JPH012260A - Inorganic non-aqueous electrolyte battery - Google Patents
Inorganic non-aqueous electrolyte batteryInfo
- Publication number
- JPH012260A JPH012260A JP62-156948A JP15694887A JPH012260A JP H012260 A JPH012260 A JP H012260A JP 15694887 A JP15694887 A JP 15694887A JP H012260 A JPH012260 A JP H012260A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic compound
- aqueous electrolyte
- electrolyte battery
- inorganic non
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 16
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 58
- 150000001491 aromatic compounds Chemical class 0.000 claims description 43
- 239000003792 electrolyte Substances 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RDQSIADLBQFVMY-UHFFFAOYSA-N 2,6-Di-tert-butylbenzoquinone Chemical compound CC(C)(C)C1=CC(=O)C=C(C(C)(C)C)C1=O RDQSIADLBQFVMY-UHFFFAOYSA-N 0.000 claims description 4
- RAASUWZPTOJQAY-UHFFFAOYSA-N Dibenz[a,c]anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C3=CC=CC=C3C2=C1 RAASUWZPTOJQAY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 3
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 claims description 3
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 2
- 229940076442 9,10-anthraquinone Drugs 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 5
- 208000028659 discharge Diseases 0.000 description 38
- 239000008151 electrolyte solution Substances 0.000 description 31
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 28
- SOZVEOGRIFZGRO-UHFFFAOYSA-N [Li].ClS(Cl)=O Chemical compound [Li].ClS(Cl)=O SOZVEOGRIFZGRO-UHFFFAOYSA-N 0.000 description 23
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 15
- 229910052744 lithium Inorganic materials 0.000 description 15
- -1 polypropylene Polymers 0.000 description 9
- 239000004709 Chlorinated polyethylene Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003115 supporting electrolyte Substances 0.000 description 5
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- CVQSWZMJOGOPAV-UHFFFAOYSA-N 2,3-dihydrothiochromen-4-one Chemical compound C1=CC=C2C(=O)CCSC2=C1 CVQSWZMJOGOPAV-UHFFFAOYSA-N 0.000 description 2
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 description 2
- RKZDZWJDQTZDLD-UHFFFAOYSA-N 4h-cyclopenta[def]phenanthrene Chemical compound C1=CC=C2CC3=CC=CC4=CC=C1C2=C34 RKZDZWJDQTZDLD-UHFFFAOYSA-N 0.000 description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- HAPOJKSPCGLOOD-UHFFFAOYSA-N Benzo[b]fluorene Chemical compound C1=CC=C2C=C3CC4=CC=CC=C4C3=CC2=C1 HAPOJKSPCGLOOD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- MBAIEZXRGAOPKH-UHFFFAOYSA-N 1,2,3,6,7,8-hexahydropyrene Chemical compound C1CCC2=CC=C3CCCC4=CC=C1C2=C43 MBAIEZXRGAOPKH-UHFFFAOYSA-N 0.000 description 1
- KWQOKLILKYKIQH-UHFFFAOYSA-N 1,2-dichlorofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=C(Cl)C(Cl)=CC=C3C2=C1 KWQOKLILKYKIQH-UHFFFAOYSA-N 0.000 description 1
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 1
- VZLJXBDMGPULPG-UHFFFAOYSA-N 2,4,6-trichloro-1-benzothiophene Chemical compound C1=C(Cl)C=C2SC(Cl)=CC2=C1Cl VZLJXBDMGPULPG-UHFFFAOYSA-N 0.000 description 1
- SBSSGOZNBNRZAQ-UHFFFAOYSA-N 2,4,7-trichlorodibenzothiophene Chemical compound C1=C(Cl)C=C2C3=CC=C(Cl)C=C3SC2=C1Cl SBSSGOZNBNRZAQ-UHFFFAOYSA-N 0.000 description 1
- LBMHPHUSGIEGHJ-UHFFFAOYSA-N 2-phenyl-1-benzothiophene Chemical compound S1C2=CC=CC=C2C=C1C1=CC=CC=C1 LBMHPHUSGIEGHJ-UHFFFAOYSA-N 0.000 description 1
- OIHMNLXCCZIWKV-UHFFFAOYSA-N 4-phenylthiophene Chemical compound S1C=CC(C=2C=CC=CC=2)=[C]1 OIHMNLXCCZIWKV-UHFFFAOYSA-N 0.000 description 1
- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 description 1
