JP4075866B2 - Flat organic electrolyte battery - Google Patents
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- JP4075866B2 JP4075866B2 JP2004187732A JP2004187732A JP4075866B2 JP 4075866 B2 JP4075866 B2 JP 4075866B2 JP 2004187732 A JP2004187732 A JP 2004187732A JP 2004187732 A JP2004187732 A JP 2004187732A JP 4075866 B2 JP4075866 B2 JP 4075866B2
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- lithium
- organic electrolyte
- imidazole
- separator
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- 239000005486 organic electrolyte Substances 0.000 title claims description 29
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 81
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 239000003365 glass fiber Substances 0.000 claims description 18
- 238000010248 power generation Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000004734 Polyphenylene sulfide Substances 0.000 description 8
- 229920000069 polyphenylene sulfide Polymers 0.000 description 8
- -1 polypropylene Polymers 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000004696 Poly ether ether ketone Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229920002530 polyetherether ketone Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005383 fluoride glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920013653 perfluoroalkoxyethylene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910020879 Sn-Li Inorganic materials 0.000 description 1
- 229910008888 Sn—Li Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 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 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Cell Separators (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Description
本発明は、高温多湿環境下での使用に耐えることができ、低温放電特性に優れる偏平形の有機電解液電池に関するものである。 The present invention relates to a flat organic electrolyte battery that can withstand use in a high-temperature and high-humidity environment and has excellent low-temperature discharge characteristics.
最近、タイヤ内部の圧力センサーなどのような１００℃を超す高温雰囲気と、多湿環境下、および−４０℃などの低温雰囲気下などの厳しい環境下で使用する機器の電源として、電池が要望されている。その仕様を満たす候補として、０℃以下の低凝固点と１００℃以上の高沸点の有機電解液を用いるリチウム一次電池やリチウム二次電池などの有機電解液電池が有望であり、様々な研究・開発が盛んに行われている。 Recently, a battery has been demanded as a power source for equipment used in severe environments such as a high temperature atmosphere exceeding 100 ° C. such as a pressure sensor inside a tire, a humid environment, and a low temperature atmosphere such as −40 ° C. Yes. Candidates satisfying the specifications are promising organic electrolyte batteries such as lithium primary batteries and lithium secondary batteries that use organic electrolytes with a low freezing point of 0 ° C or lower and a high boiling point of 100 ° C or higher. Has been actively conducted.
有機電解液電池の形状としては、必要な放電容量、大きさ、実装性、コストなどから偏平形（ボタン型、コイン型、扁平角型）が最適である。 As the shape of the organic electrolyte battery, a flat type (button type, coin type, flat rectangular type) is optimal in view of necessary discharge capacity, size, mountability, cost, and the like.
上記の温度範囲での要求特性に対して、従来の電池構成材料のガスケット、セパレータ、電解液などを変更することが特許文献１に開示されている。これによれば、ガスケットには従来使用しているポリプリピレン（ＰＰ）は１００℃以上の温度では軟化して十分な強度が得られないため、エンジニアリングプラスチックであるポリフェニレンスルフィド（ＰＰＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、テトラフルオロエチレン−パーフルオロアルコキシエチレン共重合体（ＰＦＡ）などの樹脂は１００℃以上の高温雰囲気下でも強度を維持することができるために、最適であるとされており、また、セパレータについても同様に、低融点のポリエチレン（ＰＥ）、ポリプリピレン（ＰＰ）に変えて、ポリブチレンテレフタレート（ＰＢＴ）、ポリフェニレンスルフィド（ＰＰＳ）などを用いることが提案されており、また、電解液には高沸点・低凝固点の溶媒を用いることが提案されている。 Japanese Patent Application Laid-Open No. H10-228707 discloses changing the gasket, separator, electrolytic solution, and the like of conventional battery constituent materials with respect to the required characteristics in the above temperature range. According to this, since the conventionally used polypropylene (PP) is softened at a temperature of 100 ° C. or higher and sufficient strength cannot be obtained, engineering plastics such as polyphenylene sulfide (PPS), polyetheretherketone Resins such as (PEEK) and tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA) are considered optimal because they can maintain strength even in a high temperature atmosphere of 100 ° C. or higher, Similarly, it has been proposed to use polybutylene terephthalate (PBT), polyphenylene sulfide (PPS) or the like instead of low melting point polyethylene (PE) or polypropylene (PP) for the separator. Proposal to use a solvent with high boiling point and low freezing point It has been.
