WO2022239818A1 - Electric power storage element and electric power storage device - Google Patents
Electric power storage element and electric power storage device Download PDFInfo
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- WO2022239818A1 WO2022239818A1 PCT/JP2022/020004 JP2022020004W WO2022239818A1 WO 2022239818 A1 WO2022239818 A1 WO 2022239818A1 JP 2022020004 W JP2022020004 W JP 2022020004W WO 2022239818 A1 WO2022239818 A1 WO 2022239818A1
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- ZKOGUIGAVNCCKH-UHFFFAOYSA-N 4-phenyl-1,3-dioxolan-2-one Chemical compound O1C(=O)OCC1C1=CC=CC=C1 ZKOGUIGAVNCCKH-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005933 Ge—P Inorganic materials 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
- 229910000578 Li2CoPO4F Inorganic materials 0.000 description 1
- 229910010142 Li2MnSiO4 Inorganic materials 0.000 description 1
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013375 LiC Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- WLLOZRDOFANZMZ-UHFFFAOYSA-N bis(2,2,2-trifluoroethyl) carbonate Chemical compound FC(F)(F)COC(=O)OCC(F)(F)F WLLOZRDOFANZMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XVOCEVMHNRHJMX-UHFFFAOYSA-N ethyl-hydroxy-oxogermane Chemical compound CC[Ge](O)=O XVOCEVMHNRHJMX-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical class O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 239000003273 ketjen black Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 159000000003 magnesium salts Chemical class 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000010703 silicon Substances 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The electric power storage element according to an embodiment of the present invention is provided with an electrode body in which a first electrode and a second electrode are stacked in the thickness direction with a separator interposed therebetween, a non-aqueous electrolyte, and a vessel containing the electrode body and the non-aqueous electrolyte. The first electrode has a first electrode active material layer that includes first electrode active material particles, and the second electrode has a second electrode active material layer that includes second electrode active material particles and is harder than the first electrode active material layer. The separator has a base material layer and a protective layer. The protective layer is arranged on a surface on the second electrode side of the base material layer and is harder than the base material layer, the average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles, and the average thickness of the base material layer is equal to or greater than the average diameter of the first electrode active material particles. The electrode body is pressed in the thickness direction of the electrode body.
Description
本発明は、蓄電素子及び蓄電装置に関する。
The present invention relates to an electric storage element and an electric storage device.
リチウムイオン二次電池に代表される非水電解質二次電池は、エネルギー密度の高さから、パーソナルコンピュータ、通信端末等の電子機器、自動車等に多用されている。上記非水電解質二次電池は、一般的には、一対の電極及びセパレータを有する電極体と、非水電解質と、これら電極体及び非水電解質を収容する容器とを有し、両電極間でイオンの受け渡しを行うことで充放電するよう構成される。
Non-aqueous electrolyte secondary batteries, typified by lithium-ion secondary batteries, are widely used in electronic devices such as personal computers, communication terminals, and automobiles due to their high energy density. The non-aqueous electrolyte secondary battery generally has an electrode body having a pair of electrodes and a separator, a non-aqueous electrolyte, and a container containing the electrode body and the non-aqueous electrolyte. It is configured to be charged and discharged by transferring ions.
このような非水電解質二次電池では、内部抵抗が増加したり、微小短絡等による自己放電が発生したりするおそれがある。
In such a non-aqueous electrolyte secondary battery, the internal resistance may increase, or self-discharge may occur due to a micro short circuit or the like.
そこで、内部抵抗の増加を抑制すべく、セパレータと、活物質粒子を含む活物質層と、上記セパレータ及び上記活物質層の間に配置され且つ第一粒子を含む中間層を備え、上記セパレータが第二粒子を含有する基材層を有する蓄電素子が提案されている（特開２０１９－４６６４８号公報参照）。
Therefore, in order to suppress the increase in internal resistance, a separator, an active material layer containing active material particles, and an intermediate layer disposed between the separator and the active material layer and containing the first particles are provided, and the separator is A power storage device having a substrate layer containing second particles has been proposed (see Japanese Patent Application Laid-Open No. 2019-46648).
一方、短絡の発生を抑制すべく、正極及び負極がセパレータを介して積層された構造を有する電極体を備え、上記正極及び負極の少なくとも一方の電極と上記セパレータとの間に多孔質のフィラー層が形成された非水電解質二次電池が提案されている（国際公報第２０１２／１５０６３５号参照）。
On the other hand, in order to suppress the occurrence of a short circuit, an electrode body having a structure in which a positive electrode and a negative electrode are laminated with a separator interposed therebetween is provided, and a porous filler layer is provided between at least one electrode of the positive electrode and the negative electrode and the separator. is proposed (see International Publication No. 2012/150635).
しかし、上述した蓄電素子及び非水電解質二次電池は、電極体がその厚さ方向に押圧された状態での内部抵抗の増加抑制及び自己放電の抑制が十分とはいい難い。
However, it is difficult to say that the electric storage element and the non-aqueous electrolyte secondary battery described above sufficiently suppress the increase in internal resistance and the suppression of self-discharge when the electrode body is pressed in the thickness direction.
上記事情に鑑み、本発明の目的は、電極体がその厚さ方向に押圧された状態で、内部抵抗の増加が抑制され、かつ自己放電が抑制された蓄電素子、及びそれを備える蓄電装置を提供することである。
In view of the above circumstances, an object of the present invention is to provide a power storage element in which an increase in internal resistance and self-discharge are suppressed in a state in which an electrode body is pressed in its thickness direction, and a power storage device comprising the same. to provide.
上記課題を解決するためになされた本発明の一態様に係る蓄電素子は、第１電極と、第２電極とが、セパレータを介して厚さ方向に重ね合わされてなる電極体と、非水電解質と、上記電極体及び非水電解質を収容する容器とを備え、上記第１電極が第１電極活物質粒子を含む第１電極活物質層を有し、上記第２電極が第２電極活物質粒子を含み、かつ上記第１電極活物質層よりも硬い第２電極活物質層を有し、上記セパレータが、基材層及び保護層を有し、上記保護層が、上記基材層における上記第２電極側の表面に配置され、かつ上記基材層よりも硬く、上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であり、上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であり、上記電極体の厚さ方向に上記電極体が押圧された状態である。
A power storage element according to one aspect of the present invention, which has been made to solve the above problems, includes an electrode body in which a first electrode and a second electrode are superimposed in the thickness direction with a separator interposed therebetween; and a container containing the electrode body and the non-aqueous electrolyte, the first electrode having a first electrode active material layer containing first electrode active material particles, and the second electrode having a second electrode active material A second electrode active material layer containing particles and harder than the first electrode active material layer, the separator having a base material layer and a protective layer, the protective layer having the above It is arranged on the surface on the second electrode side and is harder than the base layer, the average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles, and the average thickness of the base layer is It is equal to or greater than the average diameter of the first electrode active material particles, and is a state in which the electrode body is pressed in the thickness direction of the electrode body.
本発明の他の一態様に係る蓄電装置は、当該１又は複数の蓄電素子と、上記１又は複数の蓄電素子を拘束する拘束部材とを備え、上記拘束部材による拘束により上記１又は複数の蓄電素子の上記電極体が上記厚さ方向に押圧された状態である。
A power storage device according to another aspect of the present invention includes the one or more power storage elements and a restraining member that restrains the one or more power storage elements, and the one or more power storage elements are restrained by the restraining member. The electrode body of the element is pressed in the thickness direction.
本発明によれば、電極体がその厚さ方向に押圧された状態で、内部抵抗の増加が抑制され、かつ自己放電が抑制された蓄電素子及びそれを備える蓄電装置が提供される。
According to the present invention, a power storage element and a power storage device including the same are provided in which an increase in internal resistance is suppressed and self-discharge is suppressed in a state in which the electrode body is pressed in the thickness direction.
本発明の一実施形態は以下の各態様を提供する。
One embodiment of the present invention provides the following aspects.
項１．
第１電極と、第２電極とが、セパレータを介して厚さ方向に重ね合わされてなる電極体と、
非水電解質と、
上記電極体及び非水電解質を収容する容器と
を備え、
上記第１電極が、第１電極活物質粒子を含む第１電極活物質層を有し、
上記第２電極が、第２電極活物質粒子を含み、かつ上記第１電極活物質層よりも硬い第２電極活物質層を有し、
上記セパレータが、基材層及び保護層を有し、
上記保護層が、上記基材層における上記第２電極側の表面に配置され、かつ上記基材層よりも硬く、
上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であり、
上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であり、
上記電極体の厚さ方向に上記電極体が押圧された状態である蓄電素子。Section 1.
an electrode body in which a first electrode and a second electrode are superimposed in a thickness direction with a separator interposed therebetween;
a non-aqueous electrolyte;
and a container containing the electrode body and the non-aqueous electrolyte,
The first electrode has a first electrode active material layer containing first electrode active material particles,
The second electrode has a second electrode active material layer containing second electrode active material particles and harder than the first electrode active material layer,
The separator has a base material layer and a protective layer,
The protective layer is disposed on the surface of the base layer on the second electrode side and is harder than the base layer,
The average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles,
The average thickness of the substrate layer is equal to or greater than the average diameter of the first electrode active material particles,
A storage element in which the electrode body is pressed in the thickness direction of the electrode body.
第１電極と、第２電極とが、セパレータを介して厚さ方向に重ね合わされてなる電極体と、
非水電解質と、
上記電極体及び非水電解質を収容する容器と
を備え、
上記第１電極が、第１電極活物質粒子を含む第１電極活物質層を有し、
上記第２電極が、第２電極活物質粒子を含み、かつ上記第１電極活物質層よりも硬い第２電極活物質層を有し、
上記セパレータが、基材層及び保護層を有し、
上記保護層が、上記基材層における上記第２電極側の表面に配置され、かつ上記基材層よりも硬く、
上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であり、
上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であり、
上記電極体の厚さ方向に上記電極体が押圧された状態である蓄電素子。
an electrode body in which a first electrode and a second electrode are superimposed in a thickness direction with a separator interposed therebetween;
a non-aqueous electrolyte;
and a container containing the electrode body and the non-aqueous electrolyte,
The first electrode has a first electrode active material layer containing first electrode active material particles,
The second electrode has a second electrode active material layer containing second electrode active material particles and harder than the first electrode active material layer,
The separator has a base material layer and a protective layer,
The protective layer is disposed on the surface of the base layer on the second electrode side and is harder than the base layer,
The average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles,
The average thickness of the substrate layer is equal to or greater than the average diameter of the first electrode active material particles,
A storage element in which the electrode body is pressed in the thickness direction of the electrode body.
項２．
上記保護層が上記第２電極活物質層よりも硬い項１に記載の蓄電素子。Section 2.
Item 2. The electric storage element according to Item 1, wherein the protective layer is harder than the second electrode active material layer.
上記保護層が上記第２電極活物質層よりも硬い項１に記載の蓄電素子。
項３．
上記第２電極活物質粒子の平均直径が上記第１電極活物質粒子の平均直径よりも小さい項１又は項２に記載の蓄電素子。Item 3.
Item 3. The power storage element according to item 1 or item 2, wherein the average diameter of the second electrode active material particles is smaller than the average diameter of the first electrode active material particles.
上記第２電極活物質粒子の平均直径が上記第１電極活物質粒子の平均直径よりも小さい項１又は項２に記載の蓄電素子。
項４．
上記第１電極活物質層が上記基材層よりも硬い項１、項２又は項３に記載の蓄電素子。Section 4.
Item 1, Item 2, or Item 3, wherein the first electrode active material layer is harder than the substrate layer.
上記第１電極活物質層が上記基材層よりも硬い項１、項２又は項３に記載の蓄電素子。
項５．
上記電極体の厚さ方向に上記電極体に加えられる押圧力は０．３ＭＰａ以上である項１から項４のいずれか１項に記載の蓄電素子。Item 5.
Item 5. The electric storage element according to any one of Items 1 to 4, wherein a pressing force applied to the electrode body in the thickness direction of the electrode body is 0.3 MPa or more.
上記電極体の厚さ方向に上記電極体に加えられる押圧力は０．３ＭＰａ以上である項１から項４のいずれか１項に記載の蓄電素子。
項６．
項１から項５のいずれか１項に記載の１又は複数の蓄電素子と、
上記１又は複数の蓄電素子を拘束する拘束部材と
を備え、
上記拘束部材による拘束により上記１又は複数の蓄電素子の上記電極体が上記厚さ方向に押圧された状態である蓄電装置。 Item 6.
1 or a plurality of power storage elements according to any one ofitems 1 to 5;
a restraining member that restrains the one or more power storage elements,
A power storage device in which the electrode bodies of the one or more power storage elements are pressed in the thickness direction by restraint by the restraining member.
項１から項５のいずれか１項に記載の１又は複数の蓄電素子と、
上記１又は複数の蓄電素子を拘束する拘束部材と
を備え、
上記拘束部材による拘束により上記１又は複数の蓄電素子の上記電極体が上記厚さ方向に押圧された状態である蓄電装置。 Item 6.
1 or a plurality of power storage elements according to any one of
a restraining member that restrains the one or more power storage elements,
A power storage device in which the electrode bodies of the one or more power storage elements are pressed in the thickness direction by restraint by the restraining member.
初めに、本明細書によって開示される蓄電素子、蓄電素子の製造方法、及び蓄電装置の概要について説明する。
First, an outline of the power storage element, the method for manufacturing the power storage element, and the power storage device disclosed by the present specification will be described.
本発明の一態様に係る蓄電素子は、第１電極と、第２電極とが、セパレータを介して厚さ方向に重ね合わされてなる電極体と、非水電解質と、上記電極体及び非水電解質を収容する容器とを備え、上記第１電極が、第１電極活物質粒子を含む第１電極活物質層を有し、上記第２電極が、第２電極活物質粒子を含み、かつ上記第１電極活物質層よりも硬い第２電極活物質層を有し、上記セパレータが、基材層及び保護層を有し、上記保護層が、上記基材層における上記第２電極側の表面に配置され、かつ上記基材層よりも硬く、上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であり、上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であり、上記電極体の厚さ方向に上記電極体が押圧された状態である。
A power storage device according to an aspect of the present invention includes an electrode body in which a first electrode and a second electrode are stacked in a thickness direction with a separator interposed therebetween, a non-aqueous electrolyte, the electrode body and the non-aqueous electrolyte The first electrode has a first electrode active material layer containing first electrode active material particles, the second electrode contains second electrode active material particles, and the second It has a second electrode active material layer harder than the first electrode active material layer, the separator has a base layer and a protective layer, and the protective layer is on the surface of the base layer on the second electrode side and is harder than the substrate layer, the average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles, and the average thickness of the substrate layer is the first electrode active material particles , and the electrode body is pressed in the thickness direction of the electrode body.
このように上記第２電極活物質層が上記第１電極活物質層よりも硬く、これに応じて上記第２電極活物質層側（すなわち、第２電極側）の表面に配置された上記保護層が上記第１電極活物質層側（すなわち、第１電極側）の表面に配置された上記基材層よりも硬いことで、比較的柔らかい第１電極活物質層に対しては比較的柔らかい基材層、比較的硬い第１電極活物質層に対しては比較的硬い保護層を対向させることができる。
セパレータによって電極間の接触を抑制するにあたり、このように電極活物質層の硬さに応じて対向させる保護層及び基材層を配置することにより、これら保護層及び基材層の厚さを過度に大きくする必要がないため、これらの厚さの増加に起因する内部抵抗の増加が抑制される。
ここで、通常、電極活物質層の硬さは、これに含まれる電極活物質粒子の硬さに依存する。
よって、上記のように上記第１及び第２電極活物質層の硬さに応じて、硬さの異なる上記基材層及び保護層を適切に対向させることで、第１電極活物質粒子及び第２電極活物質粒子がそれぞれ基材層及び保護層に対してメリ込むことを抑制することができる。
加えて、上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であることで、上記第２電極活物質粒子が上記保護層にメリ込んだ場合であっても、上記第２電極活物質粒子が上記保護層を突き抜けて上記基材層に到達することを抑制することができる。
また、上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であることで、上記第１電極活物質粒子が上記基材層に対してメリ込んだ場合であっても、上記第１電極活物質粒子が上記基材層を突き抜けて上記保護層に到達することを抑制することができる。
よって、当該蓄電素子は、上記セパレータ内での上記第１電極活物質粒子と上記第２電極活物質粒子との接触が抑制されたものとなり、これにより、微小短絡等による自己放電を抑制することができる。
ここで、一般的に蓄電素子の電極体がその厚さ方向に押圧された状態である場合には、この蓄電素子は内部抵抗が増加し易く、かつ自己放電し易くなる。しかし、当該蓄電素子は、このように内部抵抗が増加し易く、かつ自己放電し易い状態であっても、上記のように内部抵抗及び自己放電を抑制することができる。
従って、当該蓄電素子は、電極体がその厚さ方向に押圧された状態で、内部抵抗の増加が抑制され、かつ自己放電が抑制されたものとなる。 In this way, the second electrode active material layer is harder than the first electrode active material layer, and accordingly the protective layer disposed on the surface on the second electrode active material layer side (that is, on the second electrode side). Since the layer is harder than the base material layer disposed on the surface of the first electrode active material layer side (that is, the first electrode side), it is relatively soft with respect to the relatively soft first electrode active material layer. A relatively hard protective layer can be opposed to the substrate layer and the relatively hard first electrode active material layer.
When suppressing the contact between the electrodes by the separator, by arranging the protective layer and the substrate layer facing each other according to the hardness of the electrode active material layer, the thickness of the protective layer and the substrate layer can be reduced excessively. , the increase in internal resistance due to the increase in thickness is suppressed.
Here, the hardness of the electrode active material layer usually depends on the hardness of the electrode active material particles contained therein.
Therefore, as described above, depending on the hardness of the first and second electrode active material layers, by appropriately facing the base material layer and the protective layer having different hardness, the first electrode active material particles and the second It is possible to prevent the two-electrode active material particles from sinking into the substrate layer and the protective layer.
In addition, since the average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles, even when the second electrode active material particles are embedded in the protective layer, the second It is possible to prevent the two-electrode active material particles from penetrating through the protective layer and reaching the substrate layer.
Further, since the average thickness of the base material layer is equal to or greater than the average diameter of the first electrode active material particles, even when the first electrode active material particles are recessed into the base material layer , the first electrode active material particles can be prevented from penetrating through the substrate layer and reaching the protective layer.
Therefore, in the electric storage element, the contact between the first electrode active material particles and the second electrode active material particles in the separator is suppressed, thereby suppressing self-discharge due to a micro short circuit or the like. can be done.
Here, in general, when the electrode body of the storage element is pressed in its thickness direction, the storage element tends to increase its internal resistance and self-discharge. However, the electric storage element can suppress the internal resistance and the self-discharge as described above even in a state where the internal resistance is likely to increase and the self-discharge is likely to occur.
Therefore, in the electric storage element, an increase in internal resistance is suppressed and self-discharge is suppressed in a state in which the electrode body is pressed in the thickness direction.
セパレータによって電極間の接触を抑制するにあたり、このように電極活物質層の硬さに応じて対向させる保護層及び基材層を配置することにより、これら保護層及び基材層の厚さを過度に大きくする必要がないため、これらの厚さの増加に起因する内部抵抗の増加が抑制される。
ここで、通常、電極活物質層の硬さは、これに含まれる電極活物質粒子の硬さに依存する。
よって、上記のように上記第１及び第２電極活物質層の硬さに応じて、硬さの異なる上記基材層及び保護層を適切に対向させることで、第１電極活物質粒子及び第２電極活物質粒子がそれぞれ基材層及び保護層に対してメリ込むことを抑制することができる。
加えて、上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であることで、上記第２電極活物質粒子が上記保護層にメリ込んだ場合であっても、上記第２電極活物質粒子が上記保護層を突き抜けて上記基材層に到達することを抑制することができる。
また、上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であることで、上記第１電極活物質粒子が上記基材層に対してメリ込んだ場合であっても、上記第１電極活物質粒子が上記基材層を突き抜けて上記保護層に到達することを抑制することができる。
よって、当該蓄電素子は、上記セパレータ内での上記第１電極活物質粒子と上記第２電極活物質粒子との接触が抑制されたものとなり、これにより、微小短絡等による自己放電を抑制することができる。
ここで、一般的に蓄電素子の電極体がその厚さ方向に押圧された状態である場合には、この蓄電素子は内部抵抗が増加し易く、かつ自己放電し易くなる。しかし、当該蓄電素子は、このように内部抵抗が増加し易く、かつ自己放電し易い状態であっても、上記のように内部抵抗及び自己放電を抑制することができる。
従って、当該蓄電素子は、電極体がその厚さ方向に押圧された状態で、内部抵抗の増加が抑制され、かつ自己放電が抑制されたものとなる。 In this way, the second electrode active material layer is harder than the first electrode active material layer, and accordingly the protective layer disposed on the surface on the second electrode active material layer side (that is, on the second electrode side). Since the layer is harder than the base material layer disposed on the surface of the first electrode active material layer side (that is, the first electrode side), it is relatively soft with respect to the relatively soft first electrode active material layer. A relatively hard protective layer can be opposed to the substrate layer and the relatively hard first electrode active material layer.
When suppressing the contact between the electrodes by the separator, by arranging the protective layer and the substrate layer facing each other according to the hardness of the electrode active material layer, the thickness of the protective layer and the substrate layer can be reduced excessively. , the increase in internal resistance due to the increase in thickness is suppressed.
Here, the hardness of the electrode active material layer usually depends on the hardness of the electrode active material particles contained therein.
Therefore, as described above, depending on the hardness of the first and second electrode active material layers, by appropriately facing the base material layer and the protective layer having different hardness, the first electrode active material particles and the second It is possible to prevent the two-electrode active material particles from sinking into the substrate layer and the protective layer.
In addition, since the average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles, even when the second electrode active material particles are embedded in the protective layer, the second It is possible to prevent the two-electrode active material particles from penetrating through the protective layer and reaching the substrate layer.