- LUBXLGUQZVKOFP-UHFFFAOYSA-N 9-phenylanthracene Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=CC2=CC=CC=C12 LUBXLGUQZVKOFP-UHFFFAOYSA-N 0.000 description 1
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- FMMWHPNWAFZXNH-UHFFFAOYSA-N ERM-AC051 Natural products C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- 229910013470 LiC1 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- VEGOPIRPQIZFRD-UVHWXNHCSA-N [(2s,3r,4r,5r,6s)-3,4,5-trihydroxy-6-methyloxan-2-yl] (e)-3-(4-hydroxyphenyl)prop-2-enoate Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC(=O)\C=C\C1=CC=C(O)C=C1 VEGOPIRPQIZFRD-UVHWXNHCSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- JTRPLRMCBJSBJV-UHFFFAOYSA-N benzonaphthacene Natural products C1=CC=C2C3=CC4=CC5=CC=CC=C5C=C4C=C3C=CC2=C1 JTRPLRMCBJSBJV-UHFFFAOYSA-N 0.000 description 1
- IFVTZJHWGZSXFD-UHFFFAOYSA-N biphenylene Chemical group C1=CC=C2C3=CC=CC=C3C2=C1 IFVTZJHWGZSXFD-UHFFFAOYSA-N 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- CUIWZLHUNCCYBL-UHFFFAOYSA-N decacyclene Chemical compound C12=C([C]34)C=CC=C4C=CC=C3C2=C2C(=C34)C=C[CH]C4=CC=CC3=C2C2=C1C1=CC=CC3=CC=CC2=C31 CUIWZLHUNCCYBL-UHFFFAOYSA-N 0.000 description 1
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- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
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- 239000004021 humic acid Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
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Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はオキシハロゲン化物を正極活物質および電解液
の溶媒とし、アルカリ金属を負極活物質とする無機非水
電解液電池に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an inorganic non-aqueous electrolyte battery in which an oxyhalide is used as a positive electrode active material and an electrolyte solvent, and an alkali metal is used as a negative electrode active material.
塩化チオニル−リチウム電池で代表されるような塩化チ
オニル、塩化スルフリル、塩化ホスホリルなどのオキシ
ハロゲン化物を正極活物質および電解液の溶媒とし、リ
チウム、ナトリウム、カリウムなどのアルカリ金属を負
極活物質とする無機非水電解’ａＴ１池では、その代表
的電池である塩化チオニル−リチウム電池を例にあげて
説明すると、正極活物質である塩化チオニルがリチウム
負極と直接接触しているため、リチウムｆ′ｔＶｉＡ上
に塩化リチウムの被膜が形成される。この塩化リチウム
被膜は形成当初は疎な被膜であるが、高温貯蔵または長
期間貯蔵した場合、緻密な被膜となって成長し、リチウ
ム負極の不働態化を引き起こすことになる。その結果、
この電池を高温ないしは長期間貯蔵した後に使用すると
、放電初期に電圧降下が生じ、所望の電圧値にまで達し
ないため、この電池を駆動電源として使用した機器が作
動できないという問題がある。しかも、このような放電
初期の電圧降下現象は、未放電の電池を貯蔵した場合の
みならず、電池をある程度使用してから貯蔵した場合に
も、その貯蔵ごとに繰り返し現れるという特異性がある
。Oxyhalides such as thionyl chloride, sulfuryl chloride, and phosphoryl chloride, as typified by thionyl chloride-lithium batteries, are used as the positive electrode active material and the solvent for the electrolyte, and alkali metals such as lithium, sodium, and potassium are used as the negative electrode active material. In an inorganic non-aqueous electrolytic 'aT1 cell, using a thionyl chloride-lithium battery as an example, which is a typical battery, thionyl chloride, which is a positive electrode active material, is in direct contact with a lithium negative electrode, so lithium f'tViA A coating of lithium chloride is formed on top. This lithium chloride film is a loose film at the beginning of formation, but when stored at high temperatures or for a long period of time, it grows into a dense film, causing passivation of the lithium negative electrode. the result,
If this battery is used after being stored at high temperatures or for a long period of time, a voltage drop will occur at the beginning of discharge and the desired voltage will not be reached, resulting in a problem that devices using this battery as a driving power source will not be able to operate. Moreover, such a voltage drop phenomenon at the initial stage of discharge has the peculiarity that it repeatedly appears not only when an undischarged battery is stored, but also when the battery is stored after being used for some time.