また、特許文献２では、イオン透過性に優れ、高い強度を持ち、薄くかつ絶縁性に優れ、耐熱性にも優れるセパレータ材料として、ガラス繊維からなるものが提案されており、他のセパレータに比べて抵抗成分が小さくなり、様々な条件での放電特性が向上する。
しかし、高沸点・低凝固点の溶媒を用いた電解液は、総じて粘性が非常に高いので、セパレータへの含浸性が非常に低くく、セパレータ内での抵抗成分が高くなり負荷特性が非常に悪くなる恐れがある。 However, electrolytes using a solvent with a high boiling point and a low freezing point generally have very high viscosity, so the impregnation into the separator is very low, the resistance component in the separator is high, and the load characteristics are very poor. There is a fear.
また、有機電解液に一般的に使用されている溶質である六フッ化燐酸リチウム（ＬｉＰＦ6）、四フッ化ホウ酸リチウム（ＬｉＢＦ4）は水分と容易に反応してフッ酸を形成し、電池構成材料に悪影響する。そのため、電池製造時の厳しい水分監理や電池内部への水分侵入に対して封止性能を向上する取り組みが行われている。しかし、偏平形の有機電解液電池の封止はカシメ封口により行われ、他のレーザ封口やガラスハーメチックシールなどに比べて気密性が劣る。加えて、タイヤ内部の圧力センサーなどのような電源として偏平形電池が高温多湿雰囲気下にさらされると、電池外部からの水分進入を阻止するのは困難な状況にある。 In addition, lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF 4 ), which are solutes commonly used in organic electrolytes, easily react with moisture to form hydrofluoric acid, It adversely affects battery components. For this reason, efforts are being made to improve sealing performance against strict moisture monitoring during battery manufacture and moisture intrusion into the battery. However, the flat organic electrolyte battery is sealed with a caulking seal, which is less airtight than other laser seals or glass hermetic seals. In addition, when a flat battery is exposed to a hot and humid atmosphere as a power source such as a pressure sensor inside the tire, it is difficult to prevent moisture from entering from the outside of the battery.
このような状況のもとでは、ガラス繊維からなるセパレータは、ガラス特有の問題として、フッ酸（ＨＦ）との急激な反応によりフッ化ガラス（ＳｉＦ4）となり、セパレータとしての機能が極度に低下してしまう。すなわち、無色透明または白色のガラスセパレータがフッ酸との反応により黒色のフッ化ガラスとなり、セパレータ機能が低下に伴って、放電性能が著しく低下する恐れがある。 Under such circumstances, a separator made of glass fiber becomes a fluoride glass (SiF 4 ) due to a rapid reaction with hydrofluoric acid (HF) as a problem peculiar to glass, and the function as a separator is extremely lowered. Resulting in. That is, the colorless and transparent or white glass separator becomes a black fluoride glass due to the reaction with hydrofluoric acid, and the discharge performance may be remarkably lowered as the separator function is lowered.
本発明は、高温多湿環境下での信頼性の確保と低温雰囲気下での高負荷放電特性に優れる偏平形有機電解液電池を目的とする。 An object of the present invention is to provide a flat organic electrolyte battery that is excellent in ensuring reliability in a high-temperature and high-humidity environment and having high-load discharge characteristics in a low-temperature atmosphere.
