JP7478508B2 - Inorganic solid electrolyte secondary battery - Google Patents
Inorganic solid electrolyte secondary battery Download PDFInfo
- Publication number
- JP7478508B2 JP7478508B2 JP2018220614A JP2018220614A JP7478508B2 JP 7478508 B2 JP7478508 B2 JP 7478508B2 JP 2018220614 A JP2018220614 A JP 2018220614A JP 2018220614 A JP2018220614 A JP 2018220614A JP 7478508 B2 JP7478508 B2 JP 7478508B2
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- JP
- Japan
- Prior art keywords
- solid electrolyte
- inorganic solid
- secondary battery
- ion
- electrolyte secondary
- Prior art date
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- 239000007784 solid electrolyte Substances 0.000 title claims description 105
- 229910003480 inorganic solid Inorganic materials 0.000 title claims description 92
- -1 lithium salt compound Chemical class 0.000 claims description 66
- 229920001940 conductive polymer Polymers 0.000 claims description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 13
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- 229910018497 SFO2 Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- 229910013131 LiN Inorganic materials 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 239000003999 initiator Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000011149 active material Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052732 germanium Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052718 tin Inorganic materials 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052733 gallium Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 6
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
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- 239000004014 plasticizer Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
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- 239000000843 powder Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
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- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
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- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002227 LISICON Substances 0.000 description 2
- 229910012329 Li3BO3—Li2SO4 Inorganic materials 0.000 description 2
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 1
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 description 1
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- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QXOYPGTWWXJFDI-UHFFFAOYSA-N nonanedinitrile Chemical compound N#CCCCCCCCC#N QXOYPGTWWXJFDI-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- AVNANMSIFNUHNY-MQQKCMAXSA-N oxiran-2-ylmethyl (2e,4e)-hexa-2,4-dienoate Chemical compound C\C=C\C=C\C(=O)OCC1CO1 AVNANMSIFNUHNY-MQQKCMAXSA-N 0.000 description 1
- JUVGLPRIQOJMIR-UHFFFAOYSA-N oxiran-2-ylmethyl 3-phenylprop-2-enoate Chemical compound C=1C=CC=CC=1C=CC(=O)OCC1CO1 JUVGLPRIQOJMIR-UHFFFAOYSA-N 0.000 description 1
- NZSXYXVUIOHHSF-UHFFFAOYSA-N oxiran-2-ylmethyl hex-4-enoate Chemical compound CC=CCCC(=O)OCC1CO1 NZSXYXVUIOHHSF-UHFFFAOYSA-N 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- IRAPFUAOCHNONS-UHFFFAOYSA-N potassium;phenylmethylbenzene Chemical compound [K+].C=1C=CC=CC=1[CH-]C1=CC=CC=C1 IRAPFUAOCHNONS-UHFFFAOYSA-N 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- GJSGYPDDPQRWPK-UHFFFAOYSA-N tetrapentylammonium Chemical compound CCCCC[N+](CCCCC)(CCCCC)CCCCC GJSGYPDDPQRWPK-UHFFFAOYSA-N 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Description
本発明は、無機固体電解質二次電池に関する。 The present invention relates to an inorganic solid electrolyte secondary battery.
従来、リチウムイオン電池に代表される非水電解質二次電池は、電解質にイオン伝導性の点から溶液またはペースト状のものが用いられている。しかし、液漏れによる機器の損傷の恐れがあることから、種々の安全対策が必要であり、大型電池開発の障壁になっている。 Conventionally, non-aqueous electrolyte secondary batteries, such as lithium-ion batteries, use a solution or paste-like electrolyte for its ionic conductivity. However, various safety measures are required to prevent leakage of the electrolyte, which can damage the device, and this is an obstacle to the development of large batteries.
これに対し高分子固体電解質、無機固体電解質などの電解質が固体化された固体電解質が提案されている。高分子固体電解質は、一般に柔軟性、曲げ加工性、および成形性に優れ、応用されるデバイスの設計の自由度が高くなるなどの利点があるが、負荷特性や低温特性が悪いために、高温作動の電池用途に限られるという欠点がある。一方、無機固体電解質は、高分子固体電解質と比べて、イオン伝導性が高いものの、電解質が結晶質あるいは非晶質からなり、充放電時の正負極活物質による体積変化の緩和が難しく、更に、電極と電解質の界面抵抗が高いため、充放電特性が不十分という問題がある。 In response to this, solid electrolytes have been proposed, such as polymer solid electrolytes and inorganic solid electrolytes, which are solidified electrolytes. Polymer solid electrolytes generally have advantages such as excellent flexibility, bendability, and moldability, which allows greater freedom in the design of devices to which they are applied, but they have the disadvantage that their use is limited to batteries that operate at high temperatures due to poor load characteristics and low-temperature characteristics. On the other hand, inorganic solid electrolytes have higher ionic conductivity than polymer solid electrolytes, but the electrolyte is crystalline or amorphous, making it difficult to alleviate the volume change caused by the positive and negative electrode active materials during charging and discharging, and furthermore, the high interfacial resistance between the electrodes and the electrolyte results in insufficient charging and discharging characteristics.
特許文献１、２には、ポリエチレンオキシドとリチウム塩を含む高分子固体電解質を無機固体電解質と電極層との間に介在させた電池が開示されている。しかしながら、ポリエチレンオキシドは、結晶性が高く、融点（６０℃）以下になると、結晶化に伴い、柔軟性がなくなり、結着性が弱くなる。また、融点以上になると、ポリエチレンオキシドが溶融するため形状維持ができなくなり、結着性が弱くなるという問題がある。ポリエチレンオキシドを含む固体電解質では無機固体電解質との界面を良好に保つことは困難である。 Patent Documents 1 and 2 disclose batteries in which a polymer solid electrolyte containing polyethylene oxide and a lithium salt is interposed between an inorganic solid electrolyte and an electrode layer. However, polyethylene oxide is highly crystalline, and when it is below its melting point (60°C), it loses flexibility and its binding properties weaken as it crystallizes. Furthermore, when it is above its melting point, the polyethylene oxide melts and is unable to maintain its shape, resulting in a problem of weakened binding properties. It is difficult to maintain a good interface with an inorganic solid electrolyte when using a solid electrolyte containing polyethylene oxide.
本発明は、優れた充放電特性を発揮する新規な無機固体電解質二次電池を提供することを主な目的とする。 The main objective of the present invention is to provide a new inorganic solid electrolyte secondary battery that exhibits excellent charge/discharge characteristics.
本発明者は、上記の課題を解決すべく鋭意検討を行った。その結果、正極、無機固体電解質、負極、及び架橋フィルムを備える無機固体電解質二次電池であって、前記架橋フィルムは、リチウム塩化合物、及び側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーを含む組成物の架橋体であり、正極と無機固体電解質との間、及び負極と無機固体電解質との間の少なくとも一方に、前記架橋フィルムを有する無機固体電解質二次電池は、優れた充放電特性を発揮することを見出した。本発明は、このような知見に基づいて、さらに検討を重ねることにより完成したものである。 The present inventors conducted extensive research to solve the above problems. As a result, they discovered that an inorganic solid electrolyte secondary battery having a positive electrode, an inorganic solid electrolyte, a negative electrode, and a crosslinked film, the crosslinked film being a crosslinked body of a composition containing a lithium salt compound and an ion-conductive polymer having an ethylene oxide unit in a side chain, and an inorganic solid electrolyte secondary battery having the crosslinked film at least one between the positive electrode and the inorganic solid electrolyte and between the negative electrode and the inorganic solid electrolyte, exhibits excellent charge/discharge characteristics. The present invention was completed based on this knowledge and through further research.
即ち、本発明は、下記に掲げる態様の発明を提供する。
項１． 正極、無機固体電解質、負極、及び架橋フィルムを備える、無機固体電解質二次電池であって、
前記架橋フィルムは、リチウム塩化合物、及び側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーを含む組成物の架橋体であり、
前記正極と前記無機固体電解質との間、及び前記負極と前記無機固体電解質との間の少なくとも一方に、前記架橋フィルムを有する、無機固体電解質二次電池。
項２． 前記リチウム塩化合物は、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2（ＬｉＴＦＳＩ）、ＬｉＮ（ＳＦＯ2）2（ＬｉＦＳＩ）、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、及びＬｉＮ［ＣＦ3ＳＣ（Ｃ2Ｆ5ＳＯ2）3］2からなる群より選択される少なくとも１種である、項１に記載の無機固体電解質二次電池。
項３． 前記無機固体電解質と、前記架橋フィルムとが接触している、項１または２に記載の無機固体電解質二次電池。
項４． 前記無機固体電解質は、酸化物系固体電解質又は硫化物系固体電解質である、項１～３のいずれか１項に記載の無機固体電解質二次電池。
That is, the present invention provides the following aspects.
Item 1. An inorganic solid electrolyte secondary battery comprising a positive electrode, an inorganic solid electrolyte, a negative electrode, and a crosslinked film,
the crosslinked film is a crosslinked product of a composition including a lithium salt compound and an ion conductive polymer having an ethylene oxide unit in a side chain,
an inorganic solid electrolyte secondary battery having the crosslinked film at least one between the positive electrode and the inorganic solid electrolyte and between the negative electrode and the inorganic solid electrolyte.
Item 2. The inorganic solid electrolyte secondary battery according to Item 1, wherein the lithium salt compound is at least one selected from the group consisting of LiBF4 , LiPF6 , LiClO4, LiCF3SO3, LiN(CF3SO2 ) 2 ( LiTFSI ), LiN(SFO2) 2 ( LiFSI), LiN ( C2F5SO2 ) 2 , and LiN[ CF3SC ( C2F5SO2 ) 3 ] 2 .
Item 3. The inorganic solid electrolyte secondary battery according to item 1 or 2, wherein the inorganic solid electrolyte and the crosslinked film are in contact with each other.
Item 4. The inorganic solid electrolyte secondary battery according to any one of Items 1 to 3, wherein the inorganic solid electrolyte is an oxide-based solid electrolyte or a sulfide-based solid electrolyte.
