiO2)、锰酸锂(LiMn2O4)、LiCo1/3Ni1/3Mn1/3O2、由Li1+xMn2-x-yMyO4(M是选自Al、Mg、Co、Fe、Ni和Zn中的1种以上金属元素)表示的组成的异种元素置换Li-Mn尖晶石等,但是不限定于它们。
作为导电助剂,没有特别限定。例如,导电助剂可以是VGCF(气相生长法碳纤维,Vapor Grown Carbon Fiber)和碳纳米纤维等碳材料和金属材料等,但是不限定于它们。
作为粘合剂,没有特别限定。例如,粘合剂可以是聚偏二氟乙烯(PVdF)、羧甲基纤维素(CMC)、丁二烯橡胶(BR)或者丁苯橡胶(SBR)等材料,或它们的组合,但是不限定于它们。
(固体电解质层)
固体电解质层至少包含固体电解质。作为固体电解质没有特别限定,可使用能够用作全固体电池的固体电解质的材料。例如,固体电解质可以是硫化物固体电解质、氧化物固体电解质、或聚合物电解质等,但是不限定于它们。
作为硫化物固体电解质的例子,可列举硫化物系非晶质固体电解质、硫化物系晶质固体电解质、或硫银锗矿(アルジロダイト)型固体电解质等,但是不限定于它们。作为具体的硫化物固体电解质的例子,可列举Li2S-P2S5系(Li7P3S11、Li3PS4、Li8P2S9等)、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Li2S-P2S5、LiI-LiBr-Li2S-P2S5、Li2S-P2S5-GeS2(Li13GeP3S16、Li10GeP2S12等)、LiI-Li2S-P2O5、LiI-Li3PO4-P2S5、Li7-xPS6-xClx等;或它们的组合,但是不限定于它们。
作为氧化物固体电解质的例子,可列举Li7La3Zr2O12、Li7-xLa3Zr1-xNbxO12、Li7- 3xLa3Zr2AlxO12、Li3xLa2/3-xTiO3、Li1+xAlxTi2-x(PO4)3、Li1+xAlxGe2-x(PO4)3、Li3PO4或Li3+xPO4-xNx(LiPON)等,但是不限定于它们。
(聚合物电解质)
作为聚合物电解质,可列举聚环氧乙烷(PEO)、聚环氧丙烷(PPO)、和它们的共聚物等,但是不限定于它们。
固体电解质可以是玻璃,也可以是结晶玻璃(玻璃陶瓷)。另外,固体电解质层除了包含上述的固体电解质以外,也可根据需要而包含粘合剂等。作为具体例子与上述的“正极活性材料层”中列举的“粘合剂”相同,此处省略说明。
(负极活性材料层)
负极活性材料层至少包含负极活性材料,优选还包含上述的固体电解质。此外,可根据使用用途、使用目的等,包含例如导电助剂、粘合剂等在全固体电池的负极活性材料层中使用的添加剂。
作为负极活性材料的材料没有特别限定,优选能够吸藏和释放锂离子等金属离子。例如,负极活性材料可以是合金系负极活性材料或碳材料等,但是不限定于它们。
作为合金系负极活性材料,没有特别限定,例如可列举Si合金系负极活性材料、或Sn合金系负极活性材料等。在Si合金系负极活性材料中,存在硅、硅氧化物、硅碳化物、硅氮化物、或它们的固溶体等。另外,在Si合金系负极活性材料中,可包含除了硅以外的元素,例如Fe、Co、Sb、Bi、Pb、Ni、Cu、Zn、Ge、In、Sn、Ti等。在Sn合金系负极活性材料中,存在锡、锡氧化物、锡氮化物、或它们的固溶体等。另外,在Sn合金系负极活性材料中,可包含除了锡以外的元素,例如Fe、Co、Sb、Bi、Pb、Ni、Cu、Zn、Ge、In、Ti、Si等。它们之中,优选Si合金系负极活性材料。
作为碳材料,没有特别限定,例如可列举硬碳、软碳、或石墨等。
关于在负极活性材料层中使用的固体电解质、导电助剂、粘合剂等其它的添加剂,可合适地采用上述的“正极活性材料层”和“固体电解质层”的项目中说明的材料。
(负极集电器层)