Further, since the average thickness of the base material layer is equal to or greater than the average diameter of the first electrode active material particles, even when the first electrode active material particles are recessed into the base material layer , the first electrode active material particles can be prevented from penetrating through the substrate layer and reaching the protective layer.
Therefore, in the electric storage element, the contact between the first electrode active material particles and the second electrode active material particles in the separator is suppressed, thereby suppressing self-discharge due to a micro short circuit or the like. can be done.
Here, in general, when the electrode body of the storage element is pressed in its thickness direction, the storage element tends to increase its internal resistance and self-discharge. However, the electric storage element can suppress the internal resistance and the self-discharge as described above even in a state where the internal resistance is likely to increase and the self-discharge is likely to occur.
Therefore, in the electric storage element, an increase in internal resistance is suppressed and self-discharge is suppressed in a state in which the electrode body is pressed in the thickness direction.
ここで、上記保護層が上記第２電極活物質層よりも硬くてもよい。
Here, the protective layer may be harder than the second electrode active material layer.
このように上記保護層が上記第２電極活物質層よりも硬ければ、上記第２電極活物質粒子が上記保護層にメリ込むことをより抑制することができる。
If the protective layer is harder than the second electrode active material layer, it is possible to further suppress the second electrode active material particles from sinking into the protective layer.
ここで、上記第２電極活物質粒子の平均直径が上記第１電極活物質粒子の平均直径よりも小さくてもよい。
Here, the average diameter of the second electrode active material particles may be smaller than the average diameter of the first electrode active material particles.
このように比較的硬い上記第２電極活物質粒子の平均直径が比較的柔らかい上記第１電極活物質粒子の平均直径よりも小さければ、比較的硬い上記保護層の平均厚さを比較的柔らかい上記基材層の平均厚さよりも小さくすることができる。よって、比較的硬いことから比較的形成し難い保護層の平均厚さを小さくすることができるため、当該蓄電素子がより製造し易いものとなる。
Thus, if the average diameter of the relatively hard second electrode active material particles is smaller than the average diameter of the relatively soft first electrode active material particles, the average thickness of the relatively hard protective layer is set to the relatively soft thickness. It can be smaller than the average thickness of the substrate layer. Therefore, the average thickness of the protective layer, which is relatively hard and therefore relatively difficult to form, can be reduced, so that the electric storage element can be manufactured more easily.
ここで、上記第１電極活物質層が上記基材層よりも硬くてもよい。
Here, the first electrode active material layer may be harder than the base material layer.
このように上記第１電極活物質層が上記基材層よりも硬ければ、すなわち、上記基材層が上記第１電極活物質層よりも柔らかければ、上記第１電極活物質層に含まれる比較的柔らかい上記第１電極活物質粒子の上記基材層に対するメリ込みを、主として上記基材層が有する弾性力によって抑制しつつ、上記第１電極活物質粒子の基材層に対する突き抜けを、主として上記基材層が有する厚さによって抑制することができる。よって、より適切に上記基材層を上記第１電極活物質粒子が突き抜けることを抑制することができる。
Thus, if the first electrode active material layer is harder than the substrate layer, that is, if the substrate layer is softer than the first electrode active material layer, While suppressing the penetration of the relatively soft first electrode active material particles into the base material layer mainly by the elastic force of the base material layer, the penetration of the first electrode active material particles into the base material layer is suppressed, It can be suppressed mainly by the thickness of the base material layer. Therefore, it is possible to more appropriately suppress penetration of the first electrode active material particles through the base material layer.
本発明の他の一態様に係る蓄電装置は、当該１又は複数の蓄電素子と、上記１又は複数の蓄電素子を拘束する拘束部材とを備え、上記拘束部材による拘束により上記１又は複数の蓄電素子の上記電極体が上記厚さ方向に押圧された状態である。
A power storage device according to another aspect of the present invention includes the one or more power storage elements and a restraining member that restrains the one or more power storage elements, and the one or more power storage elements are restrained by the restraining member. The electrode body of the element is pressed in the thickness direction.
当該蓄電装置は、上述した当該蓄電素子を備えるため、上述と同様、各蓄電素子の電極体が上記厚さ方向に押圧された状態で、内部抵抗の増加が抑制され、かつ自己放電が抑制されたものとなる。
Since the power storage device includes the power storage elements described above, an increase in internal resistance and self-discharge are suppressed in a state in which the electrode bodies of the power storage elements are pressed in the thickness direction, as described above. It becomes a thing.
本発明の一実施形態に係る蓄電素子の構成、蓄電装置の構成、及び蓄電素子の製造方法、並びにその他の実施形態について詳述する。なお、各実施形態に用いられる各構成部材（各構成要素）の名称は、背景技術に用いられる各構成部材（各構成要素）の名称と異なる場合がある。
The configuration of the storage element, the configuration of the storage device, the method for manufacturing the storage element, and other embodiments according to one embodiment of the present invention will be described in detail. Note that the name of each component (each component) used in each embodiment may be different from the name of each component (each component) used in the background art.
＜蓄電素子の構成＞
本発明の一実施形態に係る蓄電素子は、第１電極と、第２電極と、非水電解質とを備える。第１電極及び第２電極は、セパレータを介して厚さ方向に重ね合わされ、通常、積層又は巻回された電極体を形成する。この電極体は容器に収納され、この容器内に非水電解質が充填される。非水電解質は、第１電極と第２電極との間に介在する。蓄電素子の一例として、第２電極が正極であり、第１電極が負極である非水電解質二次電池（以下、単に「二次電池」ともいう。）について説明する。 <Structure of power storage element>
A power storage device according to one embodiment of the present invention includes a first electrode, a second electrode, and a non-aqueous electrolyte. The first electrode and the second electrode are stacked in the thickness direction with the separator interposed therebetween, usually forming a laminated or wound electrode assembly. This electrode assembly is housed in a container, and the container is filled with a non-aqueous electrolyte. A non-aqueous electrolyte is interposed between the first electrode and the second electrode. As an example of the storage element, a non-aqueous electrolyte secondary battery (hereinafter also simply referred to as "secondary battery") having a second electrode as a positive electrode and a first electrode as a negative electrode will be described.
本発明の一実施形態に係る蓄電素子は、第１電極と、第２電極と、非水電解質とを備える。第１電極及び第２電極は、セパレータを介して厚さ方向に重ね合わされ、通常、積層又は巻回された電極体を形成する。この電極体は容器に収納され、この容器内に非水電解質が充填される。非水電解質は、第１電極と第２電極との間に介在する。蓄電素子の一例として、第２電極が正極であり、第１電極が負極である非水電解質二次電池（以下、単に「二次電池」ともいう。）について説明する。 <Structure of power storage element>
A power storage device according to one embodiment of the present invention includes a first electrode, a second electrode, and a non-aqueous electrolyte. The first electrode and the second electrode are stacked in the thickness direction with the separator interposed therebetween, usually forming a laminated or wound electrode assembly. This electrode assembly is housed in a container, and the container is filled with a non-aqueous electrolyte. A non-aqueous electrolyte is interposed between the first electrode and the second electrode. As an example of the storage element, a non-aqueous electrolyte secondary battery (hereinafter also simply referred to as "secondary battery") having a second electrode as a positive electrode and a first electrode as a negative electrode will be described.
（正極）
正極（第２電極）は、正極基材と、当該正極基材に直接又は中間層を介して配される正極活物質（第２電極活物質）層とを有する。 (positive electrode)
The positive electrode (second electrode) has a positive electrode base material and a positive electrode active material (second electrode active material) layer directly or via an intermediate layer disposed on the positive electrode base material.
正極（第２電極）は、正極基材と、当該正極基材に直接又は中間層を介して配される正極活物質（第２電極活物質）層とを有する。 (positive electrode)
The positive electrode (second electrode) has a positive electrode base material and a positive electrode active material (second electrode active material) layer directly or via an intermediate layer disposed on the positive electrode base material.
正極基材は、導電性を有する。「導電性」を有するとは、ＪＩＳ－Ｈ－０５０５（１９７５年）に準拠して測定される体積抵抗率が１０７Ω・ｃｍ以下であることを意味し、「非導電性」とは、上記体積抵抗率が１０７Ω・ｃｍ超であることを意味する。正極基材の材質としては、アルミニウム、チタン、タンタル、ステンレス鋼等の金属又はこれらの合金が用いられる。これらの中でも、耐電位性、導電性の高さ、及びコストの観点からアルミニウム又はアルミニウム合金が好ましい。正極基材としては、箔、蒸着膜等が挙げられ、コストの観点から箔が好ましい。したがって、正極基材としてはアルミニウム箔又はアルミニウム合金箔が好ましい。アルミニウム又はアルミニウム合金としては、ＪＩＳ－Ｈ－４０００（２０１４年）に規定されるＡ１０８５、Ａ３００３等が例示できる。
A positive electrode base material has electroconductivity. Having “conductivity” means having a volume resistivity of 10 7 Ω·cm or less as measured in accordance with JIS-H-0505 (1975), and “non-conductivity” It means that the volume resistivity is more than 10 7 Ω·cm. As the material for the positive electrode substrate, metals such as aluminum, titanium, tantalum and stainless steel, or alloys thereof are used. Among these, aluminum or an aluminum alloy is preferable from the viewpoint of potential resistance, high conductivity, and cost. Examples of positive electrode substrates include foils and deposited films, and foils are preferred from the viewpoint of cost. Therefore, aluminum foil or aluminum alloy foil is preferable as the positive electrode substrate. Examples of aluminum or aluminum alloy include A1085 and A3003 defined in JIS-H-4000 (2014).
正極基材の平均厚さは、３μｍ以上５０μｍ以下が好ましく、５μｍ以上４０μｍ以下がより好ましく、８μｍ以上３０μｍ以下がさらに好ましく、１０μｍ以上２５μｍ以下が特に好ましい。正極基材の平均厚さを上記の範囲とすることで、正極基材の強度を高めつつ、二次電池の体積当たりのエネルギー密度を高めることができる。「基材の平均厚さ」とは、所定の面積の基材を打ち抜いた際の打ち抜き質量を、基材の真密度及び打ち抜き面積で除した値をいう。他の部材等に対して「基材の平均厚さ」を用いる場合にも同様に定義される。
The average thickness of the positive electrode substrate is preferably 3 µm or more and 50 µm or less, more preferably 5 µm or more and 40 µm or less, even more preferably 8 µm or more and 30 µm or less, and particularly preferably 10 µm or more and 25 µm or less. By setting the average thickness of the positive electrode substrate within the above range, the energy density per volume of the secondary battery can be increased while increasing the strength of the positive electrode substrate. The "average thickness of the base material" refers to a value obtained by dividing the punched mass when a base material having a predetermined area is punched out by the true density and the punched area of the base material. The same definition applies when using the "average thickness of the base material" for other members and the like.
中間層は、正極基材と正極活物質層との間に配される層である。中間層は、炭素粒子等の導電性を有する粒子を含むことで正極基材と正極活物質層との接触抵抗を低減する。中間層の構成は特に限定されず、例えば、樹脂バインダ及び導電性を有する粒子を含む。
The intermediate layer is a layer arranged between the positive electrode substrate and the positive electrode active material layer. The intermediate layer reduces the contact resistance between the positive electrode substrate and the positive electrode active material layer by containing conductive particles such as carbon particles. The structure of the intermediate layer is not particularly limited, and includes, for example, a resin binder and conductive particles.
正極活物質層は、正極活物質粒子を含む。正極活物質層は、必要に応じて、導電剤、バインダ（結着剤）、増粘剤、フィラー等の任意成分を含む。
The positive electrode active material layer contains positive electrode active material particles. The positive electrode active material layer contains arbitrary components such as a conductive agent, a binder (binding agent), a thickener, a filler, etc., as required.
正極活物質粒子を構成する正極活物質としては、公知の正極活物質の中から適宜選択できる。リチウムイオン二次電池用の正極活物質としては、通常、リチウムイオンを吸蔵及び放出することができる材料が用いられる。正極活物質としては、例えば、α－ＮａＦｅＯ２型結晶構造を有するリチウム遷移金属複合酸化物、スピネル型結晶構造を有するリチウム遷移金属複合酸化物、ポリアニオン化合物、カルコゲン化合物、硫黄等が挙げられる。α－ＮａＦｅＯ２型結晶構造を有するリチウム遷移金属複合酸化物として、例えば、Ｌｉ［ＬｉｘＮｉ１－ｘ］Ｏ２（０≦ｘ＜０．５）、Ｌｉ［ＬｉｘＮｉγＣｏ１－ｘ－γ］Ｏ２（０≦ｘ＜０．５、０＜γ＜１）、Ｌｉ［ＬｉｘＣｏ１－ｘ］Ｏ２（０≦ｘ＜０．５）、Ｌｉ［ＬｉｘＮｉγＭｎ１－ｘ－γ］Ｏ２（０≦ｘ＜０．５、０＜γ＜１）、Ｌｉ［ＬｉｘＮｉγＭｎβＣｏ１－ｘ－γ－β］Ｏ２（０≦ｘ＜０．５、０＜γ、０＜β、０．５＜γ＋β＜１）、Ｌｉ［ＬｉｘＮｉγＣｏβＡｌ１－ｘ－γ－β］Ｏ２（０≦ｘ＜０．５、０＜γ、０＜β、０．５＜γ＋β＜１）等が挙げられる。スピネル型結晶構造を有するリチウム遷移金属複合酸化物として、ＬｉｘＭｎ２Ｏ４，ＬｉｘＮｉγＭｎ２－γＯ４等が挙げられる。ポリアニオン化合物として、ＬｉＦｅＰＯ４，ＬｉＭｎＰＯ４，ＬｉＮｉＰＯ４，ＬｉＣｏＰＯ４，Ｌｉ３Ｖ２（ＰＯ４）３，Ｌｉ２ＭｎＳｉＯ４，Ｌｉ２ＣｏＰＯ４Ｆ等が挙げられる。カルコゲン化合物として、二硫化チタン、二硫化モリブデン、二酸化モリブデン等が挙げられる。これらの材料中の原子又はポリアニオンは、他の元素からなる原子又はアニオン種で一部が置換されていてもよい。これらの材料は表面が他の材料で被覆されていてもよい。正極活物質層においては、これら材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。
The positive electrode active material constituting the positive electrode active material particles can be appropriately selected from known positive electrode active materials. As a positive electrode active material for lithium ion secondary batteries, a material capable of intercalating and deintercalating lithium ions is usually used. Examples of positive electrode active materials include lithium-transition metal composite oxides having an α-NaFeO 2 type crystal structure, lithium-transition metal composite oxides having a spinel-type crystal structure, polyanion compounds, chalcogen compounds, and sulfur. Examples of lithium transition metal composite oxides having an α-NaFeO 2 type crystal structure include Li[Li x Ni 1-x ]O 2 (0≦x<0.5), Li[Li x Ni γ Co 1-x -γ ]O 2 (0≦x<0.5, 0<γ<1), Li[Li x Co 1-x ]O 2 (0≦x<0.5), Li[Li x Ni γ Mn 1 -x-γ ]O 2 (0≦x<0.5, 0<γ<1), Li[Li x Ni γ Mn β Co 1-x-γ-β ]O 2 (0≦x<0.5 , 0<γ, 0<β, 0.5<γ+β<1), Li[Li x Ni γ Co β Al 1-x-γ-β ]O 2 (0≦x<0.5, 0<γ, 0<β, 0.5<γ+β<1) and the like. Li x Mn 2 O 4 , Li x Ni γ Mn 2-γ O 4 and the like are examples of lithium transition metal composite oxides having a spinel crystal structure. Examples of polyanion compounds include LiFePO4 , LiMnPO4 , LiNiPO4 , LiCoPO4, Li3V2(PO4)3 , Li2MnSiO4 , Li2CoPO4F and the like. Examples of chalcogen compounds include titanium disulfide, molybdenum disulfide, and molybdenum dioxide. The atoms or polyanions in these materials may be partially substituted with atoms or anionic species of other elements. These materials may be coated with other materials on their surfaces. In the positive electrode active material layer, one kind of these materials may be used alone, or two or more kinds may be mixed and used.
正極活物質粒子の平均直径は、例えば、０．１μｍ以上２０μｍ以下とすることが好ましく、０．５μｍ以上１０μｍ以下とすることがより好ましく、１μｍ以上５μｍ以下とすることがさらに好ましい。正極活物質粒子の平均直径を上記下限以上とすることで、正極活物質粒子の製造又は取り扱いが容易になる。正極活物質粒子の平均直径を上記上限以下とすることで、正極活物質層の電子伝導性が向上する。なお、正極活物質粒子として正極活物質と他の材料との複合体を用いる場合、該複合体の平均直径を正極活物質粒子の平均直径とする。「平均直径」とは、ＪＩＳ－Ｚ－８８２５（２０１３年）に準拠し、粒子を溶媒で希釈した希釈液に対しレーザ回折・散乱法により測定した粒径分布に基づき、ＪＩＳ－Ｚ－８８１９－２（２００１年）に準拠し計算される体積基準積算分布が５０％となる値を意味する。
The average diameter of the positive electrode active material particles is, for example, preferably 0.1 μm or more and 20 μm or less, more preferably 0.5 μm or more and 10 μm or less, and even more preferably 1 μm or more and 5 μm or less. By making the average diameter of the positive electrode active material particles equal to or more than the above lower limit, the production or handling of the positive electrode active material particles becomes easy. By making the average diameter of the positive electrode active material particles equal to or less than the above upper limit, the electron conductivity of the positive electrode active material layer is improved. Note that when a composite of a positive electrode active material and another material is used as the positive electrode active material particles, the average diameter of the composite is taken as the average diameter of the positive electrode active material particles. The "average diameter" is based on the particle size distribution measured by the laser diffraction/scattering method for a diluted solution in which the particles are diluted with a solvent in accordance with JIS-Z-8825 (2013), JIS-Z-8819- 2 (2001) at which the volume-based cumulative distribution is 50%.
正極活物質粒子の平均直径は、負極活物質粒子の平均直径よりも小さくてもよい。このように比較的硬い上記第２電極活物質粒子の平均直径が比較的柔らかい上記第１電極活物質粒子の平均直径よりも小さければ、比較的硬い上記保護層の平均厚さを比較的柔らかい上記基材層の平均厚さよりも小さくすることができる。よって、比較的硬いことから比較的形成し難い保護層の平均厚さを小さくすることができるため、当該蓄電素子がより製造し易いものとなる。
The average diameter of the positive electrode active material particles may be smaller than the average diameter of the negative electrode active material particles. Thus, if the average diameter of the relatively hard second electrode active material particles is smaller than the average diameter of the relatively soft first electrode active material particles, the average thickness of the relatively hard protective layer is set to the relatively soft thickness. It can be smaller than the average thickness of the substrate layer. Therefore, the average thickness of the protective layer, which is relatively hard and therefore relatively difficult to form, can be reduced, so that the electric storage element can be manufactured more easily.
粉体を所定の粒径で得るためには粉砕機や分級機等が用いられる。粉砕方法として、例えば、乳鉢、ボールミル、サンドミル、振動ボールミル、遊星ボールミル、ジェットミル、カウンタージェットミル、旋回気流型ジェットミル又は篩等を用いる方法が挙げられる。粉砕時には水、あるいはヘキサン等の有機溶剤を共存させた湿式粉砕を用いることもできる。分級方法としては、篩や風力分級機等が、乾式、湿式ともに必要に応じて用いられる。
Pulverizers, classifiers, etc. are used to obtain powder with a predetermined particle size. Pulverization methods include, for example, methods using a mortar, ball mill, sand mill, vibrating ball mill, planetary ball mill, jet mill, counter jet mill, whirling jet mill, or sieve. At the time of pulverization, wet pulverization in which water or an organic solvent such as hexane is allowed to coexist can also be used. As a classification method, a sieve, an air classifier, or the like is used as necessary, both dry and wet.
正極活物質粒子の硬さは、後述するように、この正極活物質粒子で形成される正極活物質層の硬さが、負極活物質粒子で形成される負極活物質層の硬さよりも大きくなるように適宜設定され得る。この点を考慮すると、例えば正極活物質粒子の硬さが、負極活物質粒子の硬さよりも大きいことが好ましい。例えばこのような正極活物質粒子の硬さは、１００Ｈｖ以上１０００Ｈｖ以下が好ましく、２００Ｈｖ以上８００Ｈｖ以下がより好ましく、３００Ｈｖ以上７００Ｈｖ以下がさらに好ましい場合がある。正極活物質粒子の硬さを上記の範囲とすることで、適度な電極成形性と適度な電極性能の両立を図ることができるという利点がある。
Regarding the hardness of the positive electrode active material particles, as will be described later, the hardness of the positive electrode active material layer formed of the positive electrode active material particles is greater than the hardness of the negative electrode active material layer formed of the negative electrode active material particles. can be set as appropriate. Considering this point, for example, the hardness of the positive electrode active material particles is preferably higher than the hardness of the negative electrode active material particles. For example, the hardness of such positive electrode active material particles is preferably 100 Hv or more and 1000 Hv or less, more preferably 200 Hv or more and 800 Hv or less, and even more preferably 300 Hv or more and 700 Hv or less. By setting the hardness of the positive electrode active material particles within the above range, there is an advantage that both moderate electrode formability and moderate electrode performance can be achieved.
「粒子の硬さ」とは、微小硬度計で測定される値をいう。この硬さは、島津製作所社製のダイナミック超微小硬度計（型番「ＤＵＨ－２１１Ｓ」等）によって測定される。測定条件は、下記の通りである。粒子の硬さは、ビッカース硬度によって表される。
試料：粒子を埋め込み樹脂で円柱状に固定して円形の表面を研磨
試料の大きさ：直径（Φ）２５ｍｍ×厚さ（ｔ）１０ｍｍ
測定圧子：稜間角１１５° 三角すい圧子（ダイヤモンド製）
試験の種類：負荷－除荷試験
試験力：４９ｍＮ
負荷速度：２．６８５ｍＮ／ｓｅｃ
保持時間：５ｓｅｃ
他の部材等の「粒子の硬さ」も同様に定義される。 "Particle hardness" refers to a value measured with a microhardness meter. This hardness is measured by a dynamic ultra-micro hardness tester manufactured by Shimadzu Corporation (model number “DUH-211S”, etc.). Measurement conditions are as follows. Particle hardness is expressed by the Vickers hardness.