上記課題を解決するため、本発明の偏平形有機電解液電池は、有底円筒状に形成された負極缶と有底円筒状に形成された正極缶との間に環状のガスケットを介在させ、前記正極缶の開口部を内側にかしめて正極、負極、セパレータ、及び有機電解液からなる発電要素を密封した偏平形有機電解液電池であって、前記セパレータはガラス繊維を主成分とし、前記有機電解液はリチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）とイミダゾールを含み、前記イミダゾールの含有量がリチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）とイミダゾールの総量に対して５〜３５ｍｏｌ％であることを特徴とする。 In order to solve the above problems, the flat organic electrolyte battery of the present invention has an annular gasket interposed between a negative electrode can formed into a bottomed cylindrical shape and a positive electrode can formed into a bottomed cylindrical shape, A flat organic electrolyte battery in which a positive electrode, a negative electrode, a separator, and a power generation element composed of an organic electrolyte are sealed by caulking the opening of the positive electrode can, wherein the separator is mainly composed of glass fiber, and the organic The electrolytic solution contains lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) and imidazole , and the content of the imidazole is lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) and imidazole. It is characterized by being 5-35 mol% with respect to the total amount.
ガラス繊維を主成分とするセパレータと、リチウム塩としてリチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）を含む有機電解液を用い、イミダゾ
ールを適量含有することで、高温多湿環境下での信頼性と低温雰囲気下での高負荷放電特性に優れた偏平形有機電解液電池を提供することができる。
Using an organic electrolytic solution containing a separator mainly composed of glass fiber and lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) as a lithium salt , imidazo
By containing an appropriate amount of the steel, it is possible to provide a flat organic electrolyte battery excellent in reliability under a high-temperature and high-humidity environment and high load discharge characteristics under a low-temperature atmosphere.
以下、本発明の好ましい実施形態について説明する。 Hereinafter, preferred embodiments of the present invention will be described.
本発明は、有底円筒状に形成された負極缶と有底円筒状に形成された正極缶との間に環状のガスケットを介在させ、前記正極缶の開口部を内側にかしめて正極、負極、セパレータ、及び有機電解液からなる発電要素を密封した偏平形有機電解液電池であって、前記セパレータはガラス繊維を主成分とし、前記有機電解液はリチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）とイミダゾールを含み、イミダゾールの含有量は、リチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）とイミダゾールの総量に対して５〜３５ｍｏｌ％であることを特徴とする。 In the present invention, an annular gasket is interposed between a negative electrode can formed in a bottomed cylindrical shape and a positive electrode can formed in a bottomed cylindrical shape, and an opening of the positive electrode can is caulked inward to form a positive electrode and a negative electrode , A separator, and a flat organic electrolyte battery in which a power generation element composed of an organic electrolyte is sealed, wherein the separator is mainly composed of glass fiber, and the organic electrolyte is lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) and imidazole , and the content of imidazole is 5 to 35 mol% with respect to the total amount of lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) and imidazole. And
偏平形有機電解液電池において、ガラス繊維を主成分とするセパレータと、イミダゾールと、ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 とを組み合わせることにより、高温多湿環境下でも、ガラスセパレータの劣化反応が抑制され、優れた信頼性と放電性能を確保することが可能となる。 In a flat organic electrolyte battery, by combining a separator mainly composed of glass fibers, imidazole, and LiN (CF 3 SO 2 ) 2 , the degradation reaction of the glass separator is suppressed even in a high temperature and high humidity environment. It is possible to ensure excellent reliability and discharge performance.
詳細な機構については定かではないが、ガラス繊維のＳｉＯ2表面にイミダゾールが化学的な親和性によって吸着しており（ガラス繊維の酸素とイミダゾールのＮＨ基の水素との水素結合）、また、ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 とイミダゾールがイオン性液体に近いような生成物を形成してガラス繊維を主成分とするセパレータの近傍への水分の移動を抑制することと、フッ酸の生成を抑制している、もしくは生成したフッ酸をイミダゾールがトラップして反応を阻害していると思われる。 Although the detailed mechanism is not clear, imidazole is adsorbed on the SiO 2 surface of the glass fiber due to chemical affinity (hydrogen bond between oxygen of the glass fiber and hydrogen of NH group of imidazole), and LiN (CF 3 SO 2 ) 2 and imidazole form a product that is close to an ionic liquid to suppress the movement of moisture to the vicinity of the separator mainly composed of glass fiber, and to suppress the generation of hydrofluoric acid It seems that imidazole traps the hydrofluoric acid produced or produced to inhibit the reaction.