そのため、従来からも、特開昭６０−２４９２５３号公
報に示されるように、電解液に塩素化ポリプロピレンを
添加して放電初期の電圧降下を抑制するこや、特開昭６
１−１９０８６３号公報に示されるように、電解液にポ
リエチレンオキサイドを添加して放電初期の電圧降下を
抑制することなどが提案されている。Therefore, as shown in Japanese Unexamined Patent Publication No. 60-249253, chlorinated polypropylene has been added to the electrolytic solution to suppress the voltage drop at the initial stage of discharge.
As disclosed in Japanese Patent No. 1-190863, it has been proposed to add polyethylene oxide to the electrolytic solution to suppress the voltage drop at the initial stage of discharge.
しかしながら、上記のように電解液に塩素化ポリエチレ
ンやポリエチレンオキサイドを添加した場合は、電池が
例えば防犯機器の主電源として使用される場合のように
０．１ｍＡ／ｃ＋！−０，５ｍＡ／ｃｄ程度の比較的小
さい電流で使用される場合には、放電初期の電圧降下を
抑制できるが、例えばガスメータや電力メータなどの主
駆動電源として使用する場合のように１ ｍＡ／ｃｄ
〜３０１ＴＩＡ１０１１程度の大電流を要する場合には
、放電初期の電圧降下を充分に防止することができなか
った。However, when chlorinated polyethylene or polyethylene oxide is added to the electrolyte as described above, the battery voltage is 0.1 mA/c+, as is the case when the battery is used as the main power source for security equipment, for example. When used with a relatively small current of about -0.5 mA/cd, the voltage drop at the initial stage of discharge can be suppressed, but for example when used as a main drive power source for a gas meter or electricity meter, a current of 1 mA/cd cd
When a large current of about 301TIA1011 is required, it was not possible to sufficiently prevent a voltage drop at the initial stage of discharge.
本発明は、上記従来製品が持っていた高温ないしは長期
間貯蔵後の大電流放電で放電初期に電圧降下が生しると
いう問題点を解決し、高温ないしは長時間貯蔵後の大電
流放電においても放電初期の電圧降下が生じない無機非
水電解液電池を提供することを目的とする。The present invention solves the problem of the voltage drop occurring at the initial stage of discharge due to large current discharge after high temperature or long-term storage, which the conventional products had. It is an object of the present invention to provide an inorganic non-aqueous electrolyte battery that does not cause a voltage drop in the initial stage of discharge.
本発明は、電解液に芳香族化合物を添加することにより
、高温ないし長期間貯蔵後の大電流放電においても、放
電初期の電圧降下が生じないようにしたものである。In the present invention, by adding an aromatic compound to the electrolytic solution, a voltage drop does not occur at the initial stage of discharge even in high-current discharge after high temperature or long-term storage.