本発明によれば、優れた充放電特性を発揮する新規な無機固体電解質二次電池を提供することができる。 The present invention provides a new inorganic solid electrolyte secondary battery that exhibits excellent charge/discharge characteristics.
本発明の無機固体電解質二次電池は、正極、無機固体電解質、負極、及び架橋フィルムを備える、無機固体電解質二次電池であって、前記架橋フィルムは、リチウム塩化合物、及び側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーを含む組成物の架橋体であり、正極と無機固体電解質との間、及び負極と無機固体電解質との間の少なくとも一方に、前記架橋フィルムを有することを特徴としている。本発明の無機固体電解質二次電池は、このような構成を備えていることにより、優れた充放電特性を発揮することができる。 The inorganic solid electrolyte secondary battery of the present invention is an inorganic solid electrolyte secondary battery comprising a positive electrode, an inorganic solid electrolyte, a negative electrode, and a crosslinked film, the crosslinked film being a crosslinked body of a composition containing a lithium salt compound and an ion-conductive polymer having an ethylene oxide unit in a side chain, and characterized in that the crosslinked film is present at least either between the positive electrode and the inorganic solid electrolyte or between the negative electrode and the inorganic solid electrolyte. The inorganic solid electrolyte secondary battery of the present invention is capable of exhibiting excellent charge and discharge characteristics by having such a configuration.
より具体的には、本発明の無機固体電解質二次電池において、前記の架橋フィルム（以下、単に「架橋フィルム」と表記することがある）は、リチウム塩化合物、及びイオン伝導性ポリマーを含む組成物の架橋体であることから、イオン伝導性を有しており、かつ、無機材料と比較して高い柔軟性を有している。従って、当該架橋フィルムは、無機固体電解質（無機固体粒子の集合体）や電極（より具体的には、活物質粒子などを含む電極材料層）との接触面積が大きくなり、その結果、固体電解質や電極との界面抵抗が効果的に低下し、本発明の無機固体電解質二次電池は優れた充放電特性を発揮するものと考えられる。なお、後述の通り、本発明の架橋フィルムは、正極及び負極の少なくとも一方と、無機固体電解質との間に配置され、かつ、無機固体電解質と接触するように設けられることが好ましい。また、無機固体電解質二次電池は、高温環境（例えば１００℃以上の高温環境）で使用されることもあるが、本発明の無機固体電解質二次電池は、高温環境において優れた充放電特性を発揮する。以下、本発明の無機固体電解質二次電池について詳述する。 More specifically, in the inorganic solid electrolyte secondary battery of the present invention, the crosslinked film (hereinafter, sometimes simply referred to as "crosslinked film") is a crosslinked body of a composition containing a lithium salt compound and an ion-conductive polymer, and therefore has ion conductivity and has high flexibility compared to inorganic materials. Therefore, the crosslinked film has a large contact area with the inorganic solid electrolyte (aggregate of inorganic solid particles) and the electrode (more specifically, an electrode material layer containing active material particles, etc.), and as a result, the interface resistance with the solid electrolyte and the electrode is effectively reduced, and it is considered that the inorganic solid electrolyte secondary battery of the present invention exhibits excellent charge and discharge characteristics. As described later, it is preferable that the crosslinked film of the present invention is disposed between at least one of the positive electrode and the negative electrode and the inorganic solid electrolyte, and is provided so as to be in contact with the inorganic solid electrolyte. In addition, although the inorganic solid electrolyte secondary battery may be used in a high-temperature environment (for example, a high-temperature environment of 100°C or higher), the inorganic solid electrolyte secondary battery of the present invention exhibits excellent charge and discharge characteristics in a high-temperature environment. The inorganic solid electrolyte secondary battery of the present invention will be described in detail below.
なお、本明細書において、「～」で結ばれた数値は、「～」の前後の数値を下限値及び上限値として含む数値範囲を意味する。複数の下限値と複数の上限値が別個に記載されている場合、任意の下限値と上限値を選択し、「～」で結ぶことができるものとする。 In this specification, a numerical value connected with "~" means a numerical range that includes the numerical values before and after "~" as the lower and upper limits. When multiple lower limits and multiple upper limits are listed separately, any lower limit and upper limit may be selected and connected with "~".
架橋フィルムは、少なくとも、リチウム塩化合物と、側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとを含む組成物を架橋することにより形成される。すなわち、架橋フィルムは、リチウム塩化合物とイオン伝導性ポリマーを含む組成物の架橋フィルムである。 The crosslinked film is formed by crosslinking a composition containing at least a lithium salt compound and an ion-conductive polymer having ethylene oxide units in its side chain. That is, the crosslinked film is a crosslinked film of a composition containing a lithium salt compound and an ion-conductive polymer.
側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーとしては、例えば、側鎖にエチレンオキシド単位を有するポリエーテル、側鎖にエチレンオキシド単位を有するホウ酸エステル、側鎖にエチレンオキシド単位を有するポリオレフィン等があり、好ましくは側鎖にエチレンオキシド単位を有するポリエーテルである。 Ion-conductive polymers having ethylene oxide units in the side chain include, for example, polyethers having ethylene oxide units in the side chain, borate esters having ethylene oxide units in the side chain, and polyolefins having ethylene oxide units in the side chain, and polyethers having ethylene oxide units in the side chain are preferred.
側鎖にエチレンオキシド単位を有するポリエーテルは、側鎖にエチレンオキシド単位を有するエポキシ化合物から形成された構成単位を含むことが好ましい。すなわち、イオン伝導性ポリマーは、側鎖にエチレンオキシド単位を有するエポキシ化合物を少なくとも単量体としたポリマーであることが好ましい。 It is preferable that the polyether having an ethylene oxide unit in the side chain contains a structural unit formed from an epoxy compound having an ethylene oxide unit in the side chain. In other words, it is preferable that the ion-conductive polymer is a polymer in which at least the monomer is an epoxy compound having an ethylene oxide unit in the side chain.
側鎖にエチレンオキシド単位を有するエポキシ化合物としては、例えば、下記式（２）で表される単量体が挙げられ、下記式（２）、必要により下記式（１）、下記式（３）で表される単量体を用いた分岐型ポリエーテルは、側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）となる。式（１）～（３）で表される単量体は、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。式（１）～（３）で表される単量体は、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。 An example of an epoxy compound having an ethylene oxide unit in the side chain is a monomer represented by the following formula (2). A branched polyether using a monomer represented by the following formula (2) and, if necessary, the following formula (1) or formula (3) is a polyether (i) having an ethylene oxide unit in the side chain. Only one type of monomer represented by formulas (1) to (3) may be used, or two or more types may be mixed together. Only one type of monomer represented by formulas (1) to (3) may be used, or two or more types may be mixed together.
［式（２）中、Ｒは－ＣＨ2Ｏ（ＣＨ2ＣＨ2Ｏ）nＲ4であり、Ｒ4は炭素数１～６のアルキル基であり、ｎは０～１２の数である。］ [In formula (2), R is —CH 2 O(CH 2 CH 2 O) n R 4 , R 4 is an alkyl group having 1 to 6 carbon atoms, and n is a number from 0 to 12.]
［式（３）中、Ｒ5は、エチレン性不飽和基を含有する基を表す。］ [In formula (3), R5 represents a group containing an ethylenically unsaturated group.]
式（３）の単量体としては、アリルグリシジルエーテル、４－ビニルシクロヘキシルグリシジルエーテル、α－テルピニルグリシジルエーテル、シクロヘキセニルメチルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、アリルフェニルグリシジルエーテル、ビニルグリシジルエーテル、３，４－エポキシ－１－ブテン、３，４－エポキシ－１－ペンテン、４，５－エポキシ－２－ペンテン、１，２－エポキシ－５，９－シクロドデカンジエン、３，４－エポキシ－１－ビニルシクロヘキセン、１，２－エポキシ－５－シクロオクテン、アクリル酸グリシジル、メタクリル酸グリシジル、ソルビン酸グリシジル、ケイ皮酸グリシジル、クロトン酸グリシジル、グリシジル－４－ヘキセノエートが用いられる。好ましくは、アリルグリシジルエーテル、アクリル酸グリシジル、メタクリル酸グリシジルである。 As the monomer of formula (3), allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinyl glycidyl ether, cyclohexenyl methyl glycidyl ether, p-vinylbenzyl glycidyl ether, allyl phenyl glycidyl ether, vinyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecanediene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl cinnamate, glycidyl crotonate, and glycidyl-4-hexenoate are used. Allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate are preferably used.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）の合成は、例えば、次のようにして行うことができる。開環重合触媒として有機アルミニウムを主体とする触媒系、有機亜鉛を主体とする触媒系、有機錫－リン酸エステル縮合物触媒系などの配位アニオン開始剤、または対イオンにＫ+を含むカリウムアルコキシド、ジフェニルメチルカリウム、水酸化カリウムなどのアニオン開始剤を用いて、各単量体を溶媒の存在下又は不存在下、反応温度１０～１２０℃、撹拌下で反応させることによってポリエーテル（ｉ）が得られる。重合度、あるいは得られる共重合体の性質などの点から、配位アニオン開始剤が好ましく、なかでも有機錫－リン酸エステル縮合物触媒系が取り扱い易く特に好ましい。 The synthesis of polyether (i) having an ethylene oxide unit in the side chain can be carried out, for example, as follows. Polyether ( i ) is obtained by reacting each monomer with stirring at a reaction temperature of 10 to 120°C in the presence or absence of a solvent using a coordination anion initiator such as an organoaluminum-based catalyst system, an organozinc-based catalyst system, or an organotin-phosphate ester condensate catalyst system as a ring-opening polymerization catalyst, or an anion initiator such as potassium alkoxide, diphenylmethyl potassium, or potassium hydroxide containing K + as a counter ion. From the viewpoint of the degree of polymerization or the properties of the resulting copolymer, coordination anion initiators are preferred, and among them, organotin-phosphate ester condensate catalyst systems are particularly preferred because of their ease of handling.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）において、式（１）の単量体に由来する繰り返し単位（Ａ）と、式（２）の単量体に由来する繰り返し単位（Ｂ）と、式（３）の単量体に由来する繰り返し単位（Ｃ）とのモル比は、（Ａ）９５～５モル％、（Ｂ）５～９５モル％、および（Ｃ）０～２０モル％が適当であり、好ましくは（Ａ）９２～９モル％、（Ｂ）７～９０モル％、および（Ｃ）１～１５モル％、更に好ましくは（Ａ）８８～１８モル％、（Ｂ）１０～８０モル％、および（Ｃ）２～１５モル％である。繰り返し単位（Ａ）が９５モル％以下であるとガラス転移温度の上昇とオキシエチレン鎖の結晶化を招かず、結果的にイオン伝導性の点で好ましい。 In the polyether (i) having ethylene oxide units in the side chain, the molar ratio of the repeating unit (A) derived from the monomer of formula (1), the repeating unit (B) derived from the monomer of formula (2), and the repeating unit (C) derived from the monomer of formula (3) is suitably 95-5 mol% for (A), 5-95 mol% for (B), and 0-20 mol% for (C), preferably 92-9 mol% for (A), 7-90 mol% for (B), and 1-15 mol% for (C), and more preferably 88-18 mol% for (A), 10-80 mol% for (B), and 2-15 mol% for (C). If the repeating unit (A) is 95 mol% or less, the glass transition temperature does not increase and the oxyethylene chains do not crystallize, which is preferable in terms of ion conductivity.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）の具体例としては、エチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル三元共重合体、エチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／メタクリル酸グリシジル三元共重合体、エチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アクリル酸グリシジル三元共重合体等が挙げられる。 Specific examples of polyethers (i) having ethylene oxide units in the side chain include ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether terpolymers, ethylene oxide/diethylene glycol methyl glycidyl ether/glycidyl methacrylate terpolymers, and ethylene oxide/diethylene glycol methyl glycidyl ether/glycidyl acrylate terpolymers.