リチウム塩としてＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 を含有する有機電解液に、イミダゾールを添加すると液の色が透明から薄いピンク色に変化し、何らかの反応または錯イオン形成などをしているのは明らかである。詳細については不明である。 The organic electrolyte containing LiN (CF 3 SO 2) 2 as a lithium salt, the clear color of the liquid upon addition of imidazole was changed to pale pink transparent, and the like any reaction or complex ions formed It is. Details are unknown.
また、スルホン基とイミド結合を有するアニオンであるＮ（ＣＦ3ＳＯ2）2 -などからなるイオン性液体は一般的に疎水性を示すことから、上記のイミダゾールとＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 と関係する生成物も同様な疎水性を発現するものと推察される。 In addition, an ionic liquid composed of N (CF 3 SO 2 ) 2 — or the like, which is an anion having a sulfone group and an imide bond, generally exhibits hydrophobicity. Therefore, the above imidazole and LiN (CF 3 SO 2 ) 2 the product associated with is also inferred that express similar hydrophobicity.
ガラス繊維を主成分とするセパレータに上記の両方を組み合わせない場合には、高温多湿環境でセパレータは酷く劣化することから、ガラス繊維を主成分とするセパレータと、イミダゾールと、ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2、の３つの組合せが非常に重要である。 When both of the above are not combined with a separator mainly composed of glass fiber, the separator deteriorates severely in a high-temperature and high-humidity environment. Therefore, a separator mainly composed of glass fiber, imidazole, LiN (CF 3 SO 2 2 ) The combination of 3 is very important.
イミダゾールの電池内部への添加方法としては、電解液または正極・負極への添加があり、より効果的なのが電解液への添加である。添加したイミダゾールは、電解液に溶解することによって電解液、正極、負極、セパレータの発電要素の任意の部位に拡散して存在する。 As a method for adding imidazole to the inside of the battery, there is an addition to the electrolytic solution or the positive electrode / negative electrode, and the more effective addition is to the electrolytic solution. The added imidazole is diffused and present in any part of the power generation element of the electrolytic solution, the positive electrode, the negative electrode, and the separator by dissolving in the electrolytic solution.
イミダゾールの添加量は、ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 とイミダゾールの総量に対して５ｍｏｌ％未満になると相互作用の効果が薄れて、高温多湿環境下でのガラスセパレータの劣化が起こりやすくなる。また、３５ｍｏｌ％を超えると電解液のリチウムイオンの導電率が小さくなるため、放電性能が低下してしまう。 When the amount of imidazole added is less than 5 mol% with respect to the total amount of LiN (CF 3 SO 2 ) 2 and imidazole, the effect of the interaction is weakened, and the glass separator is likely to be deteriorated in a high-temperature and high-humidity environment. On the other hand, if it exceeds 35 mol%, the lithium ion conductivity of the electrolytic solution is reduced, and the discharge performance is degraded.
リチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ3ＳＯ2）2）は
、フッ素を含有するＬｉＰＦ6、ＬｉＢＦ4塩に比べて水分に対して反応性が低く、耐熱性についても優れている。リチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）の濃度としては０．７５〜１．５ｍｏｌ／ｌが好ましい。
Lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) is less reactive to moisture and excellent in heat resistance than LiPF 6 and LiBF 4 salts containing fluorine. The concentration of lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) 2 ) is preferably 0.75 to 1.5 mol / l .