Sample: Particles are fixed in a cylindrical shape with embedded resin and the circular surface is polished Sample size: Diameter (Φ) 25 mm × thickness (t) 10 mm
Measurement indenter: Ridge angle 115° Triangular cone indenter (made of diamond)
Test type: load-unload test Test force: 49mN
Load speed: 2.685mN/sec
Holding time: 5 sec
The "hardness of particles" of other members and the like are similarly defined.
試料：粒子を埋め込み樹脂で円柱状に固定して円形の表面を研磨
試料の大きさ：直径（Φ）２５ｍｍ×厚さ（ｔ）１０ｍｍ
測定圧子：稜間角１１５° 三角すい圧子（ダイヤモンド製）
試験の種類：負荷－除荷試験
試験力：４９ｍＮ
負荷速度：２．６８５ｍＮ／ｓｅｃ
保持時間：５ｓｅｃ
他の部材等の「粒子の硬さ」も同様に定義される。 "Particle hardness" refers to a value measured with a microhardness meter. This hardness is measured by a dynamic ultra-micro hardness tester manufactured by Shimadzu Corporation (model number “DUH-211S”, etc.). Measurement conditions are as follows. Particle hardness is expressed by the Vickers hardness.
Sample: Particles are fixed in a cylindrical shape with embedded resin and the circular surface is polished Sample size: Diameter (Φ) 25 mm × thickness (t) 10 mm
Measurement indenter: Ridge angle 115° Triangular cone indenter (made of diamond)
Test type: load-unload test Test force: 49mN
Load speed: 2.685mN/sec
Holding time: 5 sec
The "hardness of particles" of other members and the like are similarly defined.
正極活物質層は、負極活物質層よりも硬い。すなわち、正極活物質層の硬さは、負極活物質層の硬さよりも大きい。正極活物質層の硬さは、負極活物質層の硬さよりも大きいように適宜設定され得る。例えば正極活物質層の硬さは、１００Ｈｖ以上１０００Ｈｖ以下が好ましく、２００Ｈｖ以上８００Ｈｖ以下がより好ましく、３００Ｈｖ以上７００Ｈｖ以下がさらに好ましい場合がある。正極活物質層の硬さを上記の範囲とすることで、上述した正極活物質粒子の硬さが上記範囲である場合と同様、適度な電極成形性と電極性能の両立を図ることができるという利点がある。「層の硬さ」とは、ビッカース硬さ（Ｈｖ）、すなわちビッカース硬度計で測定される値をいう。ビッカース硬さ（Ｈｖ）は、対面角が１３６°の四角錘からなるダイヤモンド圧子を用いて、試験片の一面にピラミッド形状の窪みをつけたときの荷重を、窪みの対角線の長さで割った値であり、ＪＩＳ－Ｚ－２２４４（２００９）に準拠して測定される。
他の部材等の「層の硬さ」も同様に定義される。 The positive electrode active material layer is harder than the negative electrode active material layer. That is, the hardness of the positive electrode active material layer is greater than the hardness of the negative electrode active material layer. The hardness of the positive electrode active material layer can be appropriately set to be higher than the hardness of the negative electrode active material layer. For example, the hardness of the positive electrode active material layer is preferably 100 Hv or more and 1000 Hv or less, more preferably 200 Hv or more and 800 Hv or less, and even more preferably 300 Hv or more and 700 Hv or less. By setting the hardness of the positive electrode active material layer within the above range, it is possible to achieve both appropriate electrode formability and electrode performance, as in the case where the hardness of the positive electrode active material particles is within the above range. There are advantages. "Layer hardness" refers to Vickers hardness (Hv), ie, a value measured with a Vickers hardness tester. The Vickers hardness (Hv) is obtained by dividing the load when a pyramid-shaped depression is made on one surface of the test piece using a diamond indenter consisting of a square pyramid with a facing angle of 136°, divided by the length of the diagonal line of the depression. value and is measured according to JIS-Z-2244 (2009).
"Layer hardness" of other members is similarly defined.
他の部材等の「層の硬さ」も同様に定義される。 The positive electrode active material layer is harder than the negative electrode active material layer. That is, the hardness of the positive electrode active material layer is greater than the hardness of the negative electrode active material layer. The hardness of the positive electrode active material layer can be appropriately set to be higher than the hardness of the negative electrode active material layer. For example, the hardness of the positive electrode active material layer is preferably 100 Hv or more and 1000 Hv or less, more preferably 200 Hv or more and 800 Hv or less, and even more preferably 300 Hv or more and 700 Hv or less. By setting the hardness of the positive electrode active material layer within the above range, it is possible to achieve both appropriate electrode formability and electrode performance, as in the case where the hardness of the positive electrode active material particles is within the above range. There are advantages. "Layer hardness" refers to Vickers hardness (Hv), ie, a value measured with a Vickers hardness tester. The Vickers hardness (Hv) is obtained by dividing the load when a pyramid-shaped depression is made on one surface of the test piece using a diamond indenter consisting of a square pyramid with a facing angle of 136°, divided by the length of the diagonal line of the depression. value and is measured according to JIS-Z-2244 (2009).
"Layer hardness" of other members is similarly defined.
正極活物質層の平均厚さは、特に限定されず、例えば正極活物質粒子の平均直径等に応じて適宜設定され得る。例えば正極活物質層の平均厚さは、１０μｍ以上１００μｍ以下が好ましく、１５μｍ以上８０μｍ以下がより好ましく、２０μｍ以上６０μｍ以下がさらに好ましい場合がある。正極活物質層の平均厚さを上記の範囲とすることで、電池の容量と出力とを適切な範囲で両立できるという利点がある。「層の平均厚さ」とは、任意の１０カ所で測定した厚さの平均値を意味する。他の部材等の「層の平均厚さ」も同様に定義される。
The average thickness of the positive electrode active material layer is not particularly limited, and can be set appropriately according to, for example, the average diameter of the positive electrode active material particles. For example, the average thickness of the positive electrode active material layer is preferably 10 μm or more and 100 μm or less, more preferably 15 μm or more and 80 μm or less, and even more preferably 20 μm or more and 60 μm or less. By setting the average thickness of the positive electrode active material layer within the above range, there is an advantage that both the capacity and the output of the battery can be achieved within an appropriate range. "Average layer thickness" means the average thickness measured at ten arbitrary locations. The "average layer thickness" of other members and the like is similarly defined.
正極活物質層における正極活物質粒子の含有量は、５０質量％以上９９質量％以下が好ましく、７０質量％以上９８質量％以下がより好ましく、８０質量％以上９５質量％以下がさらに好ましい。正極活物質粒子の含有量を上記の範囲とすることで、正極活物質層の高エネルギー密度化と製造性を両立できる。
The content of the positive electrode active material particles in the positive electrode active material layer is preferably 50% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and even more preferably 80% by mass or more and 95% by mass or less. By setting the content of the positive electrode active material particles within the above range, it is possible to achieve both high energy density and manufacturability of the positive electrode active material layer.
導電剤は、導電性を有する材料であれば特に限定されない。このような導電剤としては、例えば、炭素質材料、金属、導電性セラミックス等が挙げられる。炭素質材料としては、黒鉛、非黒鉛質炭素、グラフェン系炭素等が挙げられる。非黒鉛質炭素としては、カーボンナノファイバー、ピッチ系炭素繊維、カーボンブラック等が挙げられる。カーボンブラックとしては、ファーネスブラック、アセチレンブラック、ケッチェンブラック等が挙げられる。グラフェン系炭素としては、グラフェン、カーボンナノチューブ（ＣＮＴ）、フラーレン等が挙げられる。導電剤の形状としては、粉状、繊維状等が挙げられる。導電剤としては、これらの材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。また、これらの材料を複合化して用いてもよい。例えば、カーボンブラックとＣＮＴとを複合化した材料を用いてもよい。これらの中でも、電子伝導性及び塗工性の観点よりカーボンブラックが好ましく、中でもアセチレンブラックが好ましい。
The conductive agent is not particularly limited as long as it is a conductive material. Examples of such conductive agents include carbonaceous materials, metals, and conductive ceramics. Carbonaceous materials include graphite, non-graphitic carbon, graphene-based carbon, and the like. Examples of non-graphitic carbon include carbon nanofiber, pitch-based carbon fiber, and carbon black. Examples of carbon black include furnace black, acetylene black, and ketjen black. Graphene-based carbon includes graphene, carbon nanotube (CNT), fullerene, and the like. The shape of the conductive agent may be powdery, fibrous, or the like. As the conductive agent, one type of these materials may be used alone, or two or more types may be mixed and used. Also, these materials may be combined for use. For example, a composite material of carbon black and CNT may be used. Among these, carbon black is preferable from the viewpoint of electron conductivity and coatability, and acetylene black is particularly preferable.
正極活物質層における導電剤の含有量は、１質量％以上１０質量％以下が好ましく、３質量％以上９質量％以下がより好ましい。導電剤の含有量を上記の範囲とすることで、二次電池のエネルギー密度を高めることができる。
The content of the conductive agent in the positive electrode active material layer is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less. By setting the content of the conductive agent within the above range, the energy density of the secondary battery can be increased.
バインダとしては、例えば、フッ素樹脂（ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）等）、ポリエチレン、ポリプロピレン、ポリアクリル、ポリイミド等の熱可塑性樹脂；エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、スルホン化ＥＰＤＭ、スチレンブタジエンゴム（ＳＢＲ）、フッ素ゴム等のエラストマー；多糖類高分子等が挙げられる。
Binders include, for example, fluorine resins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, polyacryl, and polyimide; ethylene-propylene-diene rubber (EPDM), sulfone Elastomers such as modified EPDM, styrene-butadiene rubber (SBR) and fluororubber; polysaccharide polymers and the like.
正極活物質層におけるバインダの含有量は、１質量％以上１０質量％以下が好ましく、３質量％以上９質量％以下がより好ましい。バインダの含有量を上記の範囲とすることで、活物質を安定して保持することができる。
The content of the binder in the positive electrode active material layer is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less. By setting the content of the binder within the above range, the active material can be stably retained.
増粘剤としては、例えば、カルボキシメチルセルロース（ＣＭＣ）、メチルセルロース等の多糖類高分子が挙げられる。増粘剤がリチウム等と反応する官能基を有する場合、予めメチル化等によりこの官能基を失活させてもよい。
Examples of thickeners include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose. When the thickener has a functional group that reacts with lithium or the like, the functional group may be previously deactivated by methylation or the like.
フィラーは、特に限定されない。フィラーとしては、ポリプロピレン、ポリエチレン等のポリオレフィン、二酸化ケイ素、アルミナ、二酸化チタン、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、アルミノケイ酸塩等の無機酸化物、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物、炭酸カルシウム等の炭酸塩、フッ化カルシウム、フッ化バリウム、硫酸バリウム等の難溶性のイオン結晶、窒化アルミニウム、窒化ケイ素等の窒化物、タルク、モンモリロナイト、ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、セリサイト、ベントナイト、マイカ等の鉱物資源由来物質又はこれらの人造物等が挙げられる。
The filler is not particularly limited. Fillers include polyolefins such as polypropylene and polyethylene, inorganic oxides such as silicon dioxide, alumina, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, magnesium hydroxide, calcium hydroxide, hydroxide Hydroxides such as aluminum, carbonates such as calcium carbonate, sparingly soluble ionic crystals such as calcium fluoride, barium fluoride, and barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc, montmorillonite, boehmite, zeolite, Mineral resource-derived substances such as apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, and mica, or artificial products thereof may be used.
正極活物質層は、Ｂ、Ｎ、Ｐ、Ｆ、Ｃｌ、Ｂｒ、Ｉ等の典型非金属元素、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、Ｃａ、Ｚｎ、Ｇａ、Ｇｅ、Ｓｎ、Ｓｒ、Ｂａ等の典型金属元素、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ、Ｚｒ、Ｎｂ、Ｗ等の遷移金属元素を正極活物質、導電剤、バインダ、増粘剤、フィラー以外の成分として含有してもよい。
The positive electrode active material layer contains typical nonmetallic elements such as B, N, P, F, Cl, Br, and I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba, and the like. typical metal elements, transition metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, W are used as positive electrode active materials, conductive agents, binders, thickeners, fillers It may be contained as a component other than
（負極）
負極（第１電極）は、負極基材と、当該負極基材に直接又は中間層を介して配される負極活物質（第１電極活物質）層とを有する。中間層の構成は特に限定されず、例えば上記正極で例示した構成から選択することができる。 (negative electrode)
The negative electrode (first electrode) has a negative electrode base material and a negative electrode active material (first electrode active material) layer that is disposed on the negative electrode base material directly or via an intermediate layer. The structure of the intermediate layer is not particularly limited, and can be selected from, for example, the structures exemplified for the positive electrode.
負極（第１電極）は、負極基材と、当該負極基材に直接又は中間層を介して配される負極活物質（第１電極活物質）層とを有する。中間層の構成は特に限定されず、例えば上記正極で例示した構成から選択することができる。 (negative electrode)
The negative electrode (first electrode) has a negative electrode base material and a negative electrode active material (first electrode active material) layer that is disposed on the negative electrode base material directly or via an intermediate layer. The structure of the intermediate layer is not particularly limited, and can be selected from, for example, the structures exemplified for the positive electrode.
負極基材は、導電性を有する。負極基材の材質としては、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼、アルミニウム等の金属又はこれらの合金が用いられる。これらの中でも銅又は銅合金が好ましい。負極基材としては、箔、蒸着膜等が挙げられ、コストの観点から箔が好ましい。したがって、負極基材としては銅箔又は銅合金箔が好ましい。銅箔の例としては、圧延銅箔、電解銅箔等が挙げられる。
The negative electrode base material has conductivity. As the material of the negative electrode base material, metals such as copper, nickel, stainless steel, nickel-plated steel, and aluminum, or alloys thereof are used. Among these, copper or a copper alloy is preferred. Examples of negative electrode substrates include foils and vapor deposition films, and foils are preferred from the viewpoint of cost. Therefore, copper foil or copper alloy foil is preferable as the negative electrode substrate. Examples of copper foil include rolled copper foil and electrolytic copper foil.
負極基材の平均厚さは、２μｍ以上３５μｍ以下が好ましく、３μｍ以上３０μｍ以下がより好ましく、４μｍ以上２５μｍ以下がさらに好ましく、５μｍ以上２０μｍ以下が特に好ましい。負極基材の平均厚さを上記の範囲とすることで、負極基材の強度を高めつつ、二次電池の体積当たりのエネルギー密度を高めることができる。
The average thickness of the negative electrode substrate is preferably 2 μm or more and 35 μm or less, more preferably 3 μm or more and 30 μm or less, even more preferably 4 μm or more and 25 μm or less, and particularly preferably 5 μm or more and 20 μm or less. By setting the average thickness of the negative electrode substrate within the above range, the energy density per volume of the secondary battery can be increased while increasing the strength of the negative electrode substrate.
負極活物質層は、負極活物質粒子を含む。負極活物質層は、必要に応じて導電剤、バインダ、増粘剤、フィラー等の任意成分を含む。導電剤、バインダ、増粘剤、フィラー等の任意成分は、上記正極で例示した材料から選択できる。
The negative electrode active material layer contains negative electrode active material particles. The negative electrode active material layer contains arbitrary components such as a conductive agent, a binder, a thickener, a filler, etc., as required. Optional components such as conductive agents, binders, thickeners, and fillers can be selected from the materials exemplified for the positive electrode.
負極活物質層は、Ｂ、Ｎ、Ｐ、Ｆ、Ｃｌ、Ｂｒ、Ｉ等の典型非金属元素、Ｌｉ、Ｎａ、Ｍｇ、Ａｌ、Ｋ、Ｃａ、Ｚｎ、Ｇａ、Ｇｅ、Ｓｎ、Ｓｒ、Ｂａ等の典型金属元素、Ｓｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｍｏ、Ｚｒ、Ｔａ、Ｈｆ、Ｎｂ、Ｗ等の遷移金属元素を負極活物質、導電剤、バインダ、増粘剤、フィラー以外の成分として含有してもよい。
The negative electrode active material layer contains typical nonmetallic elements such as B, N, P, F, Cl, Br, and I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba, and the like. and transition metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Ta, Hf, Nb, and W are used as negative electrode active materials, conductive agents, binders, and thickeners. You may contain as a component other than a sticky agent and a filler.
負極活物質粒子を構成する負極活物質としては、公知の負極活物質の中から適宜選択できる。リチウムイオン二次電池用の負極活物質としては、通常、リチウムイオンを吸蔵及び放出することができる材料が用いられる。負極活物質としては、例えば、金属Ｌｉ；Ｓｉ、Ｓｎ等の金属又は半金属；Ｓｉ酸化物、Ｔｉ酸化物、Ｓｎ酸化物等の金属酸化物又は半金属酸化物；Ｌｉ４Ｔｉ５Ｏ１２、ＬｉＴｉＯ２、ＴｉＮｂ２Ｏ７等のチタン含有酸化物；ポリリン酸化合物；炭化ケイ素；黒鉛（グラファイト）、非黒鉛質炭素（易黒鉛化性炭素又は難黒鉛化性炭素）等の炭素材料等が挙げられる。これらの材料の中でも、黒鉛及び非黒鉛質炭素が好ましい。負極活物質層においては、これら材料の１種を単独で用いてもよく、２種以上を混合して用いてもよい。
The negative electrode active material constituting the negative electrode active material particles can be appropriately selected from known negative electrode active materials. Materials capable of intercalating and deintercalating lithium ions are usually used as negative electrode active materials for lithium ion secondary batteries. Examples of the negative electrode active material include metal Li; metals or metalloids such as Si and Sn; metal oxides and metalloid oxides such as Si oxide, Ti oxide and Sn oxide; Li 4 Ti 5 O 12 ; Titanium-containing oxides such as LiTiO 2 and TiNb 2 O 7 ; polyphosphate compounds; silicon carbide; carbon materials such as graphite and non-graphitizable carbon (easily graphitizable carbon or non-graphitizable carbon) be done. Among these materials, graphite and non-graphitic carbon are preferred. In the negative electrode active material layer, one type of these materials may be used alone, or two or more types may be mixed and used.
「黒鉛」とは、充放電前又は放電状態において、Ｘ線回折法により決定される（００２）面の平均格子面間隔（ｄ００２）が０．３３ｎｍ以上０．３４ｎｍ未満の炭素材料をいう。黒鉛としては、天然黒鉛、人造黒鉛が挙げられる。安定した物性の材料を入手できるという観点で、人造黒鉛が好ましい。
“Graphite” refers to a carbon material having an average lattice spacing (d 002 ) of the (002) plane determined by X-ray diffraction before charging/discharging or in a discharged state of 0.33 nm or more and less than 0.34 nm. Graphite includes natural graphite and artificial graphite. Artificial graphite is preferable from the viewpoint that a material with stable physical properties can be obtained.
「非黒鉛質炭素」とは、充放電前又は放電状態においてＸ線回折法により決定される（００２）面の平均格子面間隔（ｄ００２）が０．３４ｎｍ以上０．４２ｎｍ以下の炭素材料をいう。非黒鉛質炭素としては、難黒鉛化性炭素や、易黒鉛化性炭素が挙げられる。非黒鉛質炭素としては、例えば、樹脂由来の材料、石油ピッチまたは石油ピッチ由来の材料、石油コークスまたは石油コークス由来の材料、植物由来の材料、アルコール由来の材料等が挙げられる。
“Non-graphitic carbon” means a carbon material having an average lattice spacing (d 002 ) of the (002) plane determined by X-ray diffraction before charging/discharging or in a discharged state of 0.34 nm or more and 0.42 nm or less. Say. Non-graphitizable carbon includes non-graphitizable carbon and graphitizable carbon. Examples of non-graphitic carbon include resin-derived materials, petroleum pitch or petroleum pitch-derived materials, petroleum coke or petroleum coke-derived materials, plant-derived materials, and alcohol-derived materials.
ここで、「放電状態」とは、負極活物質として炭素材料を含む負極を作用極として、金属Ｌｉを対極として用いた単極電池において、開回路電圧が０．７Ｖ以上である状態をいう。開回路状態での金属Ｌｉ対極の電位は、Ｌｉの酸化還元電位とほぼ等しいため、上記単極電池における開回路電圧は、Ｌｉの酸化還元電位に対する炭素材料を含む負極の電位とほぼ同等である。つまり、上記単極電池における開回路電圧が０．７Ｖ以上であることは、負極活物質である炭素材料から、充放電に伴い吸蔵放出可能なリチウムイオンが十分に放出されていることを意味する。
Here, the "discharged state" refers to a state in which the open circuit voltage is 0.7 V or more in a single electrode battery using a negative electrode containing a carbon material as a negative electrode active material as a working electrode and metal Li as a counter electrode. Since the potential of the metal Li counter electrode in the open circuit state is approximately equal to the oxidation-reduction potential of Li, the open-circuit voltage in the above monopolar battery is approximately the same as the potential of the negative electrode containing the carbon material with respect to the oxidation-reduction potential of Li. . In other words, the open circuit voltage of 0.7 V or higher in the above monopolar battery means that lithium ions that can be inserted and extracted are sufficiently released from the carbon material that is the negative electrode active material during charging and discharging. .
「難黒鉛化性炭素」とは、上記ｄ００２が０．３６ｎｍ以上０．４２ｎｍ以下の炭素材料をいう。
The term “non-graphitizable carbon” refers to a carbon material having a d 002 of 0.36 nm or more and 0.42 nm or less.