側鎖にエチレンオキシド単位を有するポリエーテル（ｉ）の重量平均分子量は特に限定されないが、１万～３００万であってよく、５万～２５０万であることがより好ましく、１０万～２００万であることが特に好ましい。重量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）で、溶媒としてジメチルホルムアミド（ＤＭＦ）を使用して、標準ポリスチレン換算により算出する。 The weight average molecular weight of the polyether (i) having ethylene oxide units in the side chain is not particularly limited, but may be from 10,000 to 3,000,000, more preferably from 50,000 to 2,500,000, and particularly preferably from 100,000 to 2,000,000. The weight average molecular weight is calculated by gel permeation chromatography (GPC) using dimethylformamide (DMF) as a solvent in terms of standard polystyrene.
架橋フィルムに含まれるイオン伝導性ポリマーの含有量としては、架橋フィルム全体を１００質量部として、好ましくは５～９５質量部、より好ましくは１０～９０質量部である。 The content of the ion-conductive polymer in the crosslinked film is preferably 5 to 95 parts by mass, and more preferably 10 to 90 parts by mass, based on 100 parts by mass of the entire crosslinked film.
リチウム塩化合物としては、リチウムイオン電池に一般的に利用されているような、広い電位窓を有するリチウム塩化合物が好適である。リチウム塩化合物としては、例えば、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣｌＯ4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2（ＬｉＴＦＳＩ），ＬｉＮ（ＳＦＯ2）2（ＬｉＦＳＩ）、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、ＬｉＮ［ＣＦ3ＳＣ（Ｃ2Ｆ5ＳＯ2）3］2などを挙げられるが、これらに限定されない。これらは、単独で用いても、２種類以上を混合して用いても良い。 The lithium salt compound is preferably a lithium salt compound having a wide potential window, as is generally used in lithium ion batteries.The lithium salt compound may be, for example, LiBF4 , LiPF6 , LiClO4 , LiCF3SO3 , LiN(CF3SO2)2(LiTFSI), LiN(SFO2)2(LiFSI), LiN(C2F5SO2 ) 2 , LiN [ CF3SC ( C2F5SO2 ) 3 ] 2 , etc. , but is not limited thereto.These may be used alone or in combination of two or more.
架橋フィルムに含まれるリチウム塩化物の含有量リチウム塩化合物のモル数／イオン伝導性ポリマーのエーテル酸素原子の総モル数の値が０．０００１～５が好ましく、更に好ましくは０．００１～０．５の範囲がよい。 The content of lithium chloride in the crosslinked film (moles of lithium salt compound) / total moles of ether oxygen atoms in the ion-conductive polymer is preferably 0.0001 to 5, more preferably 0.001 to 0.5.
また、架橋フィルムには、常温溶融塩が含まれていてもよい。常温溶融塩は、常温において少なくとも一部が液状を呈する塩をいい、常温とは電源が通常作動すると想定される温度範囲をいう。電源が通常作動すると想定される温度範囲とは、上限が１２０℃程度、場合によっては６０℃程度であり、下限は－４０℃程度、場合によっては－２０℃程度である。 The crosslinked film may also contain room temperature molten salt. Room temperature molten salt refers to salt that is at least partially liquid at room temperature, and room temperature refers to the temperature range in which the power supply is expected to operate normally. The temperature range in which the power supply is expected to operate normally has an upper limit of about 120°C, and in some cases about 60°C, and a lower limit of about -40°C, and in some cases about -20°C.
常温溶融塩はイオン液体とも呼ばれており、ピリジン系、脂肪族アミン系、脂環族アミン系の４級アンモニウム有機物カチオンが知られている。４級アンモニウム有機物カチオンとしては、ジアルキルイミダゾリウム、トリアルキルイミダゾリウム、などのイミダゾリウムイオン、テトラアルキルアンモニウムイオン、アルキルピリジニウムイオン、ピラゾリウムイオン、ピロリジニウムイオン、ピペリジニウムイオンなどが挙げられる。特に、イミダゾリウムカチオンが好ましい。 Room temperature molten salts are also called ionic liquids, and pyridine-based, aliphatic amine-based, and alicyclic amine-based quaternary ammonium organic cations are known. Examples of quaternary ammonium organic cations include imidazolium ions such as dialkylimidazolium and trialkylimidazolium, tetraalkylammonium ions, alkylpyridinium ions, pyrazolium ions, pyrrolidinium ions, and piperidinium ions. In particular, imidazolium cations are preferred.
なお、テトラアルキルアンモニウムイオンとしては、トリメチルエチルアンモニウムイオン、トリメチルエチルアンモニウムイオン、トリメチルプロピルアンモニウムイオン、トリメチルヘキシルアンモニウムイオン、テトラペンチルアンモニウムイオン、トリエチルメチルアンモニウムイオンなどが挙げられるが、これらに限定されるものではない。 Examples of tetraalkylammonium ions include, but are not limited to, trimethylethylammonium ion, trimethylethylammonium ion, trimethylpropylammonium ion, trimethylhexylammonium ion, tetrapentylammonium ion, and triethylmethylammonium ion.
また、アルキルピリジウムイオンとしては、Ｎ－メチルピリジウムイオン、Ｎ－エチルピリジニウムイオン、Ｎ－プロピルピリジニウムイオン、Ｎ－ブチルピリジニウムイオン、１－エチル－２メチルピリジニウムイオン、１－ブチル－４－メチルピリジニウムイオン、１－ブチル－２，４ジメチルピリジニウムイオンなどが挙げられるが、これらに限定されるものではない。 Alkylpyridinium ions include, but are not limited to, N-methylpyridinium ion, N-ethylpyridinium ion, N-propylpyridinium ion, N-butylpyridinium ion, 1-ethyl-2-methylpyridinium ion, 1-butyl-4-methylpyridinium ion, and 1-butyl-2,4-dimethylpyridinium ion.
イミダゾリウムカチオンとしては、１，３－ジメチルイミダゾリウムイオン、１－エチル－３－メチルイミダゾリウムイオン、１－メチル－３－エチルイミダゾリウムイオン、１－メチル－３－ブチルイミダゾリウムイオン、１－ブチル－３－メチルイミダゾリウムイオン、１，２，３－トリメチルイミダゾリウムイオン、１，２－ジメチル－３－エチルイミダゾリウムイオン、１，２－ジメチル－３－プロピルイミダゾリウムイオン、１－ブチル－２，３－ジメチルイミダゾリウムイオンなどが挙げられるが、これらに限定されるものではない。 Examples of imidazolium cations include, but are not limited to, 1,3-dimethylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-ethylimidazolium ion, 1-methyl-3-butylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1,2,3-trimethylimidazolium ion, 1,2-dimethyl-3-ethylimidazolium ion, 1,2-dimethyl-3-propylimidazolium ion, and 1-butyl-2,3-dimethylimidazolium ion.
なお、これらのカチオンを有する常温溶融塩は、単独で用いてもよく、または２種以上を混合して用いても良い。 These room temperature molten salts having cations may be used alone or in combination of two or more.
架橋フィルムに常温溶融塩が含まれる場合、その含有量としては、イオン伝導性ポリマー１００質量部に対して、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 When the crosslinked film contains a room temperature molten salt, the content is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, per 100 parts by mass of the ion conductive polymer.
架橋フィルムは、可塑剤などを含んでいてもよい。可塑剤としては、特に限定されないが、ジシアノ化合物、分岐型エーテル化合物が好ましい。可塑剤を添加する場合は、イオン伝導性ポリマーを架橋することが好ましい。この架橋は、化学架橋であり、架橋フィルムからの可塑剤の流出を抑制できる。 The crosslinked film may contain a plasticizer. There are no particular limitations on the plasticizer, but dicyano compounds and branched ether compounds are preferred. When a plasticizer is added, it is preferred to crosslink the ion-conductive polymer. This crosslinking is chemical crosslinking, and can prevent the plasticizer from leaking out of the crosslinked film.