電解液を構成する有機溶媒としてはγ−ブチロラクトン、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、スルホラン、３−メチルスルホラン、テトラグライムなどの高沸点・高粘度溶媒の単独または混合系と、さらにモノグライム、ジグライム、トリグライムなどのグライム類、ジメチルカーボネート、エチルメチルカーボネート、ジエチルカーボネートなどの鎖状炭酸エステルなどの低粘度溶媒を混合したものなどが好ましい。 The organic solvent constituting the electrolyte includes γ-butyrolactone, ethylene carbonate, propylene carbonate, butylene carbonate, sulfolane, 3-methylsulfolane, tetraglyme and other high-boiling / high-viscosity solvents, or monoglyme and diglyme. A mixture of a low-viscosity solvent such as glymes such as triglyme and a chain carbonate such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate is preferred.
ガラス繊維を主体とするセパレータの目付け重量としては６０〜８０ｇ／ｍ2で、厚みとしては０．３ｍｍ以上が一般的である。放電特性を向上するためには低目付け重量として厚みを薄することが必要となる。ガラス繊維単体では目付け重量が６０ｇ／ｍ2以下にすると強度低下し、電池内部での正負極の膨張収縮に伴う応力変化に対応できずに内部短絡する危険性がある。ガラス繊維を主体にバインダーとしてアクリロニトリル重合体のアクリル繊維、ポリメタクリル酸メチル、ポリアクリル酸などを３〜２５重量％配合することでセパレータに十分な強度が確保でき、目付け重量３０〜５０ｇ／ｍ2で、厚みとしては０．１〜０．２ｍｍのものを用いることができる。 The weight of the separator mainly composed of glass fibers is generally 60 to 80 g / m 2 and the thickness is generally 0.3 mm or more. In order to improve the discharge characteristics, it is necessary to reduce the thickness as a low weight per unit area. If the weight per unit weight of glass fiber is 60 g / m 2 or less, the strength decreases, and there is a risk of internal short circuit without being able to cope with the stress change accompanying the expansion and contraction of the positive and negative electrodes inside the battery. By blending 3 to 25% by weight of acrylic fiber of polyacrylonitrile polymer, polymethyl methacrylate, polyacrylic acid, etc. with glass fiber as the main binder, sufficient strength can be secured in the separator, and the basis weight is 30 to 50 g / m 2. Thus, a thickness of 0.1 to 0.2 mm can be used.
正極材料としては弗化黒鉛、酸化銅、硫化銅、硫化鉄、二酸化マンガンなどの一次電池用の活物質、五酸化バナジウム、二硫化チタン、五酸化ニオブ、三酸化モリブデン、オキシ水酸化鉄、オキシ水酸化ニッケル、リチウムマンガン複合酸化物などの３Ｖ級の二次電
池用活物質、また、リチウムを含有するコバルト酸リチウム、ニッケル酸リチウム、スピネル型のマンガン酸リチウムなどの４Ｖ級二次電池用活物質が挙げられる。
The positive electrode materials include active materials for primary batteries such as graphite fluoride, copper oxide, copper sulfide, iron sulfide, manganese dioxide, vanadium pentoxide, titanium disulfide, niobium pentoxide, molybdenum trioxide, iron oxyhydroxide, oxy Active materials for 3V class secondary batteries such as nickel hydroxide and lithium manganese composite oxide, and actives for 4V class secondary batteries such as lithium cobaltate, lithium nickelate and spinel type lithium manganate containing lithium Substances.
負極材料としては金属リチウム、Ｓｉ−Ｌｉ、Ｓｎ−Ｌｉ、Ｇｅ−Ｌｉ、Ａｌ−Ｌｉなどのリチウム合金、黒鉛、難黒鉛性炭素などの炭素系材料、一酸化ケイ素、一酸化スズ、一酸化コバルトなどを主体とするリチウムに対して１Ｖ未満で反応する酸化物、スピネル型のリチウムチタン酸化物、五酸化ニオブ、二酸化タングステンなどのリチウムに対して１Ｖ以上で反応する酸化物が挙げられる。 Negative electrode materials include lithium alloys such as metallic lithium, Si-Li, Sn-Li, Ge-Li, and Al-Li, carbon-based materials such as graphite and non-graphitizable carbon, silicon monoxide, tin monoxide, and cobalt monoxide. Examples thereof include oxides that react at less than 1 V with lithium mainly composed of, and the like, oxides that react with lithium at 1 V or more, such as spinel lithium titanium oxide, niobium pentoxide, and tungsten dioxide.