すなわち、電解液に芳香族化合物を添加することによっ
て、リチウム負極表面に形成される塩化リチウム被膜が
非常に粗な膜となり、大電流放電 、時においても、リ
チウム負極から電解液へのリチウムイオンの拡散が塩化
リチウム被膜によって阻害されることなくスムーズに行
われるようになり、濃度分極が小さくなって、放電初期
の電圧降下が防止されるようになるのである。In other words, by adding aromatic compounds to the electrolyte, the lithium chloride film formed on the surface of the lithium negative electrode becomes a very rough film, and even during large current discharges, lithium ions may not be transferred from the lithium negative electrode to the electrolyte. Diffusion is now carried out smoothly without being inhibited by the lithium chloride film, concentration polarization is reduced, and voltage drop at the initial stage of discharge is prevented.
上記のように芳香族化合物を電解液に添加することによ
って、リチウム負極上に形成される被膜が粗な膜になる
理由は、現在のところ必ずしも明確ではないが、リチウ
ム負極表面への塩化リチウム被膜の形成時に芳香族化合
物が塩化リチウム被膜中にとり込まれるか、あるいは塩
化リチウム被膜の成長時に芳香族化合物が何らかの影響
を与えて塩化リチウム被膜を粗にすることによるものと
考えられる。The reason why the film formed on the lithium negative electrode becomes rough when an aromatic compound is added to the electrolyte as described above is not clear at present, but the lithium chloride film on the surface of the lithium negative electrode This is thought to be due to the fact that aromatic compounds are incorporated into the lithium chloride film during the formation of the lithium chloride film, or that the aromatic compounds have some influence during the growth of the lithium chloride film and roughen the lithium chloride film.
本発明において、芳香族化合物とは芳香族炭化水素およ
びその各種誘導体をいい、このような芳香族化合物とし
ては、例えば次に示すものがあげられる。なお、芳香族
化合物の例示にあたっては、英語名とその構造式を付記