ジシアノ化合物としてはスクシノニトリル、グルタロニトリル、アジポニトリル、１，５－ジシアノペンタン、１，６－ジシアノヘキサン、１，７－ジシアノヘプタン、１，８－ジシアノオクタン等が挙げられる。分岐型エーテル化合物の例として、下記の多分岐型エーテル化合物などが挙げられる。 Examples of dicyano compounds include succinonitrile, glutaronitrile, adiponitrile, 1,5-dicyanopentane, 1,6-dicyanohexane, 1,7-dicyanoheptane, and 1,8-dicyanooctane. Examples of branched ether compounds include the following multi-branched ether compounds.
架橋フィルムに可塑剤が含まれる場合、可塑剤の含有量としては、イオン伝導性ポリマー１００質量部に対して、好ましくは１０～１０００質量部、より好ましくは２０～５００質量部である。 When the crosslinked film contains a plasticizer, the content of the plasticizer is preferably 10 to 1000 parts by mass, and more preferably 20 to 500 parts by mass, per 100 parts by mass of the ion-conductive polymer.
リチウム塩化合物とイオン伝導性ポリマーを含む組成物に反応開始剤や架橋助剤を配合して、架橋フィルムを形成してもよい。反応開始剤としては、熱反応開始剤、光反応開始剤が挙げられる。 A crosslinked film may be formed by adding a reaction initiator or a crosslinking assistant to a composition containing a lithium salt compound and an ion-conductive polymer. Examples of reaction initiators include thermal reaction initiators and photoreaction initiators.
熱反応開始剤としては、有機過酸化物、アゾ化合物等から選ばれるラジカル開始剤が用いられる。有機過酸化物としては、ケトンパーオキシド、パーオキシケタール、ハイドロパーオキシド、ジアルキルパーオキシド、ジアシルパーオキシド、パーオキシエステル等、通常架橋用途に使用されているものが用いられ、アゾ化合物としてはアゾニトリル化合物、アゾアミド化合物、アゾアミジン化合物等、通常架橋用途に使用されているものが用いられる。ラジカル開始剤の添加量は種類により異なるが、通常、イオン伝導性ポリマーを１００質量部として０．１～１０質量部の範囲内である。 As the thermal reaction initiator, a radical initiator selected from organic peroxides, azo compounds, etc. is used. As the organic peroxides, those normally used for crosslinking applications such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, etc. are used, and as the azo compounds, those normally used for crosslinking applications such as azonitrile compounds, azoamide compounds, azoamidine compounds, etc. are used. The amount of radical initiator added varies depending on the type, but is usually within the range of 0.1 to 10 parts by mass per 100 parts by mass of the ion-conductive polymer.
光反応開始剤としては、アルキルフェノン系、ベンゾフェノン系、アシルフォスフィンオキサイド系、チタノセン類、トリアジン類、ビスイミダゾール類、オキシムエステル類などラジカル開始剤が用いられる。これらのラジカル重合開始剤の添加量は種類により異なるが、通常、イオン伝導性ポリマーを１００質量部として０．０１～５．０質量部の範囲内である。 As photoinitiators, radical initiators such as alkylphenones, benzophenones, acylphosphine oxides, titanocenes, triazines, bisimidazoles, and oxime esters are used. The amount of these radical polymerization initiators added varies depending on the type, but is usually within the range of 0.01 to 5.0 parts by mass per 100 parts by mass of the ion conductive polymer.
架橋助剤としては、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、オリゴエチレングリコールジアクリレート、オリゴエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、アリルメタクリレート、アリルアクリレート、ジアリルマレート、トリアリルイソシアヌレート、マレイミド、フェニルマレイミド、無水マレイン酸等を任意に用いることができる。 As crosslinking aids, any of the following can be used: ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, allyl acrylate, diallyl maleate, triallyl isocyanurate, maleimide, phenylmaleimide, maleic anhydride, etc.
リチウム塩化合物とイオン伝導性ポリマーを含む組成物には、有機溶媒を配合してもよく、有機溶媒としては、トルエン、キシレン、ベンゼン、アセトニトリル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ＴＨＦ（テトラヒドロフラン）が挙げられる。 An organic solvent may be added to the composition containing the lithium salt compound and the ionically conductive polymer. Examples of the organic solvent include toluene, xylene, benzene, acetonitrile, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and THF (tetrahydrofuran).
架橋フィルムの作製方法は、例えば、イオン伝導性ポリマー、必要に応じて反応開始剤、及びリチウム塩化合物を有機溶媒に混合して溶解して組成物を形成し、基材（例えばＰＥＴフィルムやテフロン（登録商標）板など）上に組成物をキャスティングし、溶媒を除去後、加熱又は紫外線などの活性エネルギー線照射によって架橋フィルムを作製する方法が挙げられる。また、直接、無機固体電解質の表面に当該組成物をキャスティングして、架橋フィルムを作製することもできる。 For example, a method for producing a crosslinked film includes mixing and dissolving an ion-conductive polymer, if necessary a reaction initiator, and a lithium salt compound in an organic solvent to form a composition, casting the composition on a substrate (such as a PET film or a Teflon (registered trademark) plate), removing the solvent, and then producing a crosslinked film by heating or irradiating with active energy rays such as ultraviolet rays. Alternatively, the composition can be cast directly onto the surface of an inorganic solid electrolyte to produce a crosslinked film.
架橋フィルムの膜厚は、好ましくは０．１μｍ～２００μｍ、より好ましくは０．５μｍ～１００μｍの範囲内である。 The thickness of the crosslinked film is preferably in the range of 0.1 μm to 200 μm, more preferably 0.5 μm to 100 μm.
本発明の無機固体電解質二次電池の積層構成としては、例えば、以下の構成が挙げられる。
正極、架橋フィルム、無機固体電解質、架橋フィルム、及び負極が順に積層された積層構成；
正極、架橋フィルム、無機固体電解質、及び負極が順に積層された積層構成；
正極、無機固体電解質、架橋フィルム、及び負極が順に積層された積層構成。
Examples of the laminate structure of the inorganic solid electrolyte secondary battery of the present invention include the following structures.
A laminated structure in which a positive electrode, a crosslinked film, an inorganic solid electrolyte, a crosslinked film, and a negative electrode are laminated in this order;
A laminated structure in which a positive electrode, a crosslinked film, an inorganic solid electrolyte, and a negative electrode are laminated in this order;
A laminated structure in which a positive electrode, an inorganic solid electrolyte, a crosslinked film, and a negative electrode are laminated in this order.
本発明の無機固体電解質二次電池においては、無機固体電解質と前述の架橋フィルムとが接触していることが好ましい。無機固体電解質は、一般に、電解質を構成する無機固体粒子の集合体により形成されており、粒子間には空隙が存在している。架橋フィルムは、リチウム塩化合物を含むイオン伝導性ポリマーを含む組成物の架橋体であることから、イオン伝導性を有しており、かつ、無機材料と比較して高い柔軟性を有している。従って、当該架橋フィルムは、無機固体電解質との接触面積が大きくなり、その結果、無機固体電解質の界面抵抗が効果的に低下し、本発明の無機固体電解質二次電池は優れた充放電特性を発揮するものと考えられる。なお、電極材料層に含まれる活物質粒子なども空隙を形成することから、本発明の無機固体電解質二次電池においては、架橋フィルムが電極の電極材料層と接触していることも好ましいし、架橋フィルムが電極材料層と無機固体電解質の両方と接触していることも好ましい。 In the inorganic solid electrolyte secondary battery of the present invention, it is preferable that the inorganic solid electrolyte and the crosslinked film mentioned above are in contact with each other. Inorganic solid electrolytes are generally formed by an aggregate of inorganic solid particles that constitute the electrolyte, and voids exist between the particles. The crosslinked film is a crosslinked body of a composition containing an ion-conductive polymer containing a lithium salt compound, and therefore has ion conductivity and is highly flexible compared to inorganic materials. Therefore, the crosslinked film has a large contact area with the inorganic solid electrolyte, and as a result, the interface resistance of the inorganic solid electrolyte is effectively reduced, and the inorganic solid electrolyte secondary battery of the present invention is considered to exhibit excellent charge and discharge characteristics. In addition, since the active material particles contained in the electrode material layer also form voids, it is also preferable that the crosslinked film is in contact with the electrode material layer of the electrode in the inorganic solid electrolyte secondary battery of the present invention, and it is also preferable that the crosslinked film is in contact with both the electrode material layer and the inorganic solid electrolyte.
本発明の無機固体電解質二次電池において、正極、負極ともに公知のものを用いることができるが、集電体に正極材料層、又は負極材料層を備える電極を例示することができる。 In the inorganic solid electrolyte secondary battery of the present invention, both the positive and negative electrodes can be known, but an example is an electrode that has a positive electrode material layer or a negative electrode material layer on a current collector.
正極、負極には、公知の集電体を用いることができる。具体的には、正極には、集電体として、アルミニウム、ニッケル、ステンレス、金、白金、チタン等の金属が使用される。負極には、集電体として、銅、ニッケル、ステンレス、金、白金、チタン等の金属が使用される。 A known current collector can be used for the positive and negative electrodes. Specifically, metals such as aluminum, nickel, stainless steel, gold, platinum, and titanium are used as the current collector for the positive electrode. Metals such as copper, nickel, stainless steel, gold, platinum, and titanium are used as the current collector for the negative electrode.
また、正極材料層、負極材料層は、それぞれ、少なくとも正極活物質、負極活物質を含有し、更に導電助剤、バインダー、増粘剤を含有していてもよく必要に応じて、前述の無機固体電解質を含有させてもよい。 The positive electrode material layer and the negative electrode material layer each contain at least a positive electrode active material and a negative electrode active material, and may further contain a conductive assistant, a binder, a thickener, and, if necessary, the inorganic solid electrolyte described above.