「易黒鉛化性炭素」とは、上記ｄ００２が０．３４ｎｍ以上０．３６ｎｍ未満の炭素材料をいう。
“Graphitizable carbon” refers to a carbon material having a d 002 of 0.34 nm or more and less than 0.36 nm.
負極活物質粒子の平均直径は、例えば、１ｎｍ以上１００μｍ以下とすることができる。負極活物質が例えば炭素材料である場合、負極活物質粒子の平均直径は１μｍ以上１００μｍ以下が好ましく、２μｍ以上５０μｍ以下が好ましく、５μｍ以上２０μｍ以下が好ましい場合がある。負極活物質が、金属、半金属、金属酸化物、半金属酸化物、チタン含有酸化物、ポリリン酸化合物等である場合、負極活物質粒子の平均直径は、１ｎｍ以上１μｍ以下が好ましい場合がある。負極活物質粒子の平均直径を上記下限以上とすることで、負極活物質粒子の製造又は取り扱いが容易になる。負極活物質粒子の平均直径を上記上限以下とすることで、活物質層の電子伝導性が向上する。粉体を所定の粒径で得るためには粉砕機や分級機等が用いられる。粉砕方法及び分級方法は、例えば、上記正極で例示した方法から選択できる。ここで、負極活物質粒子の平均直径は、上述した正極活物質粒子の平均直径と同様に測定される。
The average diameter of the negative electrode active material particles can be, for example, 1 nm or more and 100 μm or less. When the negative electrode active material is, for example, a carbon material, the average diameter of the negative electrode active material particles is preferably 1 μm or more and 100 μm or less, preferably 2 μm or more and 50 μm or less, and sometimes preferably 5 μm or more and 20 μm or less. When the negative electrode active material is a metal, a metalloid, a metal oxide, a metalloid oxide, a titanium-containing oxide, a polyphosphate compound, or the like, the average diameter of the negative electrode active material particles is preferably 1 nm or more and 1 μm or less. . By making the average diameter of the negative electrode active material particles equal to or greater than the above lower limit, it becomes easy to manufacture or handle the negative electrode active material particles. By setting the average diameter of the negative electrode active material particles to the above upper limit or less, the electron conductivity of the active material layer is improved. A pulverizer, a classifier, or the like is used to obtain powder having a predetermined particle size. The pulverization method and classification method can be selected from, for example, the methods exemplified for the positive electrode. Here, the average diameter of the negative electrode active material particles is measured in the same manner as the average diameter of the positive electrode active material particles described above.
上述したように、負極活物質粒子の平均直径は、正極活物質粒子の平均直径よりも大きくてもよい。
As described above, the average diameter of the negative electrode active material particles may be larger than the average diameter of the positive electrode active material particles.
負極活物質粒子の硬さは、上述及び後述するように、この負極活物質粒子で構成される負極活物質層の硬さが、正極活物質粒子で構成される正極活物質層の硬さよりも小さくなるように適宜設定され得る。この点を考慮すると、負極活物質粒子の硬さは、正極活物質粒子の硬さよりも小さいことが好ましい。例えばこのような負極活物質粒子の硬さは、１０Ｈｖ以上３００Ｈｖ以下が好ましく、３０Ｈｖ以上２５０Ｈｖ以下がより好ましく、５０Ｈｖ以上２００Ｈｖ以下がさらに好ましい場合がある。負極活物質粒子の硬さを上記の範囲とすることで、正極活物質粒子の硬さよりも小さくし易くすることができ、かつ、適度な電極成形性と適度な電極性能との両立を図ることができるという利点がある。
Regarding the hardness of the negative electrode active material particles, as described above and below, the hardness of the negative electrode active material layer composed of the negative electrode active material particles is higher than the hardness of the positive electrode active material layer composed of the positive electrode active material particles. It can be appropriately set to be small. Considering this point, the hardness of the negative electrode active material particles is preferably smaller than the hardness of the positive electrode active material particles. For example, the hardness of such negative electrode active material particles is preferably 10 Hv or more and 300 Hv or less, more preferably 30 Hv or more and 250 Hv or less, and even more preferably 50 Hv or more and 200 Hv or less. By setting the hardness of the negative electrode active material particles within the above range, it is possible to easily make the hardness smaller than that of the positive electrode active material particles, and to achieve both appropriate electrode formability and appropriate electrode performance. has the advantage of being able to
負極活物質層は、上述するように、正極活物質層よりも柔らかい。すなわち、負極活物質層の硬さは、正極活物質層の硬さよりも小さい。負極活物質層の硬さは、正極活物質層の硬さよりも小さいように適宜設定され得る。例えば負極活物質層の硬さは、１０Ｈｖ以上３００Ｈｖ以下が好ましく、３０Ｈｖ以上２５０Ｈｖ以下がより好ましく、５０Ｈｖ以上２００Ｈｖ以下がさらに好ましい場合がある。負極活物質層の硬さを上記の範囲とすることで、正極活物質層の硬さよりも小さくし易くすることができ、かつ、適度な電極成形性と適度な電極性能との両立を図ることができるという利点がある。
The negative electrode active material layer is softer than the positive electrode active material layer, as described above. That is, the hardness of the negative electrode active material layer is lower than the hardness of the positive electrode active material layer. The hardness of the negative electrode active material layer can be appropriately set to be lower than the hardness of the positive electrode active material layer. For example, the hardness of the negative electrode active material layer is preferably 10 Hv or more and 300 Hv or less, more preferably 30 Hv or more and 250 Hv or less, and even more preferably 50 Hv or more and 200 Hv or less. By setting the hardness of the negative electrode active material layer within the above range, it is possible to easily make the hardness lower than that of the positive electrode active material layer, and to achieve both appropriate electrode formability and appropriate electrode performance. has the advantage of being able to
負極活物質層の平均厚さは、特に限定されず、例えば負極活物質粒子の平均直径等に応じて適宜設定され得る。例えば負極活物質層の平均厚さは、２０μｍ以上１００μｍ以下が好ましく、２５μｍ以上９０μｍ以下がより好ましく、３０μｍ以上８０μｍ以下がさらに好ましい場合がある。負極活物質層の平均厚さを上記の範囲とすることで、二次電池の容量と出力とを適切な範囲で両立できるという利点がある。
The average thickness of the negative electrode active material layer is not particularly limited, and can be set appropriately according to, for example, the average diameter of the negative electrode active material particles. For example, the average thickness of the negative electrode active material layer is preferably 20 μm or more and 100 μm or less, more preferably 25 μm or more and 90 μm or less, and even more preferably 30 μm or more and 80 μm or less. By setting the average thickness of the negative electrode active material layer within the above range, there is an advantage that both the capacity and the output of the secondary battery can be achieved within an appropriate range.
負極活物質層における負極活物質粒子の含有量は、６０質量％以上９９質量％以下が好ましく、９０質量％以上９８質量％以下がより好ましい。負極活物質粒子の含有量を上記の範囲とすることで、負極活物質層の高エネルギー密度化と製造性を両立できる。
The content of the negative electrode active material particles in the negative electrode active material layer is preferably 60% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 98% by mass or less. By setting the content of the negative electrode active material particles within the above range, it is possible to achieve both high energy density and manufacturability of the negative electrode active material layer.
（セパレータ）
セパレータは、負極活物質層及び正極活物質層間に介在する。セパレータは、基材層及び保護層を有する。保護層は、基材層における正極活物質層側の表面に配置され、かつ基材層よりも硬い。 (separator)
The separator is interposed between the negative electrode active material layer and the positive electrode active material layer. The separator has a substrate layer and a protective layer. The protective layer is arranged on the surface of the substrate layer on the side of the positive electrode active material layer, and is harder than the substrate layer.
セパレータは、負極活物質層及び正極活物質層間に介在する。セパレータは、基材層及び保護層を有する。保護層は、基材層における正極活物質層側の表面に配置され、かつ基材層よりも硬い。 (separator)
The separator is interposed between the negative electrode active material layer and the positive electrode active material layer. The separator has a substrate layer and a protective layer. The protective layer is arranged on the surface of the substrate layer on the side of the positive electrode active material layer, and is harder than the substrate layer.
基材層は、負極活物質層及び保護層間に介在する。基材層は、多孔質の層である。基材層の形状としては、例えば、織布、不織布、多孔質樹脂フィルム等が挙げられる。これらの形状の中でも、強度の観点から多孔質樹脂フィルムが好ましく、非水電解質の保液性の観点から不織布が好ましい。基材層の材料としては、シャットダウン機能の観点から例えばポリエチレン、ポリプロピレン等のポリオレフィンが好ましく、耐酸化分解性の観点から例えばポリイミドやアラミド等が好ましい。セパレータの基材層として、これらの樹脂を複合した材料を用いてもよい。基材層が負極活物質層及び保護層間に介在することで、負極活物質粒子が基材層に対してメリ込んだ場合に、負極活物質粒子が基材層を突き抜けて保護層に到達することを抑制することができる。
The base material layer is interposed between the negative electrode active material layer and the protective layer. The substrate layer is a porous layer. Examples of the shape of the substrate layer include woven fabric, nonwoven fabric, and porous resin film. Among these shapes, a porous resin film is preferred from the viewpoint of strength, and a non-woven fabric is preferred from the viewpoint of non-aqueous electrolyte retention. As the material of the base material layer, polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of shutdown function, and polyimide, aramid, and the like are preferable from the viewpoint of resistance to oxidative decomposition. A material obtained by combining these resins may be used as the base material layer of the separator. Since the base layer is interposed between the negative electrode active material layer and the protective layer, when the negative electrode active material particles are embedded in the base layer, the negative electrode active material particles penetrate the base layer and reach the protective layer. can be suppressed.
基材層の平均厚さは、負極活物質粒子の平均直径以上である。基材層の平均厚さが負極活物質粒子の平均直径以上であることで、基材層に負極活物質粒子がメリ込んだ場合に、負極活物質粒子が基材層を突き抜けて保護層に到達することを抑制することができる。このような基材層の平均厚さは、１０μｍ以上３０μｍ以下が好ましく、１０μｍ以上２０μｍ以下がより好ましい場合がある。基材層の平均厚さが上記下限以上であれば、負極活物質粒子が基材層を突き抜けて保護層に到達することをより抑制することができる。基材層の平均厚さが上記上限以下であれば、基材層の平均厚さが大き過ぎることに起因する内部抵抗の増加を抑制することができる。
The average thickness of the base material layer is equal to or greater than the average diameter of the negative electrode active material particles. Since the average thickness of the base layer is equal to or greater than the average diameter of the negative electrode active material particles, when the negative electrode active material particles are embedded in the base layer, the negative electrode active material particles penetrate the base layer and form the protective layer. can be prevented from reaching The average thickness of such a substrate layer is preferably 10 μm or more and 30 μm or less, and more preferably 10 μm or more and 20 μm or less. When the average thickness of the substrate layer is at least the above lower limit, it is possible to further suppress the negative electrode active material particles from penetrating through the substrate layer and reaching the protective layer. If the average thickness of the base material layer is equal to or less than the above upper limit, it is possible to suppress an increase in internal resistance due to the excessively large average thickness of the base material layer.
上述したように、負極活物質層の硬さが正極活物質層の硬さよりも小さいことに対応して、基材層の硬さは保護層の硬さよりも小さい。また、基材層の硬さは、これが対向する負極活物質層の硬さよりも小さくても大きくてもよい。例えば基材層の硬さは負極活物質層よりも小さくてもよい。すなわち、負極活物質層が基材層よりも硬くてもよい。基材層が負極活物質層よりも柔らかければ、負極活物質層に含まれる比較的柔らかい負極活物質粒子の基材層に対するメリ込みを、主として基材層が有する弾性力によって抑制しつつ、負極活物質粒子が基材層を突き抜けることを、主として基材層が有する厚さによって抑制することができる。よって、より適切に基材層に対する負極活物質粒子のメリ込み及び突き抜けを抑制することができる。このような基材層の硬さは、５Ｈｖ以上２００Ｈｖ以下が好ましく、１０Ｈｖ以上１５０Ｈｖ以下がより好ましく、２０Ｈｖ以上１００Ｈｖ以下がさらに好ましい場合がある。基材層の硬さを上記の範囲とすることで、保護層の硬さよりも小さくし易くすることができ、かつ、適度な強度と適度な弾性力とを保持できるという利点がある。
As described above, the hardness of the base material layer is lower than that of the protective layer corresponding to the hardness of the negative electrode active material layer being lower than that of the positive electrode active material layer. Further, the hardness of the substrate layer may be lower or higher than the hardness of the negative electrode active material layer facing it. For example, the hardness of the base material layer may be lower than that of the negative electrode active material layer. That is, the negative electrode active material layer may be harder than the substrate layer. If the base material layer is softer than the negative electrode active material layer, the relatively soft negative electrode active material particles contained in the negative electrode active material layer are prevented from sinking into the base material layer mainly by the elastic force of the base material layer. Penetration of the negative electrode active material particles through the substrate layer can be suppressed mainly by the thickness of the substrate layer. Therefore, it is possible to more appropriately suppress the penetration and penetration of the negative electrode active material particles into the base material layer. The hardness of such a base material layer is preferably 5 Hv or more and 200 Hv or less, more preferably 10 Hv or more and 150 Hv or less, and even more preferably 20 Hv or more and 100 Hv or less. By setting the hardness of the base material layer within the above range, there is an advantage that the hardness can be easily made smaller than that of the protective layer, and an appropriate strength and an appropriate elastic force can be maintained.
保護層は、正極活物質層及び基材層間に介在する。保護層は無機粒子を含む多孔質の層である。保護層はバインダ等のその他の成分が含有されていてもよい。保護層の形態としては、保護層が基材層の表面に一体的に形成されていてもよく、保護層が正極活物質層の表面上に形成されていてもよい。正極活物質層及び基材層間に保護層が介在することで、正極活物質粒子が保護層に対してメリ込んだ場合に、正極活物質粒子が保護層を突き抜けて基材層に到達することを抑制することができる。
The protective layer is interposed between the positive electrode active material layer and the substrate layer. The protective layer is a porous layer containing inorganic particles. The protective layer may contain other components such as a binder. As for the form of the protective layer, the protective layer may be integrally formed on the surface of the substrate layer, or the protective layer may be formed on the surface of the positive electrode active material layer. By interposing the protective layer between the positive electrode active material layer and the substrate layer, when the positive electrode active material particles are embedded in the protective layer, the positive electrode active material particles penetrate the protective layer and reach the substrate layer. can be suppressed.
無機粒子を構成する材料の具体的種類としては、酸化鉄、酸化ケイ素、酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、酸化マグネシウム、アルミノケイ酸塩等の酸化物；水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の水酸化物；窒化アルミニウム、窒化ケイ素等の窒化物；炭酸カルシウム等の炭酸塩；硫酸バリウム等の硫酸塩；フッ化カルシウム、フッ化バリウム、チタン酸バリウム等の難溶性のイオン結晶；シリコン、ダイヤモンド等の共有結合性結晶；タルク、モンモリロナイト、ベーマイト、ゼオライト、アパタイト、カオリン、ムライト、スピネル、オリビン、セリサイト、ベントナイト、マイカ等の鉱物資源由来物質又はこれらの人造物等が挙げられる。無機粒子としては、軽量化の観点からこれらの中でもより密度の低いものが好ましい。無機粒子として、これらの物質の単体又は複合体を単独で用いてもよく、２種以上を混合して用いてもよい。
Specific types of materials that make up the inorganic particles include oxides such as iron oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, and aluminosilicate; Hydroxides such as magnesium, calcium hydroxide, and aluminum hydroxide; Nitrides such as aluminum nitride and silicon nitride; Carbonates such as calcium carbonate; Sulfates such as barium sulfate; Calcium fluoride, barium fluoride, and barium titanate covalent crystals such as silicon and diamond; mineral resource-derived substances such as talc, montmorillonite, boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, and mica; and the like. As the inorganic particles, those having a lower density among these are preferable from the viewpoint of weight reduction. As the inorganic particles, a single substance or a composite of these substances may be used alone, or two or more of them may be mixed and used.
保護層における無機粒子の含有量としては、５０質量％以上１００質量％以下が好ましく、６０質量％以上９９質量％以下がより好ましく、７０質量％以上９８質量％以下がさらに好ましい。
The content of the inorganic particles in the protective layer is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 99% by mass or less, and even more preferably 70% by mass or more and 98% by mass or less.
保護層がバインダを含有する場合、保護層におけるバインダの含有量としては、５０質量％以下が好ましく、４０質量％以下がより好ましく、３０質量％以下がさらに好ましい。
When the protective layer contains a binder, the content of the binder in the protective layer is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
無機粒子の平均直径の上限としては、１０μｍが好ましく、８μｍがより好ましく、５μｍがさらに好ましい。上記平均直径の下限としては特に限定されないが、例えば５ｎｍ又は５０ｎｍであってよく、５００ｎｍであってもよい。また、無機粒子は、小粒径のほうが大粒径と比較して保護層の面積あたりの細孔の数が増加することで電流分布がより均一となることから、本実施形態の効果をより奏することができる。ここで、無機粒子の平均直径は、上述した正極活物質粒子の平均直径と同様に測定される。
The upper limit of the average diameter of the inorganic particles is preferably 10 µm, more preferably 8 µm, and even more preferably 5 µm. Although the lower limit of the average diameter is not particularly limited, it may be, for example, 5 nm, 50 nm, or 500 nm. In addition, the smaller the inorganic particles, the more uniform the current distribution due to the increase in the number of pores per area of the protective layer, compared to the large particles. can play. Here, the average diameter of the inorganic particles is measured in the same manner as the average diameter of the positive electrode active material particles described above.
保護層のバインダとしては、正極活物質層のバインダと同様のものを用いることができる。
As the binder for the protective layer, the same binder as for the positive electrode active material layer can be used.
保護層の平均厚さは、正極活物質粒子の平均直径以上である。保護層の平均厚さが正極活物質粒子の平均直径以上であることで、保護層に正極活物質粒子がメリ込んだ場合に、正極活物質粒子が保護層を突き抜けて基材層に到達することを抑制することができる。このような保護層の平均厚さは、例えば１μｍ以上１０μｍ以下が好ましく、３μｍ以上６μｍ以下がより好ましい。上記保護層の平均厚さが上記下限以上であることで、微小短絡の発生をより抑制することができる。一方、上記保護層の平均厚さが上記上限以下であることで、高いエネルギー密度を維持することができる。
The average thickness of the protective layer is equal to or greater than the average diameter of the positive electrode active material particles. Since the average thickness of the protective layer is equal to or greater than the average diameter of the positive electrode active material particles, when the positive electrode active material particles are embedded in the protective layer, the positive electrode active material particles pass through the protective layer and reach the base layer. can be suppressed. The average thickness of such a protective layer is, for example, preferably 1 μm or more and 10 μm or less, more preferably 3 μm or more and 6 μm or less. When the average thickness of the protective layer is equal to or greater than the lower limit, it is possible to further suppress the occurrence of micro short circuits. On the other hand, when the average thickness of the protective layer is equal to or less than the upper limit, high energy density can be maintained.
上述したように、正極活物質層の硬さが負極活物質層の硬さよりも大きいことに対応して、保護層の硬さは基材層の硬さよりも大きい。また、保護層の硬さは、これが対向する正極活物質層の硬さよりも大きいことが好ましい。このような保護層の硬さは、５００Ｈｖ以上２５００Ｈｖ以下が好ましく、７００Ｈｖ以上２０００Ｈｖ以下がより好ましく、１０００Ｈｖ以上１５００Ｈｖ以下がさらに好ましい場合がある。保護層の硬さを上記の範囲とすることで、基材層の硬さよりも大きくし易くすることができるという利点がある。
As described above, the hardness of the protective layer is greater than that of the base material layer, corresponding to the fact that the hardness of the positive electrode active material layer is greater than that of the negative electrode active material layer. Also, the hardness of the protective layer is preferably higher than the hardness of the positive electrode active material layer facing it. The hardness of such a protective layer is preferably 500 Hv or more and 2500 Hv or less, more preferably 700 Hv or more and 2000 Hv or less, and even more preferably 1000 Hv or more and 1500 Hv or less. By setting the hardness of the protective layer within the above range, there is an advantage that the hardness can be easily made higher than that of the substrate layer.
基材層及び保護層全体の平均厚さ、すなわちセパレータ全体の平均厚さとしては、例えば１１μｍ以上３５μｍ以下が好ましく、１３μｍ以上２６μｍ以下がより好ましい。セパレータ全体の平均厚さが上記下限以上であることで、微小短絡の発生をより抑制することができる。一方、セパレータ全体の平均厚さが上記上限以下であることで、当該蓄電素子の高エネルギー密度化を図ることができる。なお、セパレータ全体の平均厚さは、任意の１０カ所で測定した厚さの平均値とする。
The average thickness of the base layer and the protective layer as a whole, that is, the average thickness of the separator as a whole is preferably, for example, 11 μm or more and 35 μm or less, more preferably 13 μm or more and 26 μm or less. When the average thickness of the entire separator is equal to or greater than the above lower limit, it is possible to further suppress the occurrence of micro short circuits. On the other hand, when the average thickness of the entire separator is equal to or less than the above upper limit, the energy density of the electric storage element can be increased. The average thickness of the entire separator is the average value of thicknesses measured at arbitrary 10 points.
セパレータ全体の空孔率は、強度の観点から８０体積％以下が好ましく、放電性能の観点から２０体積％以上が好ましい。ここで、「空孔率」とは、体積基準の値であり、水銀ポロシメータでの測定値を意味する。
The porosity of the entire separator is preferably 80% by volume or less from the viewpoint of strength, and preferably 20% by volume or more from the viewpoint of discharge performance. Here, the "porosity" is a volume-based value and means a value measured with a mercury porosimeter.