する。In the present invention, aromatic compounds refer to aromatic hydrocarbons and various derivatives thereof, and examples of such aromatic compounds include the following. In addition, when illustrating the aromatic compound, the English name and its structural formula are added.
ヘンジチオフェン（Ｂｅｎｚｏｔｈｉｏｐｈｅｎｅ）ジ
ヘンゾチオフエン（Ｄｉｂｅｎｚｏｔｈｉｏｐｈｅｎｅ
）１．２−ベンゾジフェニレンサルファイド（１，２−
Ｂｅｎｚ。Benzothiophene
)1.2-benzodiphenylene sulfide (1,2-
Benz.
ｄｉｐｈｅｎｙｌｅｎｅ ５ｕｌｆｉｄｅ）チアンスレ
ン（Ｔｈｉａｎｔｈｒｅｎｅ）チオキサンセン−９−オ
ン（Ｔｈｉｏｘａｎｔｈｅｎ−９−ｏｎｅ）２−フェニ
ル−１，３−ジチアン（２−Ｐｈｅｎｙｌ−１＋３−ｄ
ｉｔｈｉａｎｅ）チオクロマン−４−オン（Ｔｈｉｏｃ
ｈｒｏ＊ａｎ−４−ｏｎｅ）２−フェニルベンゾチオフ
ェン（２−Ｐｈｅｎｙｌｂｅｎｚｏｔｈｉｏｐｈｅｎｅ
）４−フェニルチオフヱン（４−Ｐｈｅｎｙｌｔｈｉｏ
ｐｈｅｎｅ）ジフェニルジサルファイド（Ｄｉｐｈｅｎ
ｙｌ ｄｉｓｕｌｒｉｄｅ）２．４．６−ドリクロロペ
ンゾチオフエン（２，４，６−Ｔｒｉｃｈｌｏｒｏｈｅ
ｎｚｏｔｈｉｏｐｈｅｎｅ）２．４．７− ）リクロロ
ジベンゾチオフェン（２＋ ＋Ｌ ７−Ｔｒｉｃｈｌｏ
ｒｏｄｉｂｅｎｚｏｔｈｉｏｐｈｅｎｅ）ベンゼン（［
１ｅｎｚｅｎｅ）
トルエン（Ｔｏ １ ｕｅｎｅ）
０−キシレン（ｏ −Ｘｙｌｅｎｅ）
ｍ−キシレン（ｍ −Ｘｙ １ｅｎｅ）ｐ−キシレン（
ｐ −Ｘ！／ Ｌｅｎｓ）２．０−外ターシャリブチル
ー１．４−ベン゛ノ゛キノン（２，６−Ｄｉ−ｔ−ｂｕ
ｔｙｌ−１，４−ｂｅｎｚｏｑｕｔｎｏｎｅ）ナフタレ
ン（Ｎａｐｈ ｔｈａ １ｅｎｅ）ビフェー’−ル（Ｂ
ｉｐｈｅｎｙｌ）
アントラセン（ＡｎＬｈｒａｃｅｎｅ）フェナントレン
（Ｐｈｅｎａｎｔｈｒｅｎｅ）１、畦ナフタリックアン
ハイドライド
（１，８−Ｎａｐｈｔｈａｌｉｅ ａｎｈｙｄｒｉｄｅ
）フルオランセン（Ｆ １ｕｏｒａｎ ｔｈｅｎｅ）ピ
レン（Ｐｙｒｅｎｅ）
アセナフテン（Ａｃｅｎａｐｈ ｔｈｅｎｅ）アントラ
キノン（＾ｎ ｔｈｒａｑｕ １ｎｏｎｅ）９、ｌＯ−
ジハイドロフエナンスレン
（９＋ １Ｏ−Ｄｉｈｙｄｒｏｐｈｅｎａｎｔｈｒｅｎ
ｅ）１．３，６．８．１０−ペンタクロロアントラセン
（１＋３＋６＋８＋ １Ｏ−Ｐｅｎｔａｃｈｌｏｒｏａ
ｎｔｈｒａｃｅｎｅ）２．５，８．１１−テトラクロロ
ナフタリン（２＋５＋８＋ １ｌ−Ｔｅｔｒａｃｈｌｏ
ｒｏｎａｐｈｔｈａｌｅｎｅ）２、４，６．８． ｔｏ
−ペンタクロロピレン（２，４，６，８，１Ｏ−Ｐｅｎ
ｔａｃｈｌｏｒｏｐｙｒｅｎｅ）
２．４．７− ）リクロロフルオレン（２，４，７−Ｔ
ｒｉｃｈｌｏｒｏｆｌｕｏｒｅｎｅ）Ｉ
２．４．７− ）ジクロロ−９−フルオレノン（２＋４
＋７−Ｔｒｉｃｈｌｏｒｏ−９−ｆｌｕｏｒｅｎｏｎｅ
）Ｉ
■
テトラクロロフタリックアンハイドライト（Ｔｅｔｒａ
ｃｈｌｏｒｏｐｈｔｈａｌｉｃ ａｎｈｙｄｒｉｄｅ）
ｌ ０
９、ＩＯ−アントラキノン（９，１０−八ｎｔｈｒａｑ
ｕｉｎｏｎｅ）す
２．７−ジクロロ−９−フルオレノン（２，７−Ｄｉｃ
ｈｌｏｒｏ−９−ｆｌｕｏｒｅｎｏｎｅ）