本発明で使用される正極活物質は、ＬｉＭＯ2、ＬｉＭ2Ｏ4、Ｌｉ2ＭＯ3、ＬｉＭＥＯ4のいずれかの組成からなるリチウム金属含有複合酸化物粉末である。ここで式中のＭは主として遷移金属からなり、Ｃｏ、Ｍｎ、Ｎｉ、Ｃｒ、Ｆｅ、Ｔｉの少なくとも一種を含んでいる。Ｍは遷移金属からなるが、遷移金属以外にもＡｌ、Ｇａ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ、Ｓｉ、Ｐ、Ｂなどが添加されていてもよい。ＥはＰ、Ｓｉの少なくとも１種を含んでいる。正極活物質の粒子径には５０μｍ以下が好ましく、更に好ましくは２０μｍ以下のものを用いる。これらの活物質は、３Ｖ（ｖｓ．Ｌｉ／Ｌｉ＋）以上の起電力を有するものである。 The positive electrode active material used in the present invention is a lithium metal-containing composite oxide powder consisting of any one of LiMO2 , LiM2O4 , Li2MO3 , and LiMEO4 . Here, M in the formula is mainly composed of a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe, and Ti. M is composed of a transition metal, but in addition to the transition metal, Al, Ga, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc. may be added. E contains at least one of P and Si. The particle diameter of the positive electrode active material is preferably 50 μm or less, and more preferably 20 μm or less. These active materials have an electromotive force of 3 V (vs. Li/Li+) or more.
正極活物質の具体例としては、コバルト酸リチウム、ニッケル酸リチウム、ニッケル／コバルト／マンガン酸リチウム（３元系）、スピネル型マンガン酸リチウム、リン酸鉄リチウムなどが挙げられる。 Specific examples of positive electrode active materials include lithium cobalt oxide, lithium nickel oxide, nickel/cobalt/lithium manganese oxide (ternary system), spinel-type lithium manganese oxide, and lithium iron phosphate.
本発明で使用される負極活物質は、リチウムイオンなどのアルカリ金属イオンを吸蔵・放出可能な構造（層間化合物）を有する炭素材料（天然黒鉛、人造黒鉛、非晶質炭素等）か、リチウムイオンなどのアルカリ金属イオンを吸蔵・放出可能なリチウム、アルミニウム系化合物、スズ系化合物、シリコン系化合物、チタン系化合物等の金属である。粉末の場合、粒子径は１０ｎｍ以上１００μｍ以下が好ましく、更に好ましくは２０ｎｍ以上２０μｍ以下である。また、金属と炭素材料との混合活物質として用いてもよい。 The negative electrode active material used in the present invention is a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (intercalation compound) capable of absorbing and releasing alkali metal ions such as lithium ions, or a metal such as lithium, an aluminum-based compound, a tin-based compound, a silicon-based compound, or a titanium-based compound capable of absorbing and releasing alkali metal ions such as lithium ions. In the case of a powder, the particle size is preferably 10 nm or more and 100 μm or less, and more preferably 20 nm or more and 20 μm or less. A mixed active material of a metal and a carbon material may also be used.
導電助剤を用いる場合には、公知の導電助剤を用いることができ、黒鉛、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などの導電性カーボンブラック、カーボンナノチューブなどの炭素繊維、または金属粉末等が挙げられる。これら導電助剤は１種または２種以上用いてもよい。 When a conductive assistant is used, a known conductive assistant can be used, and examples of such conductive assistant include graphite, furnace black, acetylene black, Ketjen black, and other conductive carbon blacks, carbon fibers such as carbon nanotubes, and metal powders. These conductive assistants may be used alone or in combination of two or more kinds.
バインダーとしては、例えばＰＶｄＦ等のフッ素樹脂、フッ素ゴムやアクリルゴム、変性アクリルゴム、スチレン－ブタジエンゴム、アクリル系重合体、ビニル系重合体、前記記載のイオン伝導性ポリマーから選ばれる１種以上の化合物を用いることができる。これらバインダーは活物質を１００質量部として、好ましくは５質量部以下、より好ましくは３質量部以下、例えば０．０１～２質量部添加する。 As the binder, for example, one or more compounds selected from fluororesins such as PVdF, fluororubbers, acrylic rubbers, modified acrylic rubbers, styrene-butadiene rubbers, acrylic polymers, vinyl polymers, and the ion-conducting polymers described above can be used. These binders are added in an amount of preferably 5 parts by mass or less, more preferably 3 parts by mass or less, for example 0.01 to 2 parts by mass, per 100 parts by mass of the active material.
増粘剤の具体例としては、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロースおよびこれらの塩（ナトリウム塩等のアルカリ金属塩、アンモニウム塩）、ポリビニルアルコール、ポリアクリル酸塩、ポリエチレンオキサイド等が挙げられる。これら増粘剤は１種または２種以上用いてもよい。これら増粘剤は活物質を１００質量部として、好ましくは５質量部以下、より好ましくは３質量部以下、例えば０．０１～２質量部添加する。また、塗工液の粘度が低い場合には増粘剤を併用することができる。 Specific examples of thickeners include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose and their salts (alkali metal salts such as sodium salts, ammonium salts), polyvinyl alcohol, polyacrylates, polyethylene oxide, etc. These thickeners may be used alone or in combination. These thickeners are added in an amount of preferably 5 parts by mass or less, more preferably 3 parts by mass or less, for example 0.01 to 2 parts by mass, per 100 parts by mass of active material. Furthermore, if the viscosity of the coating liquid is low, a thickener can be used in combination.
集電体と正極材料層、負極材料層を備える正極、負極の作製方法は特に限定されず一般的な方法が用いられる。例えば、正極活物質あるいは負極活物質、導電助剤、バインダー、水またはＮ-メチル-２-ピロリドン（ＮＭＰ）等の溶媒、必要に応じて増粘剤などからなる正極材料、負極材料のペースト（塗工液）をドクターブレード法やシルクスクリーン法などにより集電体表面上に適切な厚さに均一に塗布することより行われる。 The method for producing the positive and negative electrodes, which include a current collector and a positive and negative electrode material layers, is not particularly limited, and a general method can be used. For example, the method is carried out by uniformly applying a paste (coating liquid) of the positive and negative electrode materials, which are composed of a positive or negative electrode active material, a conductive assistant, a binder, a solvent such as water or N-methyl-2-pyrrolidone (NMP), and a thickener as necessary, to an appropriate thickness on the surface of the current collector using a doctor blade method, silk screen method, or the like.
例えばドクターブレード法では、負極活物質粉末や正極活物質粉末、導電助剤、バインダー等を水に分散してスラリー状にし、金属電極基板に塗布した後、所定のスリット幅を有するブレードにより適切な厚さに均一化する。電極は活物質塗布後、余分な有機溶剤を除去するため、例えば、１００℃の熱風や８０℃減圧状態で乾燥する。乾燥後の電極はプレス装置によってプレス成型することで電極が製造される。 For example, in the doctor blade method, negative electrode active material powder, positive electrode active material powder, conductive additive, binder, etc. are dispersed in water to form a slurry, which is then applied to a metal electrode substrate and then uniformized to an appropriate thickness using a blade with a specified slit width. After the active material is applied to the electrode, it is dried, for example, with hot air at 100°C or under reduced pressure at 80°C to remove excess organic solvent. After drying, the electrode is press-molded using a press device to produce the electrode.
集電体上に正極材料層、負極材料層を形成した場合には、正極材料層、負極材料の電極材料間、例えば活物質間、活物質と他の電極材料との間等に空隙を生じることになる。本発明の無機固体電解質二次電池においては、このような空隙に、イオン伝導性ポリマー、リチウム塩化合物などを含んでいてもよい。 When a positive electrode material layer and a negative electrode material layer are formed on a current collector, voids are generated between the electrode materials of the positive electrode material layer and the negative electrode material, for example, between the active materials, between the active materials and other electrode materials, etc. In the inorganic solid electrolyte secondary battery of the present invention, such voids may contain an ion-conducting polymer, a lithium salt compound, etc.
無機固体電解質としては、酸化物系固体電解質、及び硫化物系固体電解質を例示することができる。無機固体電解質は、一般に、電解質を構成する無機固体粒子の集合体である。 Examples of inorganic solid electrolytes include oxide-based solid electrolytes and sulfide-based solid electrolytes. Inorganic solid electrolytes are generally aggregates of inorganic solid particles that constitute the electrolyte.
酸化物系固体電解質は、酸素を含有し、かつ、周期律表第１族または第２族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものであれば特に限定されるものではない。 There are no particular limitations on the oxide-based solid electrolyte, so long as it contains oxygen, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation properties.