正極と負極については様々な組合せが可能であり、一次電池、二次電池ともに本発明を用いることが可能である。 Various combinations of the positive electrode and the negative electrode are possible, and the present invention can be used for both primary batteries and secondary batteries.
ガスケットは、ポリフェニレンスルフィド（ＰＰＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、テトラフルオロエチレン・パーフルオロアルコキシエチレン共重合体（ＰＦＡ）などの樹脂が好ましく、さらに強度を向上させる目的で前記樹脂に充填材としてガラスや、チタン酸カルシウムなどの無機繊維などを用いたものも好ましい。 The gasket is preferably a resin such as polyphenylene sulfide (PPS), polyether ether ketone (PEEK), tetrafluoroethylene / perfluoroalkoxyethylene copolymer (PFA), and the resin is used as a filler for the purpose of further improving the strength. Those using glass or inorganic fibers such as calcium titanate are also preferred.
以上の構成とすることにより、高温多湿環境下での信頼性の確保と低温雰囲気下での高負荷放電特性に優れる偏平形有機電解液電池を提供できる。 By adopting the above configuration, it is possible to provide a flat organic electrolyte battery that ensures reliability in a high-temperature and high-humidity environment and is excellent in high-load discharge characteristics in a low-temperature atmosphere.
以下、本発明の偏平形有機電解液電池について、実施例に基づいて具体的に説明する。 Hereinafter, the flat organic electrolyte battery of the present invention will be specifically described based on examples.
（実施例１）
図１は、本発明の実施例に係る偏平形有機電解液電池の断面図であり、厚さ５ｍｍ、直径２４ｍｍとした。図１において、発電要素を収容するコイン型の電池容器は、耐食性に優れたステンレス鋼からなる正極缶５と、同様にステンレス鋼の負極缶１と、ガスケット６により構成され、正極缶５の開口部を内側にかしめることによって、発電要素が内部に密封される。ガスケット６は正極缶５と負極缶１とを絶縁する機能に加え、物理的に発電要素を液密的に電池容器内に密閉するための機能を有している。ガスケット６には、ポリフェニレンスルフィド（ＰＰＳ）樹脂からなるものを使用した。このガスケット６と正極缶５及び負極缶１とガスケット６との間にブチルゴムをトルエンで希釈した溶液を塗布し、トルエンを蒸発させることによりブチルゴム膜からなるシーラント８とした。
Example 1
FIG. 1 is a cross-sectional view of a flat organic electrolyte battery according to an embodiment of the present invention, and has a thickness of 5 mm and a diameter of 24 mm. In FIG. 1, a coin-type battery container that houses a power generation element includes a positive electrode can 5 made of stainless steel having excellent corrosion resistance, a stainless steel negative electrode can 1, and a
正極３は、電解二酸化マンガン（ＥＭＤ）を活物質に、導電剤としてカーボンブラック及び結着剤としてフッ素樹脂粉末を９０：５：５の質量比率で混合し、ペレット状に成型した後、２５０°Ｃ中で１２時間乾燥したものである。得られたペレット状の正極材料は、正極缶５の内面にカーボン塗料を塗布することで形成された正極集電体７に接触するようにしてある。一方、負極２は、リチウムアルミニウム（Ａｌ−Ｌｉ）合金を用い、負極缶１に圧着した。また、正極３と負極２との間に配されるセパレータ４には、目付け重量が４５ｇ／ｍ2で繊維径が０．３〜１μｍ、繊維長が３００〜１０００μｍのものでガラス繊維を主体としバインダーにアクリル繊維を１５重量％含むものを使用した。電解液はプロピレンレンカーボネートとジグライムとの体積比１：１の混合溶媒にＬｉＮ（ＣＦ3ＳＯ2）2を１．０ｍｏｌ／ｌ溶解させたものに、イミダゾールをイミダゾールとＬｉＮ（ＣＦ3ＳＯ2）2の総量に対し２５ｍｏｌ％含有するように添加したものを用いた。このようにして得られた電池を電池Ａとした。
The
電池Ａのイミダゾールの含有量２５ｍｏｌ％を含有量５ｍｏｌ％〜３５ｍｏｌ％の範囲で変化させた以外は、電池Ａと同様にして作製した電池を電池Ｂ〜Ｄとした。 Batteries B to D were produced in the same manner as the battery A except that the imidazole content of the battery A was changed from 25 mol% to a content of 5 mol% to 35 mol%.