９．１０−ジクロロアントラセン（９，１Ｏ−Ｄｉｃｈ
ｌｏｒｏａｎＬｈｒＩｌｃｅｎｅ）
Ｉ
２．３，６．７−チトラクロロアントラキノン（２，３
，６，７−Ｔｅｔｒａｃｈｌｏｒｏａｎｔｈｒａｑｕｉ
ｎｏｎｅ）フルオレン（Ｆｌｕｏｒｅｎｅ）
ジベンゾフラン（Ｄｉｂｅｎｚｏｆｕｒａｎ）１．２，
３，６，７．８−ヘキサハイドロピレン（１，２，３，
６，７，８−Ｈｅｘａｈｙｄｒｏｐｙｒｅｎｅ）４ Ｈ
−シクロペンタ〔デフ〕フェナンスレン（４１１−Ｃｙ
ｃｌｏｐｅｎｔａ （ｄｅｆ ） ｐｈｅｎｉｎｔｈｒ
ｅｎｅ）２．３−ベンゾフルオレン（２＋３−Ｂｅｎｚ
ｏｆｌｕｏｒｅｎｅ）２．３−ベンズアントラセン（２
＋３−Ｂｅｎｚａｎｔｈｒａｃｅｎｅ）１．２−ベンズ
アントラセン（１＋２−ＢｅｎｚａｎＬｈｒａｃｅｎｅ
）９−フェニルフルオレン（９−Ｐｈｅｎｙｌｆｌｕｏ
ｒｅｎｅ）９−フェニルアントラセン（９−Ｉ’ｈｅｎ
ｙｌａｎｔｈｒａｃｃｎｅ）ペリレン（Ｐｅｒｙｌｅｎ
ｅ）
ペンタセン（Ｐｅｎ ｔａｃｅｎｅ）
トリフェニレン（Ｔｒｉｐｈｅｎｙｌｅｎｅ）ベンゾ（
ａ）ピレン（Ｂｅｎｚｏ Ｃａ ３ ｐｙｒｅｎｅ）９
．１０−ジフェニルアントラセン（９，１０−Ｄｉｐｈ
ｅｎｙｌａｎｔｈｒａｃｅｎｅ）
コローネン（Ｃｏｒｏｎｅｎｅ）
１，４．５．８−ナフタレンテトラカルボキシリックジ
アンヒドライド（１，４＋５＋８−Ｎａｐｈｔｈａｌｅ
ｎｅ ｔｅｔｒａｃａｒｂｏｘｙｌｉｃ ｄｉａｎｈｙ
ｄｒｉｄｅ）
１．４−ナフトキノン（１，４−Ｎａｐｈｔｈｏｑｕｉ
ｎｏｎｅ）６．１３−ペンタセンキノン（６，１３−Ｐ
ｅｎｔａｃｅｎｅｑｕｉｎｏｎｅ）キサンセン（Ｘａｎ
ｔｈｅｎｅ）
キサンソン（Ｘａｎｔｈｏｎｅ）
アセナフチンキノン（ＡｃｅｎａｐｈＬｈｅｎｅｑｕｉ
ｎｏｎｅ）アセナフチレン（Ａｃｅｎａｐｈｔｈｙｌｅ
ｎｅ）ベンゾ（ｇｈｉ）ペリレン（Ｂｅｎｚｏ （ｇｈ
ｉ） ｐｅｒｙｌｅｎｅ）５、１２−ナフタセンキノン
（５＋ １２−Ｎａｐｈｔｈａｃｅｎｅｑｕｉｎｏｎｅ
）１．２．３．４−ジベンズアントラセン（１，２，３
，４−ロ１ｂｅｎｚａｎｔｈｒａｃｅｎｅ）９，９°−
ビフルオレン（９＋ ９’−Ｂｉｆ １ｕｏｒｅｎｅ）
クリセン（Ｃｈｒｙｓｅｎｅ）
フルオレノン（Ｆ １ｕｏｒｅｎｏｎｅ）１．３−ペン
ゾジオキゾール（１，３−Ｂｅｎｚｏｄｉｏｘｏ！ｅ）
１．４−クリセンキノン（１＋４−Ｃｈｒｙｓｅｎｑｕ
ｉｎｏｎｅ）１．２．３，６，７，８．１１．１２−オ
クタハイドロベンゾ（ｅ）ピレン−９（ＩＯＨ）−オン
（１，２，３，６，７＋８．１１．１２−ＯｃＬａｈｙ
ｄｒｏｂｅｎｚｏ （ｅ ） ｐｙｒｅｎ−９（Ｌｏ
ｌｌ）−ｏｎｅ）１．２−ナフトキノン（１，２−Ｎａ
ｐｈｔｈｏｑｕｉｎｏｎｅ）３．４，９．１０−ペリレ
ンテトラ力ルポキシリノクジアンヒドライド（３＋ ４
＋ ９＋ １０−１’ｅｒｙｌｅｎｅＬｅｔｒａｃａｒ
ｂｏｘｙｌ ｉｃｄｉａｎｈｙｄｒｉｄｅ）
デカシクレン（Ｄｅｃａｃｙｃｌｅｎｅ）９．１０
ジハイドロヘンヅ〔α〕ピレン−７（８Ｈ）−オン（９
，１Ｏ−Ｄｉｈｙｄｒｏｂｅｎｚｏ （α〕ｐｙｒｅｎ
−７（８１１） −ｏｎｅ）ジハイドロクマリン（Ｄｉ
ｈｙｄｒｏｃｏｕｍａｒｉｎ）１．４．４ａ、９ａ−テ
トラハイドロアントラキノン（１，４，４ａ、９ａ−Ｔ
ｅＬｒａｈｙｄｒｏａｎｔｈｒａｑｕｉｎｏｎｅ）ヘン
ズ（ａ）アントラセン−７，１２−ジオン（Ｉｌｅｎｚ
［ａ ］ ］ａｎｔｈｒａｃｅｎ−７＋１２−
ｄｉｏｎｅ）ヘンズアンスロン（Ｂｅｎｚａｎ ｔｈｒ
ｏｎｅ）そして、上記例示の芳香族化合物の誘導体や、