酸化物系固体電解質を構成する具体的な化合物としては、ＬｉxＬａyＴｉＯ3〔ｘ＝０．３～０．７、ｙ＝０．３～０．７〕（ＬＬＴ）、ＬｉxＬａyＺｒzＭmＯn（ＭはＡｌ，Ｍｇ，Ｃａ，Ｓｒ，Ｖ，Ｎｂ，Ｔａ，Ｔｉ，Ｇｅ，Ｉｎ，Ｓｎの少なくとも１種以上の元素でありｘは５≦ｘ≦１０を満たし、ｙは１≦ｙ≦４を満たし、ｚは１≦ｚ≦４を満たし、ｍは０≦ｍ≦２を満たし、ｎは５≦ｎ≦２０を満たす。）ＬｉxＢyＭzＯn（式中ＭはＣ，Ｓ，Ａｌ，Ｓｉ，Ｇａ，Ｇｅ，Ｉｎ，Ｓｎの少なくとも１種以上の元素でありｘは０≦ｘ≦５を満たし、ｙは０≦ｙ≦１を満たし、ｚは０≦ｚ≦１を満たし、ｎは０≦ｎ≦６を満たす。）、Ｌｉx（Ａｌ，Ｇａ）y（Ｔｉ，Ｇｅ）zＳｉaＰmＯn（ただし、１≦ｘ≦３、０≦ｙ≦１、０≦ｚ≦２、０≦ａ≦１、１≦ｍ≦７、３≦ｎ≦１３）、Ｌｉ(3-2x)ＭxＤＯ（ｘは０以上０．１以下の数を表し、Ｍは２価の金属原子を表す。Ｄはハロゲン原子または２種以上のハロゲン原子の組み合わせを表す。）、ＬｉxＳｉyＯz（１≦ｘ≦５、０＜ｙ≦３、１≦ｚ≦１０）、ＬｉxＳyＯz（１≦ｘ≦３、０＜ｙ≦２、１≦ｚ≦１０）、Ｌｉ3ＢＯ3－Ｌｉ2ＳＯ4、Ｌｉ2Ｏ－Ｂ2Ｏ3－Ｐ2Ｏ5、Ｌｉ2Ｏ－ＳｉＯ2、Ｌｉ6ＢａＬａ2Ｔａ2Ｏ12、Ｌｉ3ＰＯ(4-3/2w)Ｎw（ｗはｗ＜１）、ＬＩＳＩＣＯＮ（Ｌｉｔｈｉｕｍ ｓｕｐｅｒ ｉｏｎｉｃ ｃｏｎｄｕｃｔｏｒ）型結晶構造を有するＬｉ3.5Ｚｎ0.25ＧｅＯ4、ペロブスカイト型結晶構造を有するＬａ0.55Ｌｉ0.35ＴｉＯ3、ＮＡＳＩＣＯＮ（Ｎａｔｒｉｕｍ ｓｕｐｅｒ ｉｏｎｉｃ ｃｏｎｄｕｃｔｏｒ）型結晶構造を有するＬｉＴｉ2Ｐ3Ｏ12、Ｌｉ(1+x+y)（Ａｌ，Ｇａ）x（Ｔｉ，Ｇｅ）(2-x)ＳｉyＰ(3-y)Ｏ12（ただし、０≦ｘ≦１、０≦ｙ≦１）、ガーネット型結晶構造を有するＬｉ7Ｌａ3Ｚｒ2Ｏ１2等が挙げられる。またＬｉ、Ｐ及びＯを含むリン化合物も望ましい。例えばリン酸リチウム（Ｌｉ3ＰＯ4）、リン酸リチウムの酸素の一部を窒素で置換したＬｉＰＯＮ、ＬｉＰＯＤ（Ｄは、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ａｇ、Ｔａ、Ｗ、Ｐｔ、Ａｕ等から選ばれた少なくとも１種）等が挙げられる。また、ＬｉＡＯＮ（Ａは、Ｓｉ、Ｂ、Ｇｅ、Ａｌ、Ｃ、Ｇａ等から選ばれた少なくとも１種）等も好ましく用いることができる。 Specific compounds constituting the oxide-based solid electrolyte include Li x La y TiO 3 [x=0.3-0.7, y=0.3-0.7] (LLT), Li x La y Zr z M m O n (wherein M is at least one element selected from the group consisting of Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn, where x satisfies 5≦x≦10, y satisfies 1≦y≦4, z satisfies 1≦z≦4, m satisfies 0≦m≦2, and n satisfies 5≦n≦20), Li x B y M z O n (wherein M is at least one element selected from the group consisting of C, S, Al, Si, Ga, Ge, In, and Sn, where x satisfies 0≦x≦5, y satisfies 0≦y≦1, z satisfies 0≦z≦1, and n satisfies 0≦n≦6), and Li x (Al,Ga) y (Ti,Ge) zSiaPmOn ( wherein 1≦x≦3 , 0 ≦y≦1, 0≦z≦2, 0≦a≦1, 1≦m≦7, 3≦n≦13), Li ( 3-2x) MxDO (x is a number between 0 and 0.1, M is a divalent metal atom, and D is a halogen atom or a combination of two or more halogen atoms), LixSiyOz ( 1≦x≦5, 0<y≦3, 1≦z≦10), LixSyOz (1≦x≦ 3 , 0<y≦2 , 1≦z≦ 10 ) , Li3BO3 - Li2SO4 , Li2O- B2O3 - P2O5 , Li2O - SiO2 , Li6BaLa2 Ta2O12 , Li3PO (4-3/2w) Nw (w is w<1), Li3.5Zn0.25GeO4 having a LISICON (lithium super ionic conductor) type crystal structure, La0.55Li0.35TiO3 having a perovskite type crystal structure , LiTi2P3O12 having a NASICON (sodium super ionic conductor) type crystal structure, Li (1+x+y) ( Al,Ga) x (Ti,Ge) (2-x) SiyP (3-y) O12 (where 0 ≦ x ≦ 1, 0≦y≦1), Li7 having a garnet type crystal structure, La3Zr2O12 , etc. Also preferred are phosphorus compounds containing Li, P and O. Examples include lithium phosphate ( Li3PO4 ), LiPON in which part of the oxygen in lithium phosphate is replaced with nitrogen, LiPOD (D is at least one selected from Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru , Ag, Ta, W, Pt, Au, etc.), etc. Also preferably usable is LiAON (A is at least one selected from Si, B, Ge, Al, C, Ga, etc.).
その中でも、ＬｉxＬａyＴｉＯ3〔ｘ＝０．３～０．７、ｙ＝０．３～０．７〕（ＬＬＴ）、ＬｉxＬａyＺｒzＭmＯn（ＭはＡｌ，Ｍｇ，Ｃａ，Ｓｒ，Ｖ，Ｎｂ，Ｔａ，Ｔｉ，Ｇｅ，Ｉｎ，Ｓｎの少なくとも１種以上の元素でありｘは５≦ｘ≦１０を満たし、ｙは１≦ｙ≦４を満たし、ｚは１≦ｚ≦４を満たし、ｍは０≦ｍ≦２を満たし、ｎは５≦ｎ≦２０を満たす。）、Ｌｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ）、Ｌｉ3ＢＯ3、Ｌｉ3ＢＯ3－Ｌｉ2ＳＯ4、Ｌｉ3ＢＯ3－Ｌｉ2ＣＯ3、Ｌｉx（Ａｌ，Ｇａ）y（Ｔｉ，Ｇｅ）zＳｉaＰmＯn（ただし、１≦ｘ≦３、０≦ｙ≦１、０≦ｚ≦２、０≦ａ≦１、１≦ｍ≦７、３≦ｎ≦１３）が好ましい。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Among them, Li x La y TiO 3 [x=0.3-0.7, y=0.3-0.7] (LLT), Li x La y Zr z M m O n (M is at least one element selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In, and Sn, x satisfies 5≦x≦10, y satisfies 1≦y≦4, z satisfies 1≦z≦4, m satisfies 0≦m≦2, and n satisfies 5≦n≦20), Li 7 La 3 Zr 2 O 12 (LLZ), Li 3 BO 3 , Li 3 BO 3 -Li 2 SO 4 , Li 3 BO 3 -Li 2 CO 3 , Li x (Al,Ga) y (Ti, Ge) zSiaPmOn (wherein 1≦x≦3 , 0≦y≦1 , 0≦z≦2 , 0≦a≦1, 1≦m≦7, 3≦n≦13) is preferred. These may be used alone or in combination of two or more.
硫化物系固体電解質は、硫黄を含有し、かつ、周期律表第１族または第２族に属する金属のイオン伝導性を有し、かつ、電子絶縁性を有するものであれば特に限定されるものではない。例えば下記式で示される組成を満たすリチウムイオン伝導性無機固体電解質が挙げられる。 There are no particular limitations on the sulfide-based solid electrolyte, so long as it contains sulfur, has the ionic conductivity of a metal belonging to Group 1 or 2 of the periodic table, and has electronic insulation. For example, a lithium ion conductive inorganic solid electrolyte that satisfies the composition shown in the following formula can be used.
ＬｉaＭbＰcＳdＡe Li a M b P c S d A e
式中、Ｍは、Ｂ、Ｚｎ、Ｓｎ、Ｓｉ、Ｃｕ、Ｇａ、Ｓｂ、Ａｌ及びＧｅから選択される元素を示す。なかでも、Ｂ、Ｓｎ、Ｓｉ、Ａｌ、Ｇｅが好ましく、Ｓｎ、Ａｌ、Ｇｅがより好ましい。Ａは、Ｉ、Ｂｒ、Ｃｌ、Ｆを示し、Ｉ、Ｂｒが好ましく、Ｉが特に好ましい。ａ～ｅは各元素の組成比を示し、ａ：ｂ：ｃ：ｄ：ｅは１～１２：０～１：１：２～１２：０～５を満たす。ａはさらに、１～９が好ましく、１．５～４がより好ましい。ｂは０～０．５が好ましい。ｄはさらに、３～７が好ましく、３．２５～４．５がより好ましい。ｅはさらに、０～３が好ましく、０～２がより好ましい。 In the formula, M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among them, B, Sn, Si, Al, and Ge are preferred, and Sn, Al, and Ge are more preferred. A represents I, Br, Cl, and F, and I and Br are preferred, and I is particularly preferred. a to e represent the composition ratio of each element, and a:b:c:d:e satisfies 1 to 12:0 to 1:1:2 to 12:0 to 5. a is more preferably 1 to 9, and more preferably 1.5 to 4. b is more preferably 0 to 0.5. d is more preferably 3 to 7, and more preferably 3.25 to 4.5. e is more preferably 0 to 3, and more preferably 0 to 2.
式において、Ｌｉ、Ｍ、Ｐ、Ｓ及びＡの組成比は、好ましくはｂ、ｅが０であり、より好ましくはｂ＝０、ｅ＝０で且つａ、ｃ及びｄの比（ａ：ｃ：ｄ）がａ：ｃ：ｄ＝１～９：１：３～７であり、さらに好ましくはｂ＝０、ｅ＝０で且つａ：ｃ：ｄ＝１．５～４：１：３．２５～４．５である。 In the formula, the composition ratio of Li, M, P, S, and A is preferably such that b and e are 0, more preferably b=0, e=0, and the ratio of a, c, and d (a:c:d) is a:c:d=1-9:1:3-7, and even more preferably b=0, e=0, and a:c:d=1.5-4:1:3.25-4.5.