電池Ａの溶質のＬｉＮ（ＣＦ3ＳＯ2）2に代えてＬｉＮ（Ｃ2Ｆ5ＳＯ2）2を用いた以外
は電池Ａと同様にして作製した電池を電池Ｅとした。
A battery E was prepared in the same manner as battery A except that LiN (C 2 F 5 SO 2 ) 2 was used instead of LiN (CF 3 SO 2 ) 2 as the solute of battery A.
電池Ａの溶質のＬｉＮ（ＣＦ3ＳＯ2）2に代えてＬｉＮ（Ｃ4Ｆ9ＳＯ2）（ＣＦ3ＳＯ2）を用いた以外は電池Ａと同様にして作製した電池を電池Ｆとした。 Battery F was prepared in the same manner as Battery A except that LiN (C 4 F 9 SO 2 ) (CF 3 SO 2 ) was used instead of LiN (CF 3 SO 2 ) 2 as the solute of battery A. .
電池Ａのイミダゾールの含有量２５ｍｏｌ％を無添加（０ｍｏｌ％）、含有量３ｍｏｌ％、及び含有量４０ｍｏｌ％とした以外は、電池Ａと同様にして作製した電池を電池１、２、３とした。
The batteries produced in the same manner as battery A were designated as
電池Ａの溶質のリチウム塩ＬｉＮ（ＣＦ3ＳＯ2）2に代えてＬｉＰＦ6を用いた以外は電池Ａと同様にして作製した電池を電池４とした。
A battery produced in the same manner as battery A except that LiPF 6 was used in place of the solute lithium salt LiN (CF 3 SO 2 ) 2 of battery A was designated as
本発明にかかる電池Ａ〜Ｆと比較例となる電池１〜４について、正極の二酸化マンガンの理論容量に対して１０％容量を５ｍＡの定電流放電を行った後に、１００℃で２４０時間貯蔵を行う高温保存試験と、８５℃９０％で２４０時間貯蔵を行う高温多湿保存試験を行い、それぞれの保存試験の前後で、−４０℃の環境下で３ｍＡの電流値で放電させ、放電開始から１秒後の閉回路電圧（ＣＣＶ）を測定した。その結果を（表１）に示す。
The batteries A to F according to the present invention and the
本発明に係る電池Ａ〜Ｆについては、高温保存試験後及び高温多湿保存試験後でも低温での閉回路電圧（ＣＣＶ）の極端な低下がなく、優れた低温放電特性を維持することができた。イミダゾールを添加していない電池１、含有量の少ない電池２、及び溶質にＬｉＰＦ6を用いた電池４では高温多湿保存試験後の低温での閉回路電圧（ＣＣＶ）の著しい低下が見られた。イミダゾールの含有量の多い電池３で試験前から低温での閉回路電圧（ＣＣＶ）が他の電池に比べて低レベルであった。
Regarding the batteries A to F according to the present invention, the closed circuit voltage (CCV) at a low temperature was not drastically decreased even after the high temperature storage test and the high temperature and humidity storage test, and excellent low temperature discharge characteristics could be maintained. . In
実施例では、二酸化マンガンリチウム一次電池について述べたが、これに限定されることなく、フッ化黒鉛リチウム一次電池などの一次電池、４Ｖ級のコバルト酸リチウムと黒鉛を組みあわせたリチウムイオン二次電池や、五酸化バナジウムとリチウムアルミニウム合金の組合せや、リチウム含有マンガン酸化物ちリチウムアルミニウム合金を組合せた３Ｖ級のリチウム二次電池や、コバルト酸リチウムとリチウムチタン酸化物の組合わせや、
五酸化ニオブとリチウムアルミニウム合金を組合せた２．５Ｖ級のリチウム二次電池についても同様の効果が得られる。
In the embodiments, a lithium manganese dioxide primary battery has been described. However, the present invention is not limited to this, but a primary battery such as a lithium fluoride graphite primary battery or a lithium ion secondary battery in which 4V-class lithium cobaltate and graphite are combined. Or a combination of vanadium pentoxide and a lithium aluminum alloy, a lithium secondary manganese battery containing a lithium-containing manganese oxide or a lithium aluminum alloy, a combination of lithium cobalt oxide and lithium titanium oxide,