ビチューメン類、フミン酸なども用いることができる。diphenylene 5ulfide) Thianthrene Thioxanthen-9-one (2-Phenyl-1+3-d
ithiane) thiochroman-4-one (Thioc
hro*an-4-one)2-Phenylbenzothiophene
) 4-Phenylthiophene (4-Phenylthio
phene) diphenyl disulfide (Diphen)
yl disulride) 2.4,6-Trichloropenzothiophene (2,4,6-Trichloride)
nzothiophene) 2.4.7- ) Lichlorodibenzothiophene (2+ +L 7-Trichlo
rhodibenzothiophene) benzene ([
1enzene) Toluene (To 1 uene) 0-xylene (o -Xylene) m-xylene (m -Xy 1ene) p-xylene (
p-X! / Lens) 2.0-extertiary butyl-1.4-benzenoquinone (2,6-Di-t-bu
tyl-1,4-benzoqutnone) Naphthalene (B
iphenyl) AnLhracene Phenanthrene 1, ridge naphthalie anhydride (1,8-Naphthalie anhydride)
) Fluoranthene Pyrene Acenaphthene Anthraquinone 9, lO-
Dihydrophenanthren (9+ 1O-Dihydrophenanthren)
e) 1.3,6.8.10-Pentachloroanthracene (1+3+6+8+ 1O-Pentachloroa
nthracene) 2.5,8.11-tetrachloronaphthalene (2+5+8+ 1l-Tetrachlo
ronaphthalene) 2, 4, 6.8. to
-Pentachloropyrene (2,4,6,8,1O-Pen
2.4.7- )lichlorofluorene (2,4,7-T
2.4.7-) dichloro-9-fluorenone (2+4
+7-Trichloro-9-fluorenone
) I ■ Tetrachlorophthalic anhydrite (Tetra
chlorophthalic anhydride)
l 0 9, IO-anthraquinone (9,10-8nthraq
uinone) 2,7-dichloro-9-fluorenone (2,7-Dic
hloro-9-fluorenone) 9.10-dichloroanthracene (9,1O-Dich
loroanLhrIlcene) I 2.3,6.7-Titrachloroanthraquinone (2,3
,6,7-Tetrachloroanthraqui
none) Fluorene Dibenzofuran 1.2,
3,6,7.8-hexahydropyrene (1,2,3,
6,7,8-Hexahydropyrene)4H
-cyclopenta[def]phenanthrene (411-Cy
clopenta (def) pheninthr
ene) 2,3-benzofluorene (2+3-Benz
offluorene)2,3-benzanthracene(2