無機固体電解質が粒子状である場合、その粒子径としては、例えば０．０１～１００μｍ、好ましくは０．１～２０μｍが挙げられる。 When the inorganic solid electrolyte is particulate, the particle size is, for example, 0.01 to 100 μm, preferably 0.1 to 20 μm.
無機固体電解質二次電池の製造方法
本発明の無機固体電解質二次電池の製造方法は特に限定されず、少なくとも、正極、負極、無機固体電解質、及び架橋フィルムで構成され、公知の方法にて製造される。例えば、コイン型のリチウムイオン電池の場合、正極、無機固体電解質、負極、さらに、正極と無機固体電解質との間、及び、負極と無機固体電解質との間の少なくとも一方に架橋フィルムを配置して、外装缶に挿入する。その後、封口体とタブ溶接などで接合して、封口体を封入し、カシめることで蓄電池が得られる。電池の形状は限定されないが、例としてはコイン型、円筒型、シート型などがあげられ、２個以上の電池を積層した構造でもよい。
The method of manufacturing the inorganic solid electrolyte secondary battery of the present invention is not particularly limited, and the inorganic solid electrolyte secondary battery is composed of at least a positive electrode, a negative electrode, an inorganic solid electrolyte, and a crosslinked film, and is manufactured by a known method. For example, in the case of a coin-type lithium ion battery, a positive electrode, an inorganic solid electrolyte, a negative electrode, and a crosslinked film are arranged at least one between the positive electrode and the inorganic solid electrolyte and between the negative electrode and the inorganic solid electrolyte, and then inserted into an outer can. Then, the battery is joined to the sealing body by tab welding or the like, and the sealing body is sealed and caulked to obtain a storage battery. The shape of the battery is not limited, but examples include a coin type, a cylindrical type, a sheet type, and the like, and a structure in which two or more batteries are stacked may be used.
以下の実施例において本発明をより具体的に説明するが、本発明はこれらに限定されない。 The present invention will be described in more detail in the following examples, but is not limited to these.
本実施例では、コイン電池を作製し、コイン電池の充放電特性の性能評価を以下の実験にて行った。 In this example, a coin battery was fabricated and the performance of the charge/discharge characteristics of the coin battery was evaluated in the following experiment.
［作製した電池の評価］
作製した電池の評価としては充放電装置を用いて充放電試験を行い、充電容量および放電容量を求めた。
[Evaluation of the fabricated battery]
The produced batteries were evaluated by carrying out a charge/discharge test using a charge/discharge device to determine the charge capacity and discharge capacity.
充放電測定
０．１Ｃ（１０時間率）に相当する電流で４．２ＶまでＣＣＣＶ充電（０．０１Ｃカット）後、０．１Ｃに相当する電流で、２．５ＶまでＣＣＣＶ放電（０．０１Ｃカット）を行った。試験温度は１００℃環境とした。
Charge/Discharge Measurement: The battery was CCCV charged (0.01 C cut) to 4.2 V at a current equivalent to 0.1 C (10-hour rate), and then CCCV discharged (0.01 C cut) to 2.5 V at a current equivalent to 0.1 C. The test temperature was set to a 100° C. environment.
無機固体電解質二次電池用電極の作製例
［正極の実施作製例］
（１）正極活物質としてＮＣＭ（ニッケル／コバルト／マンガン酸リチウム＝５／２／３）１００質量部に、導電助剤としてアセチレンブラック３質量部、黒鉛３質量部、バインダーとしてＰＶｄＦ３質量部を加え、さらにスラリーの固形分濃度が３５質量％となるようにＮＭＰ溶液中に加えて、十分に混合して正極用スラリーを得た。得られた正極スラリーを厚さ２０μｍのアルミ集電体上にダイコーターを用いて塗布し、１００℃で１２時間以上乾繰後、ロールプレス機にてプレスを行い、厚さ２０μｍの無機固体電解質二次電池用正極の前駆体を作製した（目付量 ６．６ｍｇ／ｃｍ2、正極密度 ３．１ｇ／ｃｍ3、空隙率 ２６％）。
Example of Electrode Preparation for Inorganic Solid Electrolyte Secondary Battery [Example of Positive Electrode Preparation]
(1) 100 parts by mass of NCM (nickel/cobalt/lithium manganate = 5/2/3) as a positive electrode active material, 3 parts by mass of acetylene black as a conductive assistant, 3 parts by mass of graphite, and 3 parts by mass of PVdF as a binder were added, and further added to an NMP solution so that the solid content concentration of the slurry was 35% by mass, and mixed thoroughly to obtain a positive electrode slurry. The obtained positive electrode slurry was applied to an aluminum collector having a thickness of 20 μm using a die coater, dried at 100 ° C. for 12 hours or more, and then pressed with a roll press machine to prepare a precursor of a positive electrode for an inorganic solid electrolyte secondary battery having a thickness of 20 μm (weight per unit area 6.6 mg/cm 2 , positive electrode density 3.1 g/cm 3 , porosity 26%).
（２）イオン伝導性ポリマーとしてエチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル＝８０／１７／３モル％三元共重合体（重量平均分子量１５０万）１００質量部、リチウム塩化合物としてホウフッ化リチウム１２質量部、架橋助剤として、トリメチロールプロパントリアクリレート １０質量部、ラジカル開始剤としてベンゾイルパーオキシド（ナイパーＢＭＴ、日油株式会社製）０．３質量部をアセトニトリル ９００質量部に完全に溶解させた正極含浸用塗工溶液を調製した。 (2) A coating solution for positive electrode impregnation was prepared by completely dissolving 100 parts by mass of ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether = 80/17/3 mol% ternary copolymer (weight average molecular weight 1.5 million) as an ion conductive polymer, 12 parts by mass of lithium borofluoride as a lithium salt compound, 10 parts by mass of trimethylolpropane triacrylate as a crosslinking aid, and 0.3 parts by mass of benzoyl peroxide (Niper BMT, manufactured by NOF Corporation) as a radical initiator in 900 parts by mass of acetonitrile.
（３）上記（１）の正極の前駆体の上に、上記（２）の正極含浸用塗工溶液を塗工した。その後、２時間静置することにより、溶媒を除去しながら、正極内の空隙にイオン伝導性ポリマーとリチウム塩化合物を含浸した。１００℃で２時間、減圧下、含浸したイオン伝導性ポリマーの架橋を行い、無機固体電解質二次電池用正極を作製した。 (3) The coating solution for impregnating the positive electrode (2) above was applied onto the positive electrode precursor (1) above. The solution was then left to stand for 2 hours to remove the solvent, and the voids in the positive electrode were impregnated with the ion-conductive polymer and the lithium salt compound. The impregnated ion-conductive polymer was crosslinked under reduced pressure at 100°C for 2 hours to produce a positive electrode for an inorganic solid electrolyte secondary battery.
［負極の実施作製例］
（１）負極活物質として人造黒鉛（粒径１０μｍ） １００質量部に、導電助剤として気相成長炭素繊維（ＶＧＣＦ）２質量部、バインダーとしてＳＢＲ ３質量部、増粘剤としてカルボキシメチルセルロースのナトリウム塩 ２質量部を加え、さらにスラリーの固形分濃度が３５質量％となるように水を加えて、十分に混合して負極用スラリーを得た。得られた負極スラリーを厚さ１６．５μｍの銅集電体上にダイコーターを用いて塗布し、１００℃で１２時間以上乾繰後、ロールプレス機にてプレスを行い、厚さ２２μｍの無機固体電解質二次電池用負極の前駆体を作製した（目付量３．１ｍｇ／ｃｍ2、負極密度１．２ｇ／ｃｍ3、空隙率２３％）。
[Example of negative electrode preparation]
(1) 100 parts by mass of artificial graphite (particle size 10 μm) as a negative electrode active material, 2 parts by mass of vapor grown carbon fiber (VGCF) as a conductive assistant, 3 parts by mass of SBR as a binder, 2 parts by mass of sodium salt of carboxymethylcellulose as a thickener, and water were added so that the solid content concentration of the slurry was 35% by mass, and the mixture was thoroughly mixed to obtain a negative electrode slurry. The obtained negative electrode slurry was applied to a copper current collector having a thickness of 16.5 μm using a die coater, dried at 100 ° C. for 12 hours or more, and then pressed with a roll press machine to prepare a precursor of a negative electrode for an inorganic solid electrolyte secondary battery having a thickness of 22 μm (weight 3.1 mg / cm 2 , negative electrode density 1.2 g / cm 3 , porosity 23%).
（２）イオン伝導性ポリマーとしてエチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル＝８０／１７／３モル％三元共重合体（重量平均分子量１５０万）１００質量部、リチウム塩化合物としてＬｉＴＦＳＩ ３８質量部を、架橋助剤として、トリメチロールプロパントリアクリレート １０質量部、ラジカル開始剤としてベンゾイルパーオキシド（ナイパーＢＭＴ、日油株式会社製）０．３質量部をアセトニトリル９００質量部に完全に溶解させた負極含浸用塗工溶液を調製した。 (2) A coating solution for impregnating the negative electrode was prepared by completely dissolving 100 parts by mass of ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether = 80/17/3 mol% ternary copolymer (weight average molecular weight 1.5 million) as an ion conductive polymer, 38 parts by mass of LiTFSI as a lithium salt compound, 10 parts by mass of trimethylolpropane triacrylate as a crosslinking aid, and 0.3 parts by mass of benzoyl peroxide (Niper BMT, manufactured by NOF Corporation) as a radical initiator in 900 parts by mass of acetonitrile.