本実施形態の蓄電素子に備えられる電極体は、上記のように正極と、負極とが、セパレータを介して厚さ方向に重ね合わされてなる。図１に本実施形態の電極体の層構成の一例を示す。電極体２は、第２電極としての正極４５、第１電極としての負極５５、及びセパレータ６０を備える。正極４５は、正極基材４６及びこの正極基材４６上に配置される正極活物質層４７を含む。正極活物質層４７は、正極活物質粒子４８を有する。負極５５は、負極基材５６及びこの負極基材５６上に配置される負極活物質層５７を含む。負極活物質層５７は、負極活物質粒子５８を有する。セパレータ６０は、正極４５及び負極５５に挟まれている。セパレータ６０は、負極活物質層５７と対向するように配置される基材層６１と、正極活物質層４７と対向するように配置される保護層６２とを含む。
As described above, the electrode body provided in the power storage device of the present embodiment is formed by stacking the positive electrode and the negative electrode in the thickness direction with the separator interposed therebetween. FIG. 1 shows an example of the layer structure of the electrode body of this embodiment. The electrode assembly 2 includes a positive electrode 45 as a second electrode, a negative electrode 55 as a first electrode, and a separator 60 . The positive electrode 45 includes a positive electrode substrate 46 and a positive electrode active material layer 47 disposed on the positive electrode substrate 46 . The positive electrode active material layer 47 has positive electrode active material particles 48 . The negative electrode 55 includes a negative electrode base material 56 and a negative electrode active material layer 57 disposed on the negative electrode base material 56 . The negative electrode active material layer 57 has negative electrode active material particles 58 . A separator 60 is sandwiched between the positive electrode 45 and the negative electrode 55 . Separator 60 includes a base layer 61 arranged to face negative electrode active material layer 57 and a protective layer 62 arranged to face positive electrode active material layer 47 .
（非水電解質）
非水電解質としては、公知の非水電解質の中から適宜選択できる。非水電解質には、非水電解液を用いてもよい。非水電解液は、非水溶媒と、この非水溶媒に溶解されている電解質塩とを含む。 (Non-aqueous electrolyte)
The non-aqueous electrolyte can be appropriately selected from known non-aqueous electrolytes. A non-aqueous electrolyte may be used as the non-aqueous electrolyte. The non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in this non-aqueous solvent.
非水電解質としては、公知の非水電解質の中から適宜選択できる。非水電解質には、非水電解液を用いてもよい。非水電解液は、非水溶媒と、この非水溶媒に溶解されている電解質塩とを含む。 (Non-aqueous electrolyte)
The non-aqueous electrolyte can be appropriately selected from known non-aqueous electrolytes. A non-aqueous electrolyte may be used as the non-aqueous electrolyte. The non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in this non-aqueous solvent.
非水溶媒としては、公知の非水溶媒の中から適宜選択できる。非水溶媒としては、環状カーボネート、鎖状カーボネート、カルボン酸エステル、リン酸エステル、スルホン酸エステル、エーテル、アミド、ニトリル等が挙げられる。非水溶媒として、これらの化合物に含まれる水素原子の一部がハロゲンに置換されたものを用いてもよい。
The non-aqueous solvent can be appropriately selected from known non-aqueous solvents. Non-aqueous solvents include cyclic carbonates, chain carbonates, carboxylic acid esters, phosphoric acid esters, sulfonic acid esters, ethers, amides, nitriles and the like. As the non-aqueous solvent, those in which some of the hydrogen atoms contained in these compounds are substituted with halogens may be used.
環状カーボネートとしては、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、ビニレンカーボネート（ＶＣ）、ビニルエチレンカーボネート（ＶＥＣ）、クロロエチレンカーボネート、フルオロエチレンカーボネート（ＦＥＣ）、ジフルオロエチレンカーボネート（ＤＦＥＣ）、スチレンカーボネート、１－フェニルビニレンカーボネート、１，２－ジフェニルビニレンカーボネート等が挙げられる。これらの中でもＥＣが好ましい。
Cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinylethylene carbonate (VEC), chloroethylene carbonate, fluoroethylene carbonate (FEC), and difluoroethylene carbonate. (DFEC), styrene carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate and the like. Among these, EC is preferred.
鎖状カーボネートとしては、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）、ジフェニルカーボネート、トリフルオロエチルメチルカーボネート、ビス（トリフルオロエチル）カーボネート等が挙げられる。これらの中でもＥＭＣが好ましい。
Examples of chain carbonates include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diphenyl carbonate, trifluoroethylmethyl carbonate, bis(trifluoroethyl) carbonate, and the like. Among these, EMC is preferred.
非水溶媒として、環状カーボネート又は鎖状カーボネートを用いることが好ましく、環状カーボネートと鎖状カーボネートとを併用することがより好ましい。環状カーボネートを用いることで、電解質塩の解離を促進して非水電解液のイオン伝導度を向上させることができる。鎖状カーボネートを用いることで、非水電解液の粘度を低く抑えることができる。環状カーボネートと鎖状カーボネートとを併用する場合、環状カーボネートと鎖状カーボネートとの体積比率（環状カーボネート：鎖状カーボネート）としては、例えば、５：９５から５０：５０の範囲とすることが好ましい。
As the non-aqueous solvent, it is preferable to use a cyclic carbonate or a chain carbonate, and it is more preferable to use a combination of a cyclic carbonate and a chain carbonate. By using a cyclic carbonate, it is possible to promote the dissociation of the electrolyte salt and improve the ionic conductivity of the non-aqueous electrolyte. By using a chain carbonate, the viscosity of the non-aqueous electrolyte can be kept low. When a cyclic carbonate and a chain carbonate are used together, the volume ratio of the cyclic carbonate to the chain carbonate (cyclic carbonate:chain carbonate) is preferably in the range of, for example, 5:95 to 50:50.
電解質塩としては、公知の電解質塩から適宜選択できる。電解質塩としては、リチウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、オニウム塩等が挙げられる。これらの中でもリチウム塩が好ましい。
The electrolyte salt can be appropriately selected from known electrolyte salts. Examples of electrolyte salts include lithium salts, sodium salts, potassium salts, magnesium salts, onium salts and the like. Among these, lithium salts are preferred.
リチウム塩としては、ＬｉＰＦ６、ＬｉＰＯ２Ｆ２、ＬｉＢＦ４、ＬｉＣｌＯ４、ＬｉＮ（ＳＯ２Ｆ）２等の無機リチウム塩、ＬｉＳＯ３ＣＦ３、ＬｉＮ（ＳＯ２ＣＦ３）２、ＬｉＮ（ＳＯ２Ｃ２Ｆ５）２、ＬｉＮ（ＳＯ２ＣＦ３）（ＳＯ２Ｃ４Ｆ９）、ＬｉＣ（ＳＯ２ＣＦ３）３、ＬｉＣ（ＳＯ２Ｃ２Ｆ５）３等のハロゲン化炭化水素基を有するリチウム塩等が挙げられる。これらの中でも、無機リチウム塩が好ましく、ＬｉＰＦ６がより好ましい。
Lithium salts include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiClO 4 and LiN(SO 2 F) 2 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C2F5 ) 2 , LiN( SO2CF3 ) ( SO2C4F9 ) , LiC(SO2CF3)3 , LiC ( SO2C2F5 )3 and other halogenated hydrocarbon groups and lithium salts having Among these, inorganic lithium salts are preferred, and LiPF6 is more preferred.
非水電解液における電解質塩の含有量は、０．１ｍｏｌ／ｄｍ３以上２．５ｍｏｌ／ｄｍ３以下であると好ましく、０．３ｍｏｌ／ｄｍ３以上２．０ｍｏｌ／ｄｍ３以下であるとより好ましく、０．５ｍｏｌ／ｄｍ３以上１．７ｍｏｌ／ｄｍ３以下であるとさらに好ましく、０．７ｍｏｌ／ｄｍ３以上１．５ｍｏｌ／ｄｍ３以下であると特に好ましい。電解質塩の含有量を上記の範囲とすることで、非水電解液のイオン伝導度を高めることができる。
The content of the electrolyte salt in the non-aqueous electrolyte is preferably 0.1 mol/dm 3 or more and 2.5 mol/dm 3 or less, more preferably 0.3 mol/dm 3 or more and 2.0 mol/dm 3 or less. , more preferably 0.5 mol/dm 3 or more and 1.7 mol/dm 3 or less, and particularly preferably 0.7 mol/dm 3 or more and 1.5 mol/dm 3 or less. By setting the content of the electrolyte salt within the above range, the ionic conductivity of the non-aqueous electrolyte can be increased.
非水電解液は、添加剤を含んでもよい。添加剤としては、例えばビフェニル、アルキルビフェニル、ターフェニル、ターフェニルの部分水素化体、シクロヘキシルベンゼン、ｔ－ブチルベンゼン、ｔ－アミルベンゼン、ジフェニルエーテル、ジベンゾフラン等の芳香族化合物；２－フルオロビフェニル、ｏ－シクロヘキシルフルオロベンゼン、ｐ－シクロヘキシルフルオロベンゼン等の前記芳香族化合物の部分ハロゲン化物；２，４－ジフルオロアニソール、２，５－ジフルオロアニソール、２，６－ジフルオロアニソール、３，５－ジフルオロアニソール等のハロゲン化アニソール化合物；無水コハク酸、無水グルタル酸、無水マレイン酸、無水シトラコン酸、無水グルタコン酸、無水イタコン酸、シクロヘキサンジカルボン酸無水物；亜硫酸エチレン、亜硫酸プロピレン、亜硫酸ジメチル、硫酸ジメチル、硫酸エチレン、スルホラン、ジメチルスルホン、ジエチルスルホン、ジメチルスルホキシド、ジエチルスルホキシド、テトラメチレンスルホキシド、ジフェニルスルフィド、４，４’－ビス（２，２－ジオキソ－１，３，２－ジオキサチオラン）、４－メチルスルホニルオキシメチル－２，２－ジオキソ－１，３，２－ジオキサチオラン、チオアニソール、ジフェニルジスルフィド、ジピリジニウムジスルフィド、パーフルオロオクタン、ホウ酸トリストリメチルシリル、リン酸トリストリメチルシリル、チタン酸テトラキストリメチルシリル等が挙げられる。これら添加剤は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。
The non-aqueous electrolyte may contain additives. Examples of additives include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran; -Partial halides of the above aromatic compounds such as cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; Halogenated anisole compounds; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride; ethylene sulfite, propylene sulfite, dimethyl sulfite, dimethyl sulfate, ethylene sulfate, sulfolane, dimethylsulfone, diethylsulfone, dimethylsulfoxide, diethylsulfoxide, tetramethylenesulfoxide, diphenylsulfide, 4,4′-bis(2,2-dioxo-1,3,2-dioxathiolane), 4-methylsulfonyloxymethyl- 2,2-dioxo-1,3,2-dioxathiolane, thioanisole, diphenyl disulfide, dipyridinium disulfide, perfluorooctane, tristrimethylsilyl borate, tristrimethylsilyl phosphate, tetrakistrimethylsilyl titanate and the like. These additives may be used singly or in combination of two or more.
非水電解液に含まれる添加剤の含有量は、非水電解液全体の質量に対して０．０１質量％以上１０質量％以下であると好ましく、０．１質量％以上７質量％以下であるとより好ましく、０．２質量％以上５質量％以下であるとさらに好ましく、０．３質量％以上３質量％以下であると特に好ましい。添加剤の含有量を上記の範囲とすることで、高温保存後の容量維持性能又はサイクル性能を向上させたり、安全性をより向上させたりすることができる。
The content of the additive contained in the non-aqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 7% by mass or less with respect to the total mass of the non-aqueous electrolyte. More preferably, it is 0.2% by mass or more and 5% by mass or less, and particularly preferably 0.3% by mass or more and 3% by mass or less. By setting the content of the additive within the above range, it is possible to improve capacity retention performance or cycle performance after high-temperature storage, or to further improve safety.
非水電解質には、固体電解質を用いてもよく、非水電解液と固体電解質とを併用してもよい。
A solid electrolyte may be used as the non-aqueous electrolyte, or a non-aqueous electrolyte and a solid electrolyte may be used together.
固体電解質としては、リチウム、ナトリウム、カルシウム等のイオン伝導性を有し、常温（例えば１５℃から２５℃）において固体である任意の材料から選択できる。固体電解質としては、例えば、硫化物固体電解質、酸化物固体電解質、及び酸窒化物固体電解質、ポリマー固体電解質等が挙げられる。
The solid electrolyte can be selected from any material that has ion conductivity, such as lithium, sodium, and calcium, and is solid at room temperature (for example, 15°C to 25°C). Examples of solid electrolytes include sulfide solid electrolytes, oxide solid electrolytes, oxynitride solid electrolytes, and polymer solid electrolytes.
硫化物固体電解質としては、リチウムイオン二次電池の場合、例えば、Ｌｉ２Ｓ－Ｐ２Ｓ５、ＬｉＩ－Ｌｉ２Ｓ－Ｐ２Ｓ５、Ｌｉ１０Ｇｅ－Ｐ２Ｓ１２等が挙げられる。
Examples of sulfide solid electrolytes for lithium ion secondary batteries include Li 2 SP 2 S 5 , LiI—Li 2 SP 2 S 5 and Li 10 Ge—P 2 S 12 .
本実施形態の蓄電素子の形状については特に限定されるものではなく、例えば、円筒型電池、角型電池、扁平型電池、コイン型電池、ボタン型電池等が挙げられる。
図２に角型電池の一例としての蓄電素子１（非水電解質蓄電素子）の容器内部を透視した図を示す。セパレータを挟んで巻回された正極及び負極を有する電極体２が角型の容器３に収納される。正極は正極リード４１を介して正極端子４と電気的に接続されている。負極は負極リード５１を介して負極端子５と電気的に接続されている。図２では、蓄電素子１における電極体２の巻回の軸線方向をＸ方向、蓄電素子１の厚さ方向をＹ方向、上記軸線方向（Ｘ方向）に垂直かつ上記厚さ方向（Ｙ方向）に垂直な方向をＺ方向として示す。なお、Ｚ方向は、蓄電素子１における電極体２の平坦部（すなわち、平坦部の表面）に平行であり、かつ上記平坦部での電極体２の巻き方向に一致する。ここでは、蓄電素子１の厚さ方向は、電極体２の厚さ方向と一致する。電極体２の厚さ方向は、正極、負極及びセパレータの積層方向に相当し、また、これら正極、負極及びセパレータの表面に垂直な方向にも相当する。 The shape of the electric storage element of the present embodiment is not particularly limited, and examples thereof include cylindrical batteries, rectangular batteries, flat batteries, coin batteries, button batteries, and the like.
FIG. 2 shows a see-through view of the inside of a container of a power storage element 1 (non-aqueous electrolyte power storage element) as an example of a square battery. Anelectrode body 2 having a positive electrode and a negative electrode wound with a separator sandwiched therebetween is housed in a rectangular container 3 . The positive electrode is electrically connected to the positive electrode terminal 4 via a positive electrode lead 41 . The negative electrode is electrically connected to the negative terminal 5 via a negative lead 51 . In FIG. 2, the axial direction of winding of the electrode body 2 in the storage element 1 is the X direction, the thickness direction of the storage element 1 is the Y direction, and the thickness direction (Y direction) is perpendicular to the axial direction (X direction). The direction perpendicular to is shown as the Z direction. The Z direction is parallel to the flat portion (that is, the surface of the flat portion) of the electrode body 2 in the electric storage element 1 and coincides with the winding direction of the electrode body 2 at the flat portion. Here, the thickness direction of the storage element 1 coincides with the thickness direction of the electrode body 2 . The thickness direction of the electrode body 2 corresponds to the stacking direction of the positive electrode, the negative electrode and the separator, and also corresponds to the direction perpendicular to the surfaces of the positive electrode, the negative electrode and the separator.
図２に角型電池の一例としての蓄電素子１（非水電解質蓄電素子）の容器内部を透視した図を示す。セパレータを挟んで巻回された正極及び負極を有する電極体２が角型の容器３に収納される。正極は正極リード４１を介して正極端子４と電気的に接続されている。負極は負極リード５１を介して負極端子５と電気的に接続されている。図２では、蓄電素子１における電極体２の巻回の軸線方向をＸ方向、蓄電素子１の厚さ方向をＹ方向、上記軸線方向（Ｘ方向）に垂直かつ上記厚さ方向（Ｙ方向）に垂直な方向をＺ方向として示す。なお、Ｚ方向は、蓄電素子１における電極体２の平坦部（すなわち、平坦部の表面）に平行であり、かつ上記平坦部での電極体２の巻き方向に一致する。ここでは、蓄電素子１の厚さ方向は、電極体２の厚さ方向と一致する。電極体２の厚さ方向は、正極、負極及びセパレータの積層方向に相当し、また、これら正極、負極及びセパレータの表面に垂直な方向にも相当する。 The shape of the electric storage element of the present embodiment is not particularly limited, and examples thereof include cylindrical batteries, rectangular batteries, flat batteries, coin batteries, button batteries, and the like.
FIG. 2 shows a see-through view of the inside of a container of a power storage element 1 (non-aqueous electrolyte power storage element) as an example of a square battery. An
容器３としては、蓄電素子の容器として通常用いられる公知の金属容器、樹脂容器等を用いることができる。電極体２は、正極と負極とセパレータとが蓄電素子１の厚さ方向（Ｙ方向）に積層され、かつ上記厚さ方向に垂直な方向（Ｘ方向）に延びる軸線（図示せず）を中心として巻回された構造を有する。図２では、電極体２は、正極と負極とセパレータとが平面状に重ね合わされている平坦部を有する。この平坦部は、上記厚さ方向（Ｙ方向）に垂直な平面に沿って配置される。すなわち、上記平坦部は、上記軸線方向（Ｘ方向）と、上記軸線方向（Ｘ方向）に垂直かつ上記厚さ方向（Ｙ方向）に垂直な方向（Ｚ方向）との双方に平行な平面に沿って配置される。上記厚さ方向は、蓄電素子１の電極体２における正極、負極及びセパレータの積層方向と一致する。容器３内には非水電解質が収容される。
As the container 3, a known metal container, resin container, or the like, which is usually used as a container for an electric storage element, can be used. The electrode body 2 is formed by stacking a positive electrode, a negative electrode, and a separator in the thickness direction (Y direction) of the storage element 1, and is centered on an axis (not shown) extending in a direction (X direction) perpendicular to the thickness direction. It has a wound structure. In FIG. 2, the electrode body 2 has a flat portion in which the positive electrode, the negative electrode, and the separator are overlaid in a plane. The flat portion is arranged along a plane perpendicular to the thickness direction (Y direction). That is, the flat portion is formed on a plane parallel to both the axial direction (X direction) and a direction (Z direction) perpendicular to the axial direction (X direction) and perpendicular to the thickness direction (Y direction). placed along. The thickness direction coincides with the stacking direction of the positive electrode, the negative electrode, and the separator in the electrode body 2 of the storage element 1 . A non-aqueous electrolyte is accommodated in the container 3 .
蓄電素子１の電極体２は、その厚さ方向（Ｙ方向）に押圧された状態である。但し、電極体２の一部（例えば、扁平状の巻回型の電極体２における一対の曲面部等）は、押圧されていなくてもよい。このように電極体２がその厚さ方向に押圧された状態であるべく、蓄電素子１は、後述するように、例えば従来公知の拘束部材等によってその厚さ方向に押圧された状態とされる。このように、蓄電素子１の電極体２がその厚さ方向に押圧された状態である場合、内部抵抗の増加及び自己放電を抑制することができる。
The electrode body 2 of the storage element 1 is in a state of being pressed in its thickness direction (Y direction). However, a part of the electrode body 2 (for example, a pair of curved surface portions of the flat wound electrode body 2, etc.) may not be pressed. In order to keep the electrode body 2 pressed in its thickness direction, the electric storage element 1 is pressed in its thickness direction by, for example, a conventionally known restraining member or the like, as will be described later. . Thus, when the electrode body 2 of the electric storage element 1 is pressed in its thickness direction, it is possible to suppress an increase in internal resistance and self-discharge.
＜蓄電装置の構成＞
本実施形態の蓄電素子は、電気自動車（ＥＶ）、ハイブリッド自動車（ＨＥＶ）、プラグインハイブリッド自動車（ＰＨＥＶ）等の自動車用電源、パーソナルコンピュータ、通信端末等の電子機器用電源、又は電力貯蔵用電源等に、複数の蓄電素子１を集合して構成した蓄電ユニット（バッテリーモジュール）として搭載することができる。この場合、蓄電ユニットに含まれる少なくとも一つの蓄電素子に対して、本発明の技術が適用されていればよい。
図３及び図４に、電気的に接続された二以上の蓄電素子１が集合した蓄電装置１０の一例を示す。図３及び図４では、各蓄電素子１における電極体２の巻回の軸線方向をＸ方向、各蓄電素子１の厚さ方向（すなわち、複数の蓄電素子１の配列方向、かつ電極体２の厚さ方向）をＹ方向、上記軸線方向に垂直かつ上記厚さ方向に垂直な方向をＺ方向（すなわち、上記平坦部での電極体２の巻き方向）として示す。なお、Ｚ方向は、各蓄電素子１における電極体２の平坦部（すなわち、平坦部の表面）に平行である。 <Configuration of power storage device>
The power storage device of the present embodiment is a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), power sources for electronic devices such as personal computers and communication terminals, or power sources for power storage. For example, it can be mounted as a power storage unit (battery module) configured by assembling a plurality ofpower storage elements 1 . In this case, the technology of the present invention may be applied to at least one power storage element included in the power storage unit.
3 and 4 show an example of apower storage device 10 in which two or more electrically connected power storage elements 1 are assembled. 3 and 4, the axial direction of the winding of the electrode body 2 in each storage element 1 is the X direction, the thickness direction of each storage element 1 (that is, the arrangement direction of the plurality of storage elements 1 and the direction of the electrode assembly 2). (thickness direction) is shown as the Y direction, and the direction perpendicular to the axial direction and perpendicular to the thickness direction is shown as the Z direction (that is, the winding direction of the electrode body 2 at the flat portion). Note that the Z direction is parallel to the flat portion (that is, the surface of the flat portion) of the electrode body 2 in each storage element 1 .