负极集电器层中使用的导电材料没有特别限定,可合适地采用在全固体电池中能够使用的导电材料。例如,在负极集电器层中使用的导电材料可以是SUS、铝、铜、镍、铁、钛或碳等,但是不限定于它们。
作为负极集电器层的形状,没有特别限定,例如可列举箔状、板状、网眼状等。它们之中,优选为箔状。
<树脂层>
在本公开内容中,树脂层的材料没有特别限定,可以与在一般的全固体电池中使用的绝缘性树脂材料相同。
例如,树脂层的材料可以是固化性树脂或热塑性树脂。另外,固化性树脂可以是热固化性树脂、光固化性树脂(例如,UV固化性树脂)、或电子束固化性树脂。更具体地,例如,树脂层的材料可以是环氧树脂、丙烯酸类树脂、聚酰亚胺树脂、聚酯树脂、聚丙烯树脂、聚酰胺树脂、聚苯乙烯树脂、聚氯乙烯树脂、或聚碳酸酯树脂,但是不限定于它们。
在本公开内容中,树脂层将全固体电池层叠体的侧面包覆。由此,在本公开内容的全固体电池的外侧,可以不具有层压膜、金属罐等外包装体。因此,本公开内容的全固体电池与需要外包装体的以往的全固体电池相比更紧凑,这也导致电池的能量密度提高。但是,本公开内容之一也可进一步具有它们的外包装体。
例如,可如图3中所示的全固体电池200那样,层叠方向的上侧的端面和下侧的端面是正极集电器层1a和1d,仅全固体电池层叠体20的侧面由多层结构的树脂层21包覆。需要说明的是,根据全固体电池层叠体的层叠顺序,层叠方向的上侧的端面和下侧的端面不限定于正极集电器层,也可以是负极集电器层。
另外,本公开内容的全固体电池可以是如下的全固体电池:全固体电池层叠体的层叠方向的上侧的端面和下侧的端面由膜等包覆,且至少全固体电池层叠体的侧面由树脂层包覆。另外,本公开内容的全固体电池也可以是如下的全固体电池:全固体电池层叠体的层叠方向的上侧的端面和/或下侧的端面也由树脂层包覆。
《全固体电池的种类》
在本公开内容中,作为全固体电池的种类,可列举全固体锂离子电池、全固体钠离子电池、全固体镁离子电池和全固体钙离子电池等。其中,优选全固体锂离子电池和全固体钠离子电池,特别优选全固体锂离子电池。
另外,本公开内容的全固体电池可以是一次电池,也可以是二次电池,但其中优选二次电池。这是因为,二次电池可反复充放电,例如可用作车载用电池。因此,本公开内容的全固体电池优选为全固体锂离子二次电池。
Claims (8)
1.全固体电池,具有:
全固体电池层叠体,所述全固体电池层叠体具有1个以上全固体单元电池,所述全固体单元电池由正极集电器层、正极活性材料层、固体电解质层、负极活性材料层和负极集电器层依次层叠而成;和
树脂层,所述树脂层将所述全固体电池层叠体的侧面包覆,
所述正极集电器层和所述负极集电器层之中至少一层的至少一个面具有层叠部和伸出部,
所述层叠部是与相邻的其它层重叠的部分,所述伸出部是与所述相邻的其它层相比伸出的部分,且
所述伸出部的表面粗糙度大于所述层叠部的表面粗糙度。
2.根据权利要求1所述的全固体电池,其中,全部的所述正极集电器层和全部的所述负极集电器层的至少一个面具有所述层叠部和所述伸出部。
3.根据权利要求1或2所述的全固体电池,其中,所述正极集电器层和所述负极集电器层之中至少一层的两个面具有所述层叠部和所述伸出部。
4.根据权利要求1至3中任一项所述的全固体电池,其中,所述正极活性材料层与所述负极活性材料层的面积是不同的。
5.根据权利要求1至4中任一项所述的全固体电池,其中,所述负极活性材料层的面积大于所述正极活性材料层的面积。
6.根据权利要求1至5中任一项所述的全固体电池,其中,所述树脂层的材料是固化性树脂或热塑性树脂。
7.根据权利要求1至6中任一项所述的全固体电池,其中,所述全固体电池层叠体在层叠方向被约束。
8.根据权利要求1至7中任一项所述的全固体电池,其中,所述全固体电池是全固体锂离子二次电池。
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