（３）上記（１）の負極の前駆体の上に、上記（２）の電極含浸用塗工溶液を塗工した。その後、２時間静置することにより、溶媒を除去しながら、負極内の空隙にイオン伝導性ポリマーとリチウム塩化合物を含浸した。１００℃で２時間、減圧下、含浸したイオン伝導性ポリマーの架橋を行い、無機固体電解質二次電池用負極を作製した。 (3) The coating solution for electrode impregnation (2) above was applied onto the precursor of the negative electrode (1) above. After that, the mixture was left to stand for 2 hours to remove the solvent, and the voids in the negative electrode were impregnated with the ion-conductive polymer and the lithium salt compound. The impregnated ion-conductive polymer was crosslinked under reduced pressure at 100°C for 2 hours to produce a negative electrode for an inorganic solid electrolyte secondary battery.
［架橋フィルムの実施作製例］
イオン伝導性ポリマーとしてエチレンオキシド／ジエチレングリコールメチルグリシジルエーテル／アリルグリシジルエーテル＝８０／１７／３モル％三元共重合体（重量平均分子量１５０万）１００質量部、リチウム塩化合物としてＬｉＴＦＳＩ ３８質量部を、架橋助剤として、トリメチロールプロパントリアクリレート１０質量部、ラジカル開始剤としてベンゾイルパーオキシド（ナイパーＢＭＴ、日油株式会社製）０．３質量部をアセトニトリル９００質量部に完全に溶解させて塗工溶液を調製した。この塗工溶液をＰＥＴフィルム上に塗工、乾燥後、１００℃、２時間、減圧下で熱架橋を行い、厚さ２０μｍの架橋フィルムを得た。
[Example of crosslinked film production]
A coating solution was prepared by completely dissolving 100 parts by mass of ethylene oxide/diethylene glycol methyl glycidyl ether/allyl glycidyl ether = 80/17/3 mol% ternary copolymer (weight average molecular weight 1.5 million) as an ion conductive polymer, 38 parts by mass of LiTFSI as a lithium salt compound, 10 parts by mass of trimethylolpropane triacrylate as a crosslinking aid, and 0.3 parts by mass of benzoyl peroxide (Niper BMT, manufactured by NOF Corporation) as a radical initiator in 900 parts by mass of acetonitrile. This coating solution was applied onto a PET film, dried, and then thermally crosslinked at 100 ° C. for 2 hours under reduced pressure to obtain a crosslinked film having a thickness of 20 μm.
［リチウム塩化合物を含むポリエチレンオキシドフィルムの比較例］
ポリエチレンオキシド（重量平均分子量１１０万）１００質量部、リチウム塩化合物としてＬｉＴＦＳＩ ３８質量部をアセトニトリル９００質量部に完全に溶解させて塗工溶液を調製した。この塗工溶液をＰＥＴフィルム上に塗工、乾燥後、厚さ３０μｍのリチウム塩化合物を含むポリエチレンオキシドフィルムを得た。
[Comparative Example of Polyethylene Oxide Film Containing Lithium Salt Compound]
A coating solution was prepared by completely dissolving 100 parts by mass of polyethylene oxide (weight average molecular weight 1.1 million) and 38 parts by mass of LiTFSI as a lithium salt compound in 900 parts by mass of acetonitrile. This coating solution was applied onto a PET film and dried to obtain a polyethylene oxide film containing a lithium salt compound having a thickness of 30 μm.
電池の製造例
［無機固体電解質二次電池の実施製造例１］
ドライルーム内において、無機固体電解質二次電池用正極の実施作製例で得た正極、実施作製例の架橋フィルム、無機固体電解質としてＬｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ， 豊島製作所製 膜厚５００μｍ）、実施作製例の架橋フィルム、負極としての金属リチウム箔の順に積層後、カシめ、試験用２０３２型コイン電池を製造した。
＜充放電条件＞
下限電圧２．５Ｖ－上限電圧４．２Ｖ、１００℃
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）充電
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）放電
＜充放電試験結果＞
充電容量１６８ｍＡｈ／ｇ、放電容量１６２ｍＡｈ／ｇ
Battery Manufacturing Example [Inorganic Solid Electrolyte Secondary Battery Manufacturing Example 1]
In a dry room, the positive electrode obtained in the working example of the positive electrode for an inorganic solid electrolyte secondary battery, the crosslinked film of the working example, Li7La3Zr2O12 ( LLZ , manufactured by Toshima Manufacturing Co., Ltd., film thickness 500 μm) as an inorganic solid electrolyte, the crosslinked film of the working example, and metallic lithium foil as a negative electrode were laminated in that order, and then crimped to produce a test 2032 type coin battery.
<Charge and discharge conditions>
Lower limit voltage 2.5V-upper limit voltage 4.2V, 100℃
Charge CC(0.1C)-CV(0.01C) Discharge CC(0.1C)-CV(0.01C) <Charge/discharge test results>
Charge capacity 168mAh/g, discharge capacity 162mAh/g
［無機固体電解質二次電池の実施製造例２］
ドライルーム内において、無機固体電解質二次電池用正極の実施作製例で得た正極、実施作製例の架橋フィルム、無機固体電解質としてＬｉ7Ｌａ3Ｚｒ2Ｏ12（ＬＬＺ， 豊島製作所製 膜厚５００μｍ）、実施作製例の架橋フィルム、無機固体電解質二次電池用負極の実施作製例で得た負極の順に積層後、カシめ、試験用２０３２型コイン電池を製造した。
＜充放電条件＞
下限電圧２．５Ｖ－上限電圧４．２Ｖ、１００℃
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）充電
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）放電
＜充放電試験結果＞
充電容量１３５ｍＡｈ／ｇ、放電容量１２２ｍＡｈ／ｇ
[Inorganic Solid Electrolyte Secondary Battery Manufacturing Example 2]
In a dry room, the positive electrode obtained in the practical preparation example of the positive electrode for an inorganic solid electrolyte secondary battery, the crosslinked film of the practical preparation example, Li7La3Zr2O12 (LLZ, manufactured by Toshima Manufacturing Co., Ltd., film thickness 500 μm ) as an inorganic solid electrolyte, the crosslinked film of the practical preparation example, and the negative electrode obtained in the practical preparation example of the negative electrode for an inorganic solid electrolyte secondary battery were stacked in that order, and then crimped to produce a test 2032 type coin battery.
<Charge and discharge conditions>
Lower limit voltage 2.5V-upper limit voltage 4.2V, 100℃
Charge CC(0.1C)-CV(0.01C) Discharge CC(0.1C)-CV(0.01C) <Charge/discharge test results>
Charge capacity 135mAh/g, discharge capacity 122mAh/g
［無機固体電解質二次電池の比較製造例１］
実施作製例の架橋フィルムの代わりに、比較例のポリエチレンオキシドフィルムを用いたこと以外は、実施製造例１と同様にして、試験用２０３２型コイン電池を製造した。
＜充放電条件＞
下限電圧２．５Ｖ－上限電圧４．２Ｖ、１００℃
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）充電
ＣＣ（０．１Ｃ）－ＣＶ（０．０１Ｃ）放電
＜充放電試験結果＞
充電容量１０２ｍＡｈ／ｇ、放電容量８３ｍＡｈ／ｇ
[Comparative Production Example 1 of Inorganic Solid Electrolyte Secondary Battery]
A test 2032 type coin battery was produced in the same manner as in Example 1, except that the crosslinked film of the Example was replaced with the polyethylene oxide film of the Comparative Example.
<Charge and discharge conditions>
Lower limit voltage 2.5V-upper limit voltage 4.2V, 100℃
Charge CC(0.1C)-CV(0.01C) Discharge CC(0.1C)-CV(0.01C) <Charge/discharge test results>
Charge capacity 102mAh/g, discharge capacity 83mAh/g
前記の架橋フィルムは、フィルム強度、柔軟性、結着性、イオン伝導性がある。実施製造例および比較例の結果から、正極及び負極と無機固体電解質との間に当該架橋フィルムが配置されている無機固体電解質二次電池は、電池特性（充電および放電容量）が優れていることがわかる。 The crosslinked film has film strength, flexibility, adhesion, and ionic conductivity. From the results of the working examples and comparative examples, it can be seen that an inorganic solid electrolyte secondary battery in which the crosslinked film is disposed between the positive and negative electrodes and the inorganic solid electrolyte has excellent battery characteristics (charge and discharge capacity).
本発明の無機固体電解質二次電池は、優れた充放電特性を発揮することができ、電気自動車やハイブリッド電気自動車などの車載用途や家庭用電力貯蔵用の蓄電池といった大型の電池用途に好適に利用可能である。 The inorganic solid electrolyte secondary battery of the present invention can exhibit excellent charge/discharge characteristics and can be suitably used for in-vehicle applications such as electric vehicles and hybrid electric vehicles, and for large battery applications such as storage batteries for home power storage.
Claims (4)
前記架橋フィルムは、リチウム塩化合物、及び側鎖にエチレンオキシド単位を有するイオン伝導性ポリマーを含む組成物の架橋体であり、
前記正極と前記無機固体電解質との間、及び前記負極と前記無機固体電解質との間の少なくとも一方に、前記架橋フィルムを有する、無機固体電解質二次電池。 An inorganic solid electrolyte secondary battery comprising a positive electrode, an inorganic solid electrolyte, a negative electrode, and a crosslinked film,
the crosslinked film is a crosslinked product of a composition including a lithium salt compound and an ion conductive polymer having an ethylene oxide unit in a side chain,
an inorganic solid electrolyte secondary battery having the crosslinked film at least one between the positive electrode and the inorganic solid electrolyte and between the negative electrode and the inorganic solid electrolyte.
The inorganic solid electrolyte secondary battery according to any one of claims 1 to 3, wherein the inorganic solid electrolyte is an oxide-based solid electrolyte or a sulfide-based solid electrolyte.
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| WO1997042251A1 (en) | 1996-05-08 | 1997-11-13 | Daiso Co., Ltd. | Cross-linked solid polyelectrolyte and use thereof |
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| WO1997042251A1 (en) | 1996-05-08 | 1997-11-13 | Daiso Co., Ltd. | Cross-linked solid polyelectrolyte and use thereof |
| JP2012014892A (en) | 2010-06-30 | 2012-01-19 | Sumitomo Electric Ind Ltd | Nonaqueous electrolyte battery |
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