本実施形態の蓄電素子は、電気自動車（ＥＶ）、ハイブリッド自動車（ＨＥＶ）、プラグインハイブリッド自動車（ＰＨＥＶ）等の自動車用電源、パーソナルコンピュータ、通信端末等の電子機器用電源、又は電力貯蔵用電源等に、複数の蓄電素子１を集合して構成した蓄電ユニット（バッテリーモジュール）として搭載することができる。この場合、蓄電ユニットに含まれる少なくとも一つの蓄電素子に対して、本発明の技術が適用されていればよい。
図３及び図４に、電気的に接続された二以上の蓄電素子１が集合した蓄電装置１０の一例を示す。図３及び図４では、各蓄電素子１における電極体２の巻回の軸線方向をＸ方向、各蓄電素子１の厚さ方向（すなわち、複数の蓄電素子１の配列方向、かつ電極体２の厚さ方向）をＹ方向、上記軸線方向に垂直かつ上記厚さ方向に垂直な方向をＺ方向（すなわち、上記平坦部での電極体２の巻き方向）として示す。なお、Ｚ方向は、各蓄電素子１における電極体２の平坦部（すなわち、平坦部の表面）に平行である。 <Configuration of power storage device>
The power storage device of the present embodiment is a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), power sources for electronic devices such as personal computers and communication terminals, or power sources for power storage. For example, it can be mounted as a power storage unit (battery module) configured by assembling a plurality of
3 and 4 show an example of a
図３及び図４に示すように、蓄電装置１０は、各蓄電素子１の厚さ方向（Ｙ方向）に並んで配置される複数の蓄電素子１と、これら複数の蓄電素子１を上記厚さ方向（複数の蓄電素子１の配列方向、Ｙ方向）の両外側から挟んで支持する一対の支持部１０１と、これら支持部１０１を連結する１又は複数（ここでは４つ）の連結部１０２とを備える。上記厚さ方向（Ｙ方向）は、各蓄電素子１の電極体２における正極、負極及びセパレータの積層方向と一致する。図３及び図４に示す態様では、一対の支持部１０１及び連結部１０２が拘束部材を構成する。なお、蓄電装置１０は、各蓄電素子１の容器３の蓋に設けられたガス排出弁（図示せず）から排出されたガスの経路として機能する排気管、電極体２と外部の出力機器とを電気的に接続する接続端子等をさらに備えていてもよい。
As shown in FIGS. 3 and 4, the power storage device 10 includes a plurality of power storage elements 1 arranged side by side in the thickness direction (Y direction) of each power storage element 1, and the plurality of power storage elements 1 having the above thickness. A pair of support portions 101 sandwiched and supported from both outer sides in the direction (the direction in which the plurality of storage elements 1 are arranged, the Y direction), and one or a plurality of (here, four) connection portions 102 that connect these support portions 101. Prepare. The thickness direction (Y direction) coincides with the stacking direction of the positive electrode, the negative electrode, and the separator in the electrode body 2 of each storage element 1 . In the mode shown in FIGS. 3 and 4, a pair of supporting portion 101 and connecting portion 102 constitutes a restraining member. The power storage device 10 includes an exhaust pipe functioning as a path for gas discharged from a gas discharge valve (not shown) provided on the lid of the container 3 of each power storage element 1, an electrode body 2, and an external output device. may further include a connection terminal or the like for electrically connecting the .
複数の蓄電素子１は、互いの側面が対向するように厚さ方向（Ｙ方向）に並んで配置され、一対の支持部１０１によって、上記厚さ方向（Ｙ方向）の両外側から挟まれる。
A plurality of power storage elements 1 are arranged side by side in the thickness direction (Y direction) so that their side surfaces face each other, and are sandwiched by a pair of support portions 101 from both outer sides in the thickness direction (Y direction).
一対の支持部１０１は、例えば板状である。図３及び図４に示す態様では、一対の支持部１０１は、複数（ここでは４つ）の連結部１０２によって連結される。一対の支持部１０１は、それぞれ、外表面から内部へと形成された複数の螺合用孔１０３を有する。螺合用孔１０３は、深部にナット部（図示せず）を有する。
The pair of support parts 101 are plate-shaped, for example. In the embodiment shown in FIGS. 3 and 4 , a pair of support portions 101 are connected by a plurality of (here, four) connection portions 102 . Each of the pair of support portions 101 has a plurality of screwing holes 103 formed from the outer surface to the inside. The screwing hole 103 has a nut portion (not shown) in its deep portion.
各連結部１０２は、例えば板状である。図３及び図４に示す態様では、各連結部１０２は、上記厚さ方向（Ｙ方向）に延びるように配置され、かつその両端部が一対の支持部１０１の外面と接触するようにそれぞれ折り曲げられた形状に形成される。各連結部１０２の両端部は、それぞれ、対応する（接触する）支持部１０１における複数の螺合用孔１０３のうちの１つに重ね合わされるように形成された貫通孔１０４を有する。
Each connecting part 102 is plate-shaped, for example. In the embodiment shown in FIGS. 3 and 4, each connecting portion 102 is arranged to extend in the thickness direction (Y direction), and both ends thereof are bent so as to come into contact with the outer surfaces of the pair of supporting portions 101. formed into the shape Both end portions of each connecting portion 102 each have a through hole 104 formed so as to overlap one of the plurality of screwing holes 103 in the corresponding (contacting) support portion 101 .
各連結部１０２の両端部の各貫通孔１０４が、それに対応する一対の支持部１０１の各螺合用孔１０３に上記厚さ方向（Ｙ方向）外側から重ね合わされ、各貫通孔１０４及び各螺合用孔１０３にそれぞれボルト（図示せず）が挿入され、各ボルトが各螺合用孔１０３に螺合される。この螺合により、一対の支持部１０１が複数の連結部１０２によって連結される。この連結において、例えば連結部１０２の長さを調整すること、上記ボルトの締め付けの程度を調整すること等によって、一対の支持部１０１の間隔が調整される。この間隔の調整により、複数の蓄電素子１が一対の支持部１０１によって両外側から押圧された状態で支持される、すなわち、複数の蓄電素子１が上記厚さ方向（Ｙ方向）に押圧された状態で支持される。
The through holes 104 at both ends of each connecting portion 102 are superimposed on the corresponding screw holes 103 of the pair of support portions 101 from the outside in the thickness direction (Y direction). A bolt (not shown) is inserted into each hole 103 and each bolt is screwed into each screwing hole 103 . A pair of support parts 101 are connected by a plurality of connecting parts 102 by this screwing. In this connection, the distance between the pair of support portions 101 is adjusted by, for example, adjusting the length of the connecting portion 102 and adjusting the tightening degree of the bolt. By adjusting this interval, the plurality of storage elements 1 are supported by the pair of support portions 101 while being pressed from both outer sides, that is, the plurality of storage elements 1 are pressed in the thickness direction (Y direction). supported by the state.
このように、一対の支持部１０１及び複数の連結部１０２で構成される拘束部材によって複数の蓄電素子１が拘束されることにより、複数の蓄電素子１は、上記厚さ方向（Ｙ方向）に押圧された状態で蓄電装置１０に備えられる。このように複数の蓄電素子１が押圧された状態となることで、各蓄電素子１の電極体２が押圧された状態となる。上記拘束部材としては、蓄電素子１を押圧（すなわち、加圧）することが可能なものであればよく、特に限定されない。なお、上記拘束部材によって蓄電素子１の電極体２を押圧する態様としては、蓄電素子１が一定の厚さになるように拘束部材によって蓄電素子１を押圧すること（定寸拘束）、蓄電素子１に加えられている押圧力が一定の値となるように拘束部材によって蓄電素子１を押圧すること（定圧拘束）等が挙げられる。
In this manner, the plurality of energy storage elements 1 are restrained by the restraining member composed of the pair of support portions 101 and the plurality of connecting portions 102, so that the plurality of energy storage elements 1 are arranged in the thickness direction (Y direction). It is provided in power storage device 10 in a pressed state. By pressing the plurality of storage elements 1 in this manner, the electrode bodies 2 of the storage elements 1 are pressed. The restraining member is not particularly limited as long as it can press (that is, pressurize) the storage element 1 . As a mode of pressing the electrode body 2 of the electric storage element 1 by the restraining member, the electric storage element 1 is pressed by the restraining member so that the electric storage element 1 has a constant thickness (fixed size restraint). For example, a restraining member presses the storage element 1 so that the pressing force applied to the storage element 1 has a constant value (constant pressure restraint).
厚さ方向（Ｙ方向）両端に配置される各蓄電素子１の一対の支持部１０１との接触面（外側面）における一対の支持部１０１によって押圧される領域（以下、押圧領域ともいう）は、特に限定されず、例えば内部抵抗の増加及び自己放電の抑制の効果と、所望の電池特性とを考慮して適宜設定され得る。
A region pressed by the pair of support portions 101 (hereinafter also referred to as a press region) on the contact surface (outer surface) with the pair of support portions 101 of each storage element 1 arranged at both ends in the thickness direction (Y direction) is is not particularly limited, and can be appropriately set in consideration of, for example, the effect of increasing internal resistance and suppressing self-discharge, and desired battery characteristics.
上記押圧領域は、上記接触面の全領域（連続した１の領域）であっても、中央部の部分領域（連続した１の領域）であっても、周縁に沿って全周にわたって延びる環状の部分領域（連続した１の領域）であっても、互いに間隔を空けて配置される複数の部分領域（互いに離間した複数の領域）であってもよい。上記押圧領域が互いに離間した複数の部分領域である場合、例えば以下の態様が挙げられる。
（１）４の部分領域が、矩形状の接触面の４隅にそれぞれ配置される態様
（２）２の部分領域が、接触面の上記軸線方向（Ｘ方向）に間隔を空けて、例えば上記軸線方向（Ｘ方向）両端部にそれぞれ、上記平坦部での電極体の巻き方向（Ｚ方向）に延びるように平行に配置される態様
（３）３以上の部分領域が、接触面の上記軸線方向（Ｘ方向）に互いに等しい間隔を空けて、上記巻き方向（Ｚ方向）に延びるように平行に配置される態様
（４）２の部分領域が接触面の上記巻き方向（Ｚ方向）に間隔を空けて、例えば上記巻き方向（Ｚ方向）の両端部にそれぞれ、上記軸線方向（Ｘ方向）に延びるように平行に配置される態様
（５）３以上の部分領域が、接触面の上記巻き方向（Ｚ方向）に互いに等しい間隔を空けて、上記軸線方向（Ｘ方向）に延びるように平行に配置される態様
（６）５以上の部分領域が接触面の周縁に沿って全周にわたって互いに間隔を空けて配置される態様
上記（１）から（６）の態様においては、複数の部分領域の全てが接触面の周縁から内側に間隔を空けて配置されてもよく、複数の部分領域の少なくとも１つが接触面の周縁に接触するように配置されてもよい。各部分領域の形状は、特に限定されず、適宜設定され得る。 The pressing area is an annular shape extending along the periphery of the entire contact surface (one continuous area) or a central partial area (one continuous area). It may be a partial area (one continuous area) or a plurality of partial areas (a plurality of mutually spaced areas) arranged at intervals. When the pressing area is a plurality of partial areas separated from each other, for example, the following aspects may be mentioned.
(1) Four partial areas are arranged at four corners of a rectangular contact surface (2) Two partial areas are spaced apart in the axial direction (X direction) of the contact surface, Aspect (3) Three or more partial regions arranged in parallel so as to extend in the winding direction (Z direction) of the electrode body at the flat portion at both ends in the axial direction (X direction) respectively, The partial areas of mode (4) 2, which are arranged in parallel so as to extend in the winding direction (Z direction), are spaced apart in the winding direction (Z direction) of the contact surface at equal intervals in the direction (X direction). Aspect (5) Three or more partial regions arranged in parallel so as to extend in the axial direction (X direction), for example, at both ends in the winding direction (Z direction) with a space between the windings of the contact surface Aspect (6) Five or more partial regions arranged parallel to each other so as to extend in the axial direction (X direction) at equal intervals in the direction (Z direction) are arranged along the periphery of the contact surface along the entire circumference Aspects Arranged at Spaces In the above aspects (1) to (6), all of the plurality of partial regions may be arranged at intervals inward from the peripheral edge of the contact surface, and the plurality of partial regions may be arranged at intervals. At least one may be arranged to contact the periphery of the contact surface. The shape of each partial region is not particularly limited and can be set as appropriate.
（１）４の部分領域が、矩形状の接触面の４隅にそれぞれ配置される態様
（２）２の部分領域が、接触面の上記軸線方向（Ｘ方向）に間隔を空けて、例えば上記軸線方向（Ｘ方向）両端部にそれぞれ、上記平坦部での電極体の巻き方向（Ｚ方向）に延びるように平行に配置される態様
（３）３以上の部分領域が、接触面の上記軸線方向（Ｘ方向）に互いに等しい間隔を空けて、上記巻き方向（Ｚ方向）に延びるように平行に配置される態様
（４）２の部分領域が接触面の上記巻き方向（Ｚ方向）に間隔を空けて、例えば上記巻き方向（Ｚ方向）の両端部にそれぞれ、上記軸線方向（Ｘ方向）に延びるように平行に配置される態様
（５）３以上の部分領域が、接触面の上記巻き方向（Ｚ方向）に互いに等しい間隔を空けて、上記軸線方向（Ｘ方向）に延びるように平行に配置される態様
（６）５以上の部分領域が接触面の周縁に沿って全周にわたって互いに間隔を空けて配置される態様
上記（１）から（６）の態様においては、複数の部分領域の全てが接触面の周縁から内側に間隔を空けて配置されてもよく、複数の部分領域の少なくとも１つが接触面の周縁に接触するように配置されてもよい。各部分領域の形状は、特に限定されず、適宜設定され得る。 The pressing area is an annular shape extending along the periphery of the entire contact surface (one continuous area) or a central partial area (one continuous area). It may be a partial area (one continuous area) or a plurality of partial areas (a plurality of mutually spaced areas) arranged at intervals. When the pressing area is a plurality of partial areas separated from each other, for example, the following aspects may be mentioned.
(1) Four partial areas are arranged at four corners of a rectangular contact surface (2) Two partial areas are spaced apart in the axial direction (X direction) of the contact surface, Aspect (3) Three or more partial regions arranged in parallel so as to extend in the winding direction (Z direction) of the electrode body at the flat portion at both ends in the axial direction (X direction) respectively, The partial areas of mode (4) 2, which are arranged in parallel so as to extend in the winding direction (Z direction), are spaced apart in the winding direction (Z direction) of the contact surface at equal intervals in the direction (X direction). Aspect (5) Three or more partial regions arranged in parallel so as to extend in the axial direction (X direction), for example, at both ends in the winding direction (Z direction) with a space between the windings of the contact surface Aspect (6) Five or more partial regions arranged parallel to each other so as to extend in the axial direction (X direction) at equal intervals in the direction (Z direction) are arranged along the periphery of the contact surface along the entire circumference Aspects Arranged at Spaces In the above aspects (1) to (6), all of the plurality of partial regions may be arranged at intervals inward from the peripheral edge of the contact surface, and the plurality of partial regions may be arranged at intervals. At least one may be arranged to contact the periphery of the contact surface. The shape of each partial region is not particularly limited and can be set as appropriate.
上記した接触面における１又は複数の押圧領域の形状及び配置は、例えば一対の支持部１０１における上記厚さ方向（Ｙ方向）の内側面に１又は複数の突出部を形成し、かつこの１又は複数の突出部を、所望の形状及び配置を有する押圧領域を形成することができるように形成することによって実現され得る。また、この１又は複数の突出部の突出量を調整することによって上記押圧力を調整することもできる。
The shape and arrangement of the one or more pressing regions on the contact surface is such that, for example, one or more protrusions are formed on the inner surface of the pair of support portions 101 in the thickness direction (Y direction), and the one or more It can be realized by forming a plurality of protrusions so as to form a pressing area having a desired shape and arrangement. Also, the pressing force can be adjusted by adjusting the amount of protrusion of the one or more protrusions.
各蓄電素子１の電極体２に加えられる押圧力は、特に限定されず、適宜設定され得る。例えば、各蓄電素子１の電極体２に加えられる押圧力（面圧）の下限としては、０．３ＭＰａが好ましく、０．５ＭＰａがより好ましく、０．７ＭＰａがさらに好ましく、１．０ＭＰａがよりさらに好ましい場合がある。上記押圧力の下限が上記下限以上である場合には、各蓄電素子１の内部抵抗の増加の抑制効果及び自己放電の抑制効果がより顕著に発揮される。一方、上記圧力の上限としては、３．７ＭＰａが好ましく、３．５ＭＰａがより好ましく、３．３ＭＰａがさらに好ましく、３．０ＭＰａがよりさらに好ましい場合がある。上記押圧力が上記上限以下である場合には、過度の押圧力が加えられることに起因するセパレータの空孔の閉塞を抑制することができる。以上の観点から、上記押圧力の範囲としては、０．３ＭＰａ以上３．７ＭＰａ以下が好ましく、０．５ＭＰａ以上３．５ＭＰａ以下がより好ましく、０．７ＭＰａ以上３．３ＭＰａ以下がさらに好ましく、１．０ＭＰａ以上３．０ＭＰａ以下がよりさらに好ましい場合がある。
The pressing force applied to the electrode body 2 of each storage element 1 is not particularly limited and can be set as appropriate. For example, the lower limit of the pressing force (surface pressure) applied to the electrode body 2 of each storage element 1 is preferably 0.3 MPa, more preferably 0.5 MPa, even more preferably 0.7 MPa, and even more preferably 1.0 MPa. Sometimes preferred. When the lower limit of the pressing force is equal to or higher than the lower limit, the effect of suppressing an increase in the internal resistance of each storage element 1 and the effect of suppressing self-discharge are exhibited more remarkably. On the other hand, the upper limit of the pressure is preferably 3.7 MPa, more preferably 3.5 MPa, still more preferably 3.3 MPa, and even more preferably 3.0 MPa. When the pressing force is equal to or less than the upper limit, it is possible to suppress clogging of the pores of the separator due to application of excessive pressing force. From the above viewpoints, the range of the pressing force is preferably 0.3 MPa or more and 3.7 MPa or less, more preferably 0.5 MPa or more and 3.5 MPa or less, further preferably 0.7 MPa or more and 3.3 MPa or less. 0 MPa or more and 3.0 MPa or less may be even more preferable.
各蓄電素子１に加えられる押圧力に応じた押圧力で、各蓄電素子１の電極体２が押圧された状態となる。このため、各蓄電素子１に加えられる押圧力は、各蓄電素子１の電極体２に加えられる押圧力とみなすことができる。上記電極体に加えられる押圧力は、以下の方法により測定された値とする。拘束部材によって押圧された状態の蓄電素子を、電圧が動作下限電圧未満となるよう放電する。「動作下限電圧」とは、蓄電素子が負荷を動作させるために必要な最小電圧をいう。「負荷」とは、蓄電素子から供給される電力を消費するものをいう。次いで、拘束部材によって押圧された状態の蓄電素子を、ロードセルを有する圧縮試験機に設置し、圧縮試験機により、拘束部材によって付与された押圧力よりも十分に小さい任意の荷重を蓄電素子に付与する。この状態で拘束部材による押圧を解き、測定される荷重の変化量を電極体へ付与された荷重とする。この電極体へ付与された荷重を、蓄電素子に荷重が付与された面積で除した値を電極体に加えられる押圧力とする。なお、通常、拘束部材によって蓄電素子の対向する一対の面に対して荷重が付与されるが、この一対の面の一方の面のみの面積を荷重が付与された面積とする。
The electrode body 2 of each storage element 1 is pressed by a pressing force corresponding to the pressing force applied to each storage element 1 . Therefore, the pressing force applied to each storage element 1 can be regarded as the pressing force applied to the electrode body 2 of each storage element 1 . Let the pressing force applied to the said electrode body be the value measured by the following method. The electric storage element pressed by the binding member is discharged so that the voltage becomes less than the operating lower limit voltage. "Lower limit operating voltage" refers to the minimum voltage required for the storage element to operate the load. A “load” refers to something that consumes the power supplied from the storage element. Next, the electric storage element pressed by the restraining member is placed in a compression tester having a load cell, and the compression tester applies an arbitrary load sufficiently smaller than the pressing force applied by the restraining member to the electric storage element. do. In this state, the pressure applied by the restraining member is released, and the amount of change in the measured load is taken as the load applied to the electrode body. The pressing force applied to the electrode body is obtained by dividing the load applied to the electrode body by the area of the storage element to which the load is applied. Although a load is normally applied to a pair of opposing surfaces of the storage element by the restraining member, the area of only one of the pair of surfaces is defined as the area to which the load is applied.
＜蓄電素子の製造方法＞
本実施形態の蓄電素子の製造方法は、公知の方法から適宜選択できる。当該製造方法は、例えば、電極体を準備することと、非水電解質を準備することと、電極体及び非水電解質を容器に収容することと、を備える。電極体を準備することは、正極及び負極を準備することと、正極及び負極を、セパレータを介して積層又は巻回することにより電極体を形成することとを備える。また、上記蓄電素子の製造方法は、電極体及び非水電解質を容器に収容した後、拘束部材等を用いて容器を電極体の厚さ方向に押圧することをさらに備える。 <Method for manufacturing power storage element>
A method for manufacturing the electric storage device of the present embodiment can be appropriately selected from known methods. The manufacturing method includes, for example, preparing an electrode body, preparing a non-aqueous electrolyte, and housing the electrode body and the non-aqueous electrolyte in a container. Preparing the electrode body includes preparing a positive electrode and a negative electrode, and forming the electrode body by laminating or winding the positive electrode and the negative electrode with a separator interposed therebetween. In addition, the method for manufacturing an electric storage element further includes pressing the container in the thickness direction of the electrode assembly using a restraining member or the like after the electrode assembly and the non-aqueous electrolyte are accommodated in the container.