The same effect can be obtained with a 2.5 V class lithium secondary battery in which niobium pentoxide and a lithium aluminum alloy are combined.
本発明は、有底円筒状に形成された負極缶と有底円筒状に形成された正極缶との間に環状のガスケットを介在させ、前記正極缶の開口部を内側にかしめて正極、負極、セパレータ、及び有機電解液からなる発電要素を密封した偏平形有機電解液電池において、ガラス繊維を主成分とするセパレータと、リチウム塩としてリチウムビスパーフルオロメチルスルホニルイミド（ＬｉＮ（ＣＦ 3 ＳＯ 2 ） 2 ）を含む有機電解液と、イミダゾールとを組み合わせることで、高温多湿環境下での信頼性と低温雰囲気下での高負荷放電特性に優れる偏平形有機電解液電池を提供することができる。 In the present invention, an annular gasket is interposed between a negative electrode can formed in a bottomed cylindrical shape and a positive electrode can formed in a bottomed cylindrical shape, and an opening of the positive electrode can is caulked inward to form a positive electrode and a negative electrode In a flat organic electrolyte battery in which a power generation element composed of a separator and an organic electrolyte is sealed, a separator mainly composed of glass fiber and lithium bisperfluoromethylsulfonylimide (LiN (CF 3 SO 2 ) as a lithium salt By combining the organic electrolyte containing 2 ) with imidazole, it is possible to provide a flat organic electrolyte battery excellent in reliability under a high temperature and humidity environment and high load discharge characteristics in a low temperature atmosphere.
また、今後の自動車の安全性を確保するためのタイヤの空気圧センサーなどの電源としての展開が可能となり、極めて有用である。 In addition, it can be deployed as a power source for tire pressure sensors to ensure the safety of future automobiles, which is extremely useful.
１ 負極缶
２ 負極
３ 正極
４ セパレータ
５ 正極缶
６ ガスケット
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| JP6056076B2 (en) * | 2012-12-10 | 2017-01-11 | 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． | Electrochemical devices |
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| US20230387379A1 (en) * | 2020-11-20 | 2023-11-30 | Nippon Telegraph And Telephone Corporation | Primary Battery |
| WO2022138085A1 (en) * | 2020-12-25 | 2022-06-30 | 日本ゼオン株式会社 | Binder composition for non-aqueous secondary battery negative electrode, slurry composition for non-aqueous secondary battery negative electrode, non-aqueous secondary battery negative electrode and method for producing same, and non-aqueous secondary battery |
| US20220311052A1 (en) | 2021-03-24 | 2022-09-29 | Lg Energy Solution, Ltd. | Non-Aqueous Electrolyte Solution for Lithium Secondary Battery and Lithium Secondary Battery Comprising Same |
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