本実施形態の蓄電素子の製造方法は、公知の方法から適宜選択できる。当該製造方法は、例えば、電極体を準備することと、非水電解質を準備することと、電極体及び非水電解質を容器に収容することと、を備える。電極体を準備することは、正極及び負極を準備することと、正極及び負極を、セパレータを介して積層又は巻回することにより電極体を形成することとを備える。また、上記蓄電素子の製造方法は、電極体及び非水電解質を容器に収容した後、拘束部材等を用いて容器を電極体の厚さ方向に押圧することをさらに備える。 <Method for manufacturing power storage element>
A method for manufacturing the electric storage device of the present embodiment can be appropriately selected from known methods. The manufacturing method includes, for example, preparing an electrode body, preparing a non-aqueous electrolyte, and housing the electrode body and the non-aqueous electrolyte in a container. Preparing the electrode body includes preparing a positive electrode and a negative electrode, and forming the electrode body by laminating or winding the positive electrode and the negative electrode with a separator interposed therebetween. In addition, the method for manufacturing an electric storage element further includes pressing the container in the thickness direction of the electrode assembly using a restraining member or the like after the electrode assembly and the non-aqueous electrolyte are accommodated in the container.
非水電解質を容器に収容することは、公知の方法から適宜選択できる。例えば、非水電解質に非水電解液を用いる場合、容器に形成された注入口から非水電解液を注入した後、注入口を封止すればよい。
Containing the non-aqueous electrolyte in the container can be appropriately selected from known methods. For example, when a non-aqueous electrolyte is used as the non-aqueous electrolyte, the non-aqueous electrolyte may be injected through an inlet formed in the container, and then the inlet may be sealed.
＜その他の実施形態＞
尚、本発明の蓄電素子は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加えてもよい。例えば、ある実施形態の構成に他の実施形態の構成を追加することができ、また、ある実施形態の構成の一部を他の実施形態の構成又は周知技術に置き換えることができる。さらに、ある実施形態の構成の一部を削除することができる。また、ある実施形態の構成に対して周知技術を付加することができる。 <Other embodiments>
It should be noted that the electric storage device of the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the gist of the present invention. For example, the configuration of another embodiment can be added to the configuration of one embodiment, and part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a known technique. Furthermore, some of the configurations of certain embodiments can be deleted. Also, well-known techniques can be added to the configuration of a certain embodiment.
尚、本発明の蓄電素子は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加えてもよい。例えば、ある実施形態の構成に他の実施形態の構成を追加することができ、また、ある実施形態の構成の一部を他の実施形態の構成又は周知技術に置き換えることができる。さらに、ある実施形態の構成の一部を削除することができる。また、ある実施形態の構成に対して周知技術を付加することができる。 <Other embodiments>
It should be noted that the electric storage device of the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the gist of the present invention. For example, the configuration of another embodiment can be added to the configuration of one embodiment, and part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a known technique. Furthermore, some of the configurations of certain embodiments can be deleted. Also, well-known techniques can be added to the configuration of a certain embodiment.
上記実施形態では、蓄電素子が充放電可能な非水電解質二次電池（例えばリチウムイオン二次電池）として用いられる場合について説明したが、蓄電素子の種類、形状、寸法、容量等は任意である。本発明は、種々の二次電池、電気二重層キャパシタ又はリチウムイオンキャパシタ等のキャパシタにも適用できる。
In the above embodiment, the storage element is used as a chargeable/dischargeable non-aqueous electrolyte secondary battery (for example, a lithium ion secondary battery), but the type, shape, size, capacity, etc. of the storage element are arbitrary. . The present invention can also be applied to capacitors such as various secondary batteries, electric double layer capacitors, and lithium ion capacitors.
上記実施形態では、第１電極が負極、第２電極が正極である場合について説明したが、第１電極が正極、第２電極が負極であってもよい。この場合、第１電極活物質が正極活物質であり、第２電極活物質が負極活物質であり、負極活物質粒子が正極活物質粒子よりも硬く、基材層が正極活物質層側、保護層が負極活物質層側に配置される。
In the above embodiment, the case where the first electrode is the negative electrode and the second electrode is the positive electrode has been described, but the first electrode may be the positive electrode and the second electrode may be the negative electrode. In this case, the first electrode active material is a positive electrode active material, the second electrode active material is a negative electrode active material, the negative electrode active material particles are harder than the positive electrode active material particles, the base layer is on the positive electrode active material layer side, A protective layer is disposed on the side of the negative electrode active material layer.
上記実施形態の他、第２電極活物質層と基材層との間に保護層（第１保護層）を配置することに加えて、第１電極活物質層と基材層との間にも上記第１保護層と同様の保護層（第２保護層）をさらに配置してもよい。すなわち、セパレータが、基材層と、この基材層の第２電極活物質層側に配置される第１保護層と、上記基材層の第１電極活物質層側に配置され、上記第１保護層と同様の第２保護層とを有してもよい。
In addition to the above embodiment, in addition to disposing a protective layer (first protective layer) between the second electrode active material layer and the base layer, between the first electrode active material layer and the base layer may further dispose a protective layer (second protective layer) similar to the first protective layer. That is, the separator includes a base layer, a first protective layer arranged on the second electrode active material layer side of the base layer, a first protective layer arranged on the first electrode active material layer side of the base layer, and the second electrode active material layer side of the base layer. It may have one protective layer and a similar second protective layer.
上記実施形態では、拘束部材として一対の支持部と、連結部とを用い、これら一対の支持部及び連結部によって複数の蓄電素子（及び電極体）が押圧された状態である場合について説明したが、複数の蓄電素子を、これらが電極体の厚さ方向に押圧された状態で例えば略直方体状の筐体に挿入することで、各蓄電素子（及び電極体）が厚さ方向に押圧された状態としてもよい。すなわち、拘束部材として上記筐体を用いてもよい。このように、複数の蓄電素子の電極体をその厚さ方向に押圧すべく上記複数の蓄電素子を押圧する拘束部材は、上記実施形態に限定されない。
In the above embodiment, a pair of supporting portions and a connecting portion are used as a restraining member, and the case where a plurality of storage elements (and electrode bodies) are pressed by the pair of supporting portions and connecting portions has been described. Each storage element (and the electrode body) is pressed in the thickness direction by inserting a plurality of storage elements pressed in the thickness direction of the electrode body into, for example, a substantially rectangular housing. state. That is, the housing may be used as the restraining member. As described above, the restraining member that presses the plurality of storage elements so as to press the electrode bodies of the plurality of storage elements in the thickness direction is not limited to the above embodiment.
上記実施形態では、蓄電装置が複数の蓄電素子を備え、これら複数の蓄電素子の電極体がその厚さ方向に押圧された状態である場合について説明したが、蓄電素子が１の蓄電素子を備え、この蓄電素子の電極体がその厚さ方向に押圧された状態であってもよい。
In the above embodiment, the power storage device includes a plurality of power storage elements, and the electrode bodies of the plurality of power storage elements are pressed in the thickness direction. Alternatively, the electrode body of the storage element may be pressed in its thickness direction.
以下、実施例によって本発明をさらに具体的に説明する。本発明は以下の実施例に限定されない。
Hereinafter, the present invention will be described more specifically by way of examples. The invention is not limited to the following examples.
［実施例１］
（正極の作製）
正極活物質粒子として、α－ＮａＦｅＯ２型結晶構造を有し、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２で表されるリチウム遷移金属複合酸化物の粒子を用いた。正極活物質粒子の平均直径を表１に示す。 [Example 1]
(Preparation of positive electrode)
As the positive electrode active material particles, particles of a lithium transition metal composite oxide having an α-NaFeO 2 type crystal structure and represented by LiNi 1/3 Co 1/3 Mn 1/3 O 2 were used. Table 1 shows the average diameter of the positive electrode active material particles.
（正極の作製）
正極活物質粒子として、α－ＮａＦｅＯ２型結晶構造を有し、ＬｉＮｉ１／３Ｃｏ１／３Ｍｎ１／３Ｏ２で表されるリチウム遷移金属複合酸化物の粒子を用いた。正極活物質粒子の平均直径を表１に示す。 [Example 1]
(Preparation of positive electrode)
As the positive electrode active material particles, particles of a lithium transition metal composite oxide having an α-NaFeO 2 type crystal structure and represented by LiNi 1/3 Co 1/3 Mn 1/3 O 2 were used. Table 1 shows the average diameter of the positive electrode active material particles.
Ｎ－メチルピロリドン（ＮＭＰ）を分散媒とし、上記正極活物質粒子、導電剤であるアセチレンブラック（ＡＢ）、及びバインダであるポリフッ化ビニリデン（ＰＶＤＦ）を９４：４．５：１．５の質量比率（固形分換算）で含有する正極ペーストを作製した。正極基材である平均厚さ２０μｍのアルミニウム箔の片面に、上記正極ペーストを塗布し、乾燥し、プレス後、切断した。このようにして、幅３０ｍｍ、長さ４０ｍｍの矩形状に正極活物質層が配置された正極を作製した。正極活物質層の硬さを表１に示す。
Using N-methylpyrrolidone (NMP) as a dispersion medium, the positive electrode active material particles, acetylene black (AB) as a conductive agent, and polyvinylidene fluoride (PVDF) as a binder were mixed at a weight ratio of 94:4.5:1.5. A positive electrode paste containing the ratio (in terms of solid content) was prepared. The positive electrode paste was applied to one side of an aluminum foil having an average thickness of 20 μm, which was a positive electrode substrate, dried, pressed, and then cut. Thus, a positive electrode in which the positive electrode active material layer was arranged in a rectangular shape with a width of 30 mm and a length of 40 mm was produced. Table 1 shows the hardness of the positive electrode active material layer.
（負極の作製）
Ｎ－メチルピロリドン（ＮＭＰ）を分散媒とし、負極活物質粒子としてのグラファイト粒子及びバインダであるＰＶＤＦを９５：５の質量比率（固形分換算）で含有する負極ペーストを作製した。負極基材である平均厚さ１０μｍの銅箔の片面に、上記負極ペーストを塗布し、乾燥し、プレス後、切断した。このようにして、幅３２ｍｍ、長さ４２ｍｍの矩形状に負極活物質層が配置された負極を作製した。負極活物質粒子の平均直径及び負極活物質層の硬さを表１に示す。 (Preparation of negative electrode)
A negative electrode paste was prepared using N-methylpyrrolidone (NMP) as a dispersion medium and containing graphite particles as negative electrode active material particles and PVDF as a binder at a mass ratio of 95:5 (in terms of solid content). The negative electrode paste was applied to one side of a copper foil having an average thickness of 10 μm, which was a negative electrode substrate, dried, pressed, and then cut. Thus, a negative electrode in which the negative electrode active material layer was arranged in a rectangular shape with a width of 32 mm and a length of 42 mm was produced. Table 1 shows the average diameter of the negative electrode active material particles and the hardness of the negative electrode active material layer.
Ｎ－メチルピロリドン（ＮＭＰ）を分散媒とし、負極活物質粒子としてのグラファイト粒子及びバインダであるＰＶＤＦを９５：５の質量比率（固形分換算）で含有する負極ペーストを作製した。負極基材である平均厚さ１０μｍの銅箔の片面に、上記負極ペーストを塗布し、乾燥し、プレス後、切断した。このようにして、幅３２ｍｍ、長さ４２ｍｍの矩形状に負極活物質層が配置された負極を作製した。負極活物質粒子の平均直径及び負極活物質層の硬さを表１に示す。 (Preparation of negative electrode)
A negative electrode paste was prepared using N-methylpyrrolidone (NMP) as a dispersion medium and containing graphite particles as negative electrode active material particles and PVDF as a binder at a mass ratio of 95:5 (in terms of solid content). The negative electrode paste was applied to one side of a copper foil having an average thickness of 10 μm, which was a negative electrode substrate, dried, pressed, and then cut. Thus, a negative electrode in which the negative electrode active material layer was arranged in a rectangular shape with a width of 32 mm and a length of 42 mm was produced. Table 1 shows the average diameter of the negative electrode active material particles and the hardness of the negative electrode active material layer.
（非水電解質の調製）
エチレンカーボネート（ＥＣ）及びエチルメチルカーボネート（ＥＭＣ）を３０：７０の体積比で混合した混合溶媒にＬｉＰＦ６を１ｍｏｌ／ｄｍ３の濃度で溶解させ、非水電解質とした。 (Preparation of non-aqueous electrolyte)
LiPF 6 was dissolved at a concentration of 1 mol/dm 3 in a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 30:70 to obtain a non-aqueous electrolyte.
エチレンカーボネート（ＥＣ）及びエチルメチルカーボネート（ＥＭＣ）を３０：７０の体積比で混合した混合溶媒にＬｉＰＦ６を１ｍｏｌ／ｄｍ３の濃度で溶解させ、非水電解質とした。 (Preparation of non-aqueous electrolyte)
LiPF 6 was dissolved at a concentration of 1 mol/dm 3 in a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) at a volume ratio of 30:70 to obtain a non-aqueous electrolyte.
（セパレータ）
セパレータの基材層として、表１に示す平均厚さを有するようにポリエチレンのみによって形成された微多孔膜を用いた。セパレータの保護層は、表１に示す平均厚さとなるように上記基材層の表面に一体的に形成した。上記保護層は、無機粒子とバインダとを質量比で９５：５となるように含有させた。無機粒子としては、アルミナを用いた。基材層の平均厚さ、硬さ、及び空孔率を表１に示す。保護層に含まれる無機粒子の平均直径、保護層の平均厚さ、及び硬さを表１に示す。 (separator)
A microporous film made of only polyethylene having an average thickness shown in Table 1 was used as the base layer of the separator. The protective layer of the separator was integrally formed on the surface of the substrate layer so as to have the average thickness shown in Table 1. The protective layer contained inorganic particles and a binder at a weight ratio of 95:5. Alumina was used as the inorganic particles. Table 1 shows the average thickness, hardness, and porosity of the substrate layer. Table 1 shows the average diameter of the inorganic particles contained in the protective layer, the average thickness of the protective layer, and the hardness.
セパレータの基材層として、表１に示す平均厚さを有するようにポリエチレンのみによって形成された微多孔膜を用いた。セパレータの保護層は、表１に示す平均厚さとなるように上記基材層の表面に一体的に形成した。上記保護層は、無機粒子とバインダとを質量比で９５：５となるように含有させた。無機粒子としては、アルミナを用いた。基材層の平均厚さ、硬さ、及び空孔率を表１に示す。保護層に含まれる無機粒子の平均直径、保護層の平均厚さ、及び硬さを表１に示す。 (separator)
A microporous film made of only polyethylene having an average thickness shown in Table 1 was used as the base layer of the separator. The protective layer of the separator was integrally formed on the surface of the substrate layer so as to have the average thickness shown in Table 1. The protective layer contained inorganic particles and a binder at a weight ratio of 95:5. Alumina was used as the inorganic particles. Table 1 shows the average thickness, hardness, and porosity of the substrate layer. Table 1 shows the average diameter of the inorganic particles contained in the protective layer, the average thickness of the protective layer, and the hardness.
（非水電解質蓄電素子の作製）
上記セパレータを介して、上記正極と上記負極とを積層することにより電極体を作製した。このとき、上記基材層が上記負極に対向し、上記保護層が上記正極に対向するように、セパレータを配置した。この電極体を容器に収納し、内部に上記非水電解質を注入した後、封口した。封口した容器を内部の圧力（押圧力）が０．５ＭＰａとなるように電極体の厚さ方向に拘束部材で押圧して、実施例１の非水電解質蓄電素子（二次電池）を得た。 (Preparation of non-aqueous electrolyte storage element)
An electrode body was produced by laminating the positive electrode and the negative electrode with the separator interposed therebetween. At this time, the separator was arranged so that the substrate layer faced the negative electrode and the protective layer faced the positive electrode. This electrode assembly was placed in a container, and after the non-aqueous electrolyte was injected therein, the container was sealed. A non-aqueous electrolyte storage element (secondary battery) of Example 1 was obtained by pressing the sealed container in the thickness direction of the electrode body with a restraining member so that the internal pressure (pressing force) was 0.5 MPa. .
上記セパレータを介して、上記正極と上記負極とを積層することにより電極体を作製した。このとき、上記基材層が上記負極に対向し、上記保護層が上記正極に対向するように、セパレータを配置した。この電極体を容器に収納し、内部に上記非水電解質を注入した後、封口した。封口した容器を内部の圧力（押圧力）が０．５ＭＰａとなるように電極体の厚さ方向に拘束部材で押圧して、実施例１の非水電解質蓄電素子（二次電池）を得た。 (Preparation of non-aqueous electrolyte storage element)
An electrode body was produced by laminating the positive electrode and the negative electrode with the separator interposed therebetween. At this time, the separator was arranged so that the substrate layer faced the negative electrode and the protective layer faced the positive electrode. This electrode assembly was placed in a container, and after the non-aqueous electrolyte was injected therein, the container was sealed. A non-aqueous electrolyte storage element (secondary battery) of Example 1 was obtained by pressing the sealed container in the thickness direction of the electrode body with a restraining member so that the internal pressure (pressing force) was 0.5 MPa. .
［実施例２から６］
上記基材層又は上記保護層を表１に示すように変更したこと以外は、実施例１と同様にして、実施例２から６の非水電解質蓄電素子を得た。 [Examples 2 to 6]
Non-aqueous electrolyte storage elements of Examples 2 to 6 were obtained in the same manner as in Example 1, except that the substrate layer or the protective layer was changed as shown in Table 1.
上記基材層又は上記保護層を表１に示すように変更したこと以外は、実施例１と同様にして、実施例２から６の非水電解質蓄電素子を得た。 [Examples 2 to 6]
Non-aqueous electrolyte storage elements of Examples 2 to 6 were obtained in the same manner as in Example 1, except that the substrate layer or the protective layer was changed as shown in Table 1.
［比較例１から４］
上記セパレータを、上記基材層が上記正極に対向し、上記保護層が上記負極に対向するように配置したこと以外は、実施例１と同様にして、比較例１の非水電解質蓄電素子を得た。上記基材層又は上記保護層を表１に示すように変更したこと以外は、実施例１と同様にして、比較例２から４の非水電解質蓄電素子を得た。なお、表１の比較例３における「－」は、保護層を用いなかったことを示す。 [Comparative Examples 1 to 4]
A non-aqueous electrolyte storage element of Comparative Example 1 was fabricated in the same manner as in Example 1, except that the separator was arranged so that the base material layer faced the positive electrode and the protective layer faced the negative electrode. Obtained. Non-aqueous electrolyte storage elements of Comparative Examples 2 to 4 were obtained in the same manner as in Example 1, except that the substrate layer or the protective layer was changed as shown in Table 1. "-" in Comparative Example 3 in Table 1 indicates that no protective layer was used.
上記セパレータを、上記基材層が上記正極に対向し、上記保護層が上記負極に対向するように配置したこと以外は、実施例１と同様にして、比較例１の非水電解質蓄電素子を得た。上記基材層又は上記保護層を表１に示すように変更したこと以外は、実施例１と同様にして、比較例２から４の非水電解質蓄電素子を得た。なお、表１の比較例３における「－」は、保護層を用いなかったことを示す。 [Comparative Examples 1 to 4]
A non-aqueous electrolyte storage element of Comparative Example 1 was fabricated in the same manner as in Example 1, except that the separator was arranged so that the base material layer faced the positive electrode and the protective layer faced the negative electrode. Obtained. Non-aqueous electrolyte storage elements of Comparative Examples 2 to 4 were obtained in the same manner as in Example 1, except that the substrate layer or the protective layer was changed as shown in Table 1. "-" in Comparative Example 3 in Table 1 indicates that no protective layer was used.
［比較例５］
上記容器の封口後に上記容器を圧迫しないこと以外は、実施例１と同様にして、比較例５の非水電解質蓄電素子を得た。 [Comparative Example 5]
A non-aqueous electrolyte storage element of Comparative Example 5 was obtained in the same manner as in Example 1, except that the container was not pressed after it was sealed.
上記容器の封口後に上記容器を圧迫しないこと以外は、実施例１と同様にして、比較例５の非水電解質蓄電素子を得た。 [Comparative Example 5]
A non-aqueous electrolyte storage element of Comparative Example 5 was obtained in the same manner as in Example 1, except that the container was not pressed after it was sealed.
［比較例６から８］
上記正極活物質粒子の平均直径、上記負極活物質粒子の平均直径及び上記基材層の平均厚さを表１に示すように変更したこと以外は、比較例５と同様にして、比較例６から８の非水電解質蓄電素子を得た。 [Comparative Examples 6 to 8]
Comparative Example 6 was carried out in the same manner as in Comparative Example 5, except that the average diameter of the positive electrode active material particles, the average diameter of the negative electrode active material particles, and the average thickness of the base material layer were changed as shown in Table 1. 8 non-aqueous electrolyte storage elements were obtained.
上記正極活物質粒子の平均直径、上記負極活物質粒子の平均直径及び上記基材層の平均厚さを表１に示すように変更したこと以外は、比較例５と同様にして、比較例６から８の非水電解質蓄電素子を得た。 [Comparative Examples 6 to 8]
Comparative Example 6 was carried out in the same manner as in Comparative Example 5, except that the average diameter of the positive electrode active material particles, the average diameter of the negative electrode active material particles, and the average thickness of the base material layer were changed as shown in Table 1. 8 non-aqueous electrolyte storage elements were obtained.
（初期充放電）
得られた各非水電解質蓄電素子について、以下の条件にて初期充放電を行った。２５℃において、充電電流０．１Ｃ、充電終止電圧４．３Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０２Ｃとなるまでとした。その後、１０分間の休止期間を設けた。その後、放電電流０．１Ｃ、放電終止電圧２．０Ｖとして定電流放電を行い、その後、１０分間の休止期間を設けた。この充放電を２サイクル行った。 (initial charge/discharge)
Initial charge/discharge was performed on each obtained non-aqueous electrolyte storage element under the following conditions. At 25° C., constant-current and constant-voltage charging was performed with a charging current of 0.1 C and a charge termination voltage of 4.3 V. The charging termination condition was until the charging current reached 0.02C. A rest period of 10 minutes was then provided. Thereafter, constant current discharge was performed with a discharge current of 0.1 C and a discharge final voltage of 2.0 V, followed by a rest period of 10 minutes. Two cycles of this charging and discharging were performed.
得られた各非水電解質蓄電素子について、以下の条件にて初期充放電を行った。２５℃において、充電電流０．１Ｃ、充電終止電圧４．３Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０２Ｃとなるまでとした。その後、１０分間の休止期間を設けた。その後、放電電流０．１Ｃ、放電終止電圧２．０Ｖとして定電流放電を行い、その後、１０分間の休止期間を設けた。この充放電を２サイクル行った。 (initial charge/discharge)
Initial charge/discharge was performed on each obtained non-aqueous electrolyte storage element under the following conditions. At 25° C., constant-current and constant-voltage charging was performed with a charging current of 0.1 C and a charge termination voltage of 4.3 V. The charging termination condition was until the charging current reached 0.02C. A rest period of 10 minutes was then provided. Thereafter, constant current discharge was performed with a discharge current of 0.1 C and a discharge final voltage of 2.0 V, followed by a rest period of 10 minutes. Two cycles of this charging and discharging were performed.
（充放電サイクル試験）
次いで、以下の充放電サイクル試験を行った。６０℃において、充電電流０．２Ｃ、充電終止電圧４．３Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０５Ｃとなるまでとした。その後、１０分間の休止期間を設けた。その後、放電電流０．１Ｃ、放電終止電圧２．５Ｖとして定電流放電を行い、その後、１０分間の休止期間を設けた。この充放電のサイクルを５００回繰り返し、初期充放電後及び５００サイクル後の非水電解質蓄電素子の直流抵抗をそれぞれ測定した。非水電解質蓄電素子の直流抵抗は、以下の条件にて測定した。非水電解質蓄電素子を２５℃において、充電電流０．１Ｃで４．１Ｖまで定電流充電した後、０．５、２、５、１０Ａの各電流でそれぞれ３０秒ずつ放電した。各放電終了後には、充電電流０．１Ｃで４．１Ｖまで定電流充電した。各放電における放電開始後１０秒目の各電圧を測定し、得られたデータからＶ－Ｉプロットを作成し、これらプロットを最小二乗法で直線近似して得られた直線の傾きから、直流抵抗を求めた。初期充放電後及び５００サイクル後の直流抵抗を測定した後、初期充放電後の直流抵抗に対する５００サイクル後の直流抵抗の上昇率を、下記式（１）を用いて算出し「抵抗上昇率」とした。そして、実施例１の抵抗上昇率を１００％とし、この抵抗上昇率に対する実施例２から７、比較例１から８の抵抗上昇率の比率（％）を算出した。結果を表１に示す。
抵抗上昇率（％）＝｛（５００サイクル後の直流抵抗）／（初期充放電後の直流抵抗）｝×１００ ・・・（１） (Charge-discharge cycle test)
Then, the following charge/discharge cycle test was performed. At 60° C., constant-current and constant-voltage charging was performed with a charging current of 0.2 C and a charge termination voltage of 4.3 V. The charging termination condition was until the charging current reached 0.05C. A rest period of 10 minutes was then provided. Thereafter, constant current discharge was performed with a discharge current of 0.1 C and a discharge final voltage of 2.5 V, followed by a rest period of 10 minutes. This charge/discharge cycle was repeated 500 times, and the DC resistance of the non-aqueous electrolyte storage element after the initial charge/discharge and after 500 cycles was measured. The DC resistance of the non-aqueous electrolyte storage element was measured under the following conditions. The non-aqueous electrolyte storage element was charged at a constant current of 0.1 C to 4.1 V at 25° C., and then discharged at currents of 0.5, 2, 5 and 10 A for 30 seconds each. After completion of each discharge, constant current charging was performed to 4.1 V at a charging current of 0.1C. Measure each voltage at 10 seconds after the start of discharge in each discharge, create a VI plot from the obtained data, linearly approximate these plots by the least squares method From the slope of the straight line obtained, DC resistance asked for After measuring the DC resistance after the initial charging and discharging and after 500 cycles, the rate of increase in the DC resistance after 500 cycles with respect to the DC resistance after the initial charging and discharging was calculated using the following formula (1). and Taking the resistance increase rate of Example 1 as 100%, the ratio (%) of the resistance increase rate of Examples 2 to 7 and Comparative Examples 1 to 8 to this resistance increase rate was calculated. Table 1 shows the results.
Resistance increase rate (%)={(DC resistance after 500 cycles)/(DC resistance after initial charging/discharging)}×100 (1)
次いで、以下の充放電サイクル試験を行った。６０℃において、充電電流０．２Ｃ、充電終止電圧４．３Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０５Ｃとなるまでとした。その後、１０分間の休止期間を設けた。その後、放電電流０．１Ｃ、放電終止電圧２．５Ｖとして定電流放電を行い、その後、１０分間の休止期間を設けた。この充放電のサイクルを５００回繰り返し、初期充放電後及び５００サイクル後の非水電解質蓄電素子の直流抵抗をそれぞれ測定した。非水電解質蓄電素子の直流抵抗は、以下の条件にて測定した。非水電解質蓄電素子を２５℃において、充電電流０．１Ｃで４．１Ｖまで定電流充電した後、０．５、２、５、１０Ａの各電流でそれぞれ３０秒ずつ放電した。各放電終了後には、充電電流０．１Ｃで４．１Ｖまで定電流充電した。各放電における放電開始後１０秒目の各電圧を測定し、得られたデータからＶ－Ｉプロットを作成し、これらプロットを最小二乗法で直線近似して得られた直線の傾きから、直流抵抗を求めた。初期充放電後及び５００サイクル後の直流抵抗を測定した後、初期充放電後の直流抵抗に対する５００サイクル後の直流抵抗の上昇率を、下記式（１）を用いて算出し「抵抗上昇率」とした。そして、実施例１の抵抗上昇率を１００％とし、この抵抗上昇率に対する実施例２から７、比較例１から８の抵抗上昇率の比率（％）を算出した。結果を表１に示す。
抵抗上昇率（％）＝｛（５００サイクル後の直流抵抗）／（初期充放電後の直流抵抗）｝×１００ ・・・（１） (Charge-discharge cycle test)
Then, the following charge/discharge cycle test was performed. At 60° C., constant-current and constant-voltage charging was performed with a charging current of 0.2 C and a charge termination voltage of 4.3 V. The charging termination condition was until the charging current reached 0.05C. A rest period of 10 minutes was then provided. Thereafter, constant current discharge was performed with a discharge current of 0.1 C and a discharge final voltage of 2.5 V, followed by a rest period of 10 minutes. This charge/discharge cycle was repeated 500 times, and the DC resistance of the non-aqueous electrolyte storage element after the initial charge/discharge and after 500 cycles was measured. The DC resistance of the non-aqueous electrolyte storage element was measured under the following conditions. The non-aqueous electrolyte storage element was charged at a constant current of 0.1 C to 4.1 V at 25° C., and then discharged at currents of 0.5, 2, 5 and 10 A for 30 seconds each. After completion of each discharge, constant current charging was performed to 4.1 V at a charging current of 0.1C. Measure each voltage at 10 seconds after the start of discharge in each discharge, create a VI plot from the obtained data, linearly approximate these plots by the least squares method From the slope of the straight line obtained, DC resistance asked for After measuring the DC resistance after the initial charging and discharging and after 500 cycles, the rate of increase in the DC resistance after 500 cycles with respect to the DC resistance after the initial charging and discharging was calculated using the following formula (1). and Taking the resistance increase rate of Example 1 as 100%, the ratio (%) of the resistance increase rate of Examples 2 to 7 and Comparative Examples 1 to 8 to this resistance increase rate was calculated. Table 1 shows the results.
Resistance increase rate (%)={(DC resistance after 500 cycles)/(DC resistance after initial charging/discharging)}×100 (1)
（充放電サイクル後の放置試験）
上記充放電サイクル試験後の非水電解質蓄電素子を、２５℃において、充電電流０．１Ｃ、充電終止電圧４．３Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０２Ｃとなるまでとした。このときの充電電気量を、放置前の充電電気量とした。その後、６０℃の恒温槽中において、非水電解質蓄電素子を１週間放置した。上記放置後の非水電解質蓄電素子を、２５℃において、放電電流０．１Ｃ、放電終止電圧２．０Ｖとして定電流放電を行った。このときの放電容量を、放置後の放電電気量とした。非水電解質蓄電素子の５００サイクル後、さらに６０℃１週間放置後の自己放電量を、下記式（２）を用いて放置前の充電電気量から放置後の放電電気量を差し引くことによって算出した。そして、実施例１の自己放電量を１００％とし、この自己放電量に対する実施例２から６、比較例１から８の自己放電量の比率（％）を算出した。結果を表１に示す。
自己放電量（ｍＡｈ）＝（放置前の充電電気量）－（放置後の放電電気量） ・・・（２） (Standing test after charge/discharge cycle)
After the charge-discharge cycle test, the non-aqueous electrolyte storage element was charged at 25° C. with a charging current of 0.1 C and a charge termination voltage of 4.3 V at constant current and constant voltage. The charging termination condition was until the charging current reached 0.02C. The charge amount of electricity at this time was taken as the charge amount of electricity before leaving. After that, the non-aqueous electrolyte power storage element was left for one week in a constant temperature bath at 60°C. The non-aqueous electrolyte storage element after standing was subjected to constant current discharge at 25° C. with a discharge current of 0.1 C and a discharge final voltage of 2.0 V. The discharge capacity at this time was taken as the amount of discharged electricity after standing. After 500 cycles of the non-aqueous electrolyte storage element and after standing at 60° C. for 1 week, the self-discharge amount was calculated by subtracting the discharged amount of electricity after standing from the charged amount of electricity before standing using the following formula (2). . Taking the self-discharge amount of Example 1 as 100%, the ratio (%) of the self-discharge amount of Examples 2 to 6 and Comparative Examples 1 to 8 to this self-discharge amount was calculated. Table 1 shows the results.
Self-discharge amount (mAh) = (charged electricity amount before leaving) - (discharged electricity amount after leaving) (2)
上記充放電サイクル試験後の非水電解質蓄電素子を、２５℃において、充電電流０．１Ｃ、充電終止電圧４．３Ｖとして定電流定電圧充電した。充電の終了条件は、充電電流が０．０２Ｃとなるまでとした。このときの充電電気量を、放置前の充電電気量とした。その後、６０℃の恒温槽中において、非水電解質蓄電素子を１週間放置した。上記放置後の非水電解質蓄電素子を、２５℃において、放電電流０．１Ｃ、放電終止電圧２．０Ｖとして定電流放電を行った。このときの放電容量を、放置後の放電電気量とした。非水電解質蓄電素子の５００サイクル後、さらに６０℃１週間放置後の自己放電量を、下記式（２）を用いて放置前の充電電気量から放置後の放電電気量を差し引くことによって算出した。そして、実施例１の自己放電量を１００％とし、この自己放電量に対する実施例２から６、比較例１から８の自己放電量の比率（％）を算出した。結果を表１に示す。
自己放電量（ｍＡｈ）＝（放置前の充電電気量）－（放置後の放電電気量） ・・・（２） (Standing test after charge/discharge cycle)
After the charge-discharge cycle test, the non-aqueous electrolyte storage element was charged at 25° C. with a charging current of 0.1 C and a charge termination voltage of 4.3 V at constant current and constant voltage. The charging termination condition was until the charging current reached 0.02C. The charge amount of electricity at this time was taken as the charge amount of electricity before leaving. After that, the non-aqueous electrolyte power storage element was left for one week in a constant temperature bath at 60°C. The non-aqueous electrolyte storage element after standing was subjected to constant current discharge at 25° C. with a discharge current of 0.1 C and a discharge final voltage of 2.0 V. The discharge capacity at this time was taken as the amount of discharged electricity after standing. After 500 cycles of the non-aqueous electrolyte storage element and after standing at 60° C. for 1 week, the self-discharge amount was calculated by subtracting the discharged amount of electricity after standing from the charged amount of electricity before standing using the following formula (2). . Taking the self-discharge amount of Example 1 as 100%, the ratio (%) of the self-discharge amount of Examples 2 to 6 and Comparative Examples 1 to 8 to this self-discharge amount was calculated. Table 1 shows the results.
Self-discharge amount (mAh) = (charged electricity amount before leaving) - (discharged electricity amount after leaving) (2)
上記容器が圧迫されている場合、表１の実施例１から６及び比較例１から４に示されるように、比較的硬い正極活物質粒子を含む正極活物質層に対向して保護層を配置し、比較的柔らかい負極活物質粒子を含む負極活物質層に対向して基材層を配置し、保護層の平均厚さを正極活物物質粒子の平均直径以上とし、基材層の平均厚さを負極活物質粒子の平均直径以上とすることで、上記５００サイクル後の抵抗上昇率が抑制され、かつ上記高温放置後の自己放電量の増大が抑制されることがわかった。
When the container is pressed, as shown in Examples 1 to 6 and Comparative Examples 1 to 4 in Table 1, a protective layer is placed facing the positive electrode active material layer containing relatively hard positive electrode active material particles. Then, the substrate layer is arranged to face the negative electrode active material layer containing the relatively soft negative electrode active material particles, the average thickness of the protective layer is equal to or greater than the average diameter of the positive electrode active material particles, and the average thickness of the substrate layer is It has been found that the resistance increase rate after 500 cycles is suppressed and the increase in self-discharge amount after being left at high temperature is suppressed by setting the thickness to be equal to or greater than the average diameter of the negative electrode active material particles.
上記容器が圧迫されていない場合には、表１の比較例５、６、８に示されるように、比較的硬い正極活物質粒子を含む正極活物質層に対向して保護層を配置し、比較的柔らかい負極活物質粒子を含む負極活物質層に対向して基材層を配置し、保護層の平均厚さを正極活物物質粒子の平均直径以上とし、基材層の平均厚さを負極活物質粒子の平均直径以上としても、上記５００サイクル後の抵抗上昇率が抑制されず、しかも上記高温放置後の自己放電量の上昇も抑制されないことがわかった。また、比較例５、６、８と、比較例７とを比較すると、上記容器が圧迫されていない場合には、保護層の平均厚さが正極活物質粒子の平均直径よりも小さい比較例７の方が、保護層の平均厚さが正極活物質粒子の平均直径よりも大きい比較例５、６、８よりも相対的に上記５００サイクル後の抵抗上昇率が抑制され、かつ上記高温放置後の自己放電量の増大が抑制される傾向にあることがわかった。
When the container is not pressed, as shown in Comparative Examples 5, 6, and 8 in Table 1, a protective layer is disposed facing the positive electrode active material layer containing relatively hard positive electrode active material particles, A substrate layer is arranged to face a negative electrode active material layer containing relatively soft negative electrode active material particles, the average thickness of the protective layer is equal to or greater than the average diameter of the positive electrode active material particles, and the average thickness of the substrate layer is It has been found that even if the average diameter of the negative electrode active material particles or more is used, the resistance increase rate after 500 cycles is not suppressed, and the increase in self-discharge amount after being left at high temperature is not suppressed. Further, when comparing Comparative Examples 5, 6, and 8 with Comparative Example 7, when the container is not pressed, the average thickness of the protective layer is smaller than the average diameter of the positive electrode active material particles. In Comparative Examples 5, 6, and 8, in which the average thickness of the protective layer is larger than the average diameter of the positive electrode active material particles, the resistance increase rate after the 500 cycles is relatively suppressed, and after the high temperature standing It was found that the increase in the amount of self-discharge tends to be suppressed.
従って、当該蓄電素子は、電極体がその厚さ方向に押圧された状態である場合に、内部抵抗の増加の抑制効果、及び自己放電の抑制効果が高いことが示された。
Therefore, it was shown that the power storage element has a high effect of suppressing an increase in internal resistance and a high effect of suppressing self-discharge when the electrode body is pressed in the thickness direction.
本発明は、パーソナルコンピュータ、通信端末等の電子機器、自動車等の電源として使用される蓄電素子に適用できる。
The present invention can be applied to electrical storage devices used as power sources for personal computers, electronic devices such as communication terminals, and automobiles.
１ 蓄電素子
２ 電極体
３ 容器
４ 正極端子
４１ 正極リード
５ 負極端子
５１ 負極リード
１０ 蓄電装置
４５ 正極
４６ 正極基材
４７ 正極活物質層
４８ 正極活物質粒子
５５ 負極
５６ 負極基材
５７ 負極活物質層
５８ 負極活物質粒子
６０ セパレータ
６１ 基材層
６２ 保護層
１０１ 支持部
１０２ 連結部
１０３ 螺合用孔
１０４ 貫通孔
1Electric storage element 2 Electrode body 3 Container 4 Positive electrode terminal 41 Positive electrode lead 5 Negative electrode terminal 51 Negative electrode lead 10 Electric storage device 45 Positive electrode 46 Positive electrode substrate 47 Positive electrode active material layer 48 Positive electrode active material particles 55 Negative electrode 56 Negative electrode substrate 57 Negative electrode active material layer 58 negative electrode active material particles 60 separator 61 base layer 62 protective layer 101 support portion 102 connecting portion 103 screwing hole 104 through hole
２ 電極体
３ 容器
４ 正極端子
４１ 正極リード
５ 負極端子
５１ 負極リード
１０ 蓄電装置
４５ 正極
４６ 正極基材
４７ 正極活物質層
４８ 正極活物質粒子
５５ 負極
５６ 負極基材
５７ 負極活物質層
５８ 負極活物質粒子
６０ セパレータ
６１ 基材層
６２ 保護層
１０１ 支持部
１０２ 連結部
１０３ 螺合用孔
１０４ 貫通孔
1
Claims (6)
- 第１電極と、第２電極とが、セパレータを介して厚さ方向に重ね合わされてなる電極体と、
非水電解質と、
上記電極体及び非水電解質を収容する容器と
を備え、
上記第１電極が、第１電極活物質粒子を含む第１電極活物質層を有し、
上記第２電極が、第２電極活物質粒子を含み、かつ上記第１電極活物質層よりも硬い第２電極活物質層を有し、
上記セパレータが、基材層及び保護層を有し、
上記保護層が、上記基材層における上記第２電極側の表面に配置され、かつ上記基材層よりも硬く、
上記保護層の平均厚さが上記第２電極活物質粒子の平均直径以上であり、
上記基材層の平均厚さが上記第１電極活物質粒子の平均直径以上であり、
上記電極体の厚さ方向に上記電極体が押圧された状態である蓄電素子。 an electrode body in which a first electrode and a second electrode are superimposed in a thickness direction with a separator interposed therebetween;
a non-aqueous electrolyte;
and a container containing the electrode body and the non-aqueous electrolyte,
The first electrode has a first electrode active material layer containing first electrode active material particles,
The second electrode has a second electrode active material layer containing second electrode active material particles and harder than the first electrode active material layer,
The separator has a base material layer and a protective layer,
The protective layer is disposed on the surface of the base layer on the second electrode side and is harder than the base layer,
The average thickness of the protective layer is equal to or greater than the average diameter of the second electrode active material particles,
The average thickness of the substrate layer is equal to or greater than the average diameter of the first electrode active material particles,
A storage element in which the electrode body is pressed in the thickness direction of the electrode body. - 上記保護層が上記第２電極活物質層よりも硬い請求項１に記載の蓄電素子。 The electric storage element according to claim 1, wherein the protective layer is harder than the second electrode active material layer.
- 上記第２電極活物質粒子の平均直径が上記第１電極活物質粒子の平均直径よりも小さい請求項１又は請求項２に記載の蓄電素子。 The electric storage element according to claim 1 or 2, wherein the average diameter of the second electrode active material particles is smaller than the average diameter of the first electrode active material particles.
- 上記第１電極活物質層が上記基材層よりも硬い請求項１、請求項２又は請求項３に記載の蓄電素子。 The electric storage element according to claim 1, claim 2, or claim 3, wherein the first electrode active material layer is harder than the base material layer.
- 上記電極体の厚さ方向に上記電極体に加えられる押圧力は０．３ＭＰａ以上である請求項１から請求項４のいずれか１項に記載の蓄電素子。 The electric storage element according to any one of claims 1 to 4, wherein the pressing force applied to the electrode body in the thickness direction of the electrode body is 0.3 MPa or more.
- 請求項１から請求項５のいずれか１項に記載の１又は複数の蓄電素子と、
上記１又は複数の蓄電素子を拘束する拘束部材と
を備え、
上記拘束部材による拘束により上記１又は複数の蓄電素子の上記電極体が上記厚さ方向に押圧された状態である蓄電装置。 one or more storage elements according to any one of claims 1 to 5;
a restraining member that restrains the one or more power storage elements,
A power storage device in which the electrode bodies of the one or more power storage elements are pressed in the thickness direction by restraint by the restraining member.
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| WO2012150635A1 (en) * | 2011-05-02 | 2012-11-08 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
| JP2020527833A (en) * | 2017-09-15 | 2020-09-10 | エルジー・ケム・リミテッド | Negative electrode for lithium secondary battery and lithium secondary battery including it |
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|---|---|---|---|---|
| WO2012150635A1 (en) * | 2011-05-02 | 2012-11-08 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
| JP2020527833A (en) * | 2017-09-15 | 2020-09-10 | エルジー・ケム・リミテッド | Negative electrode for lithium secondary battery and lithium secondary battery including it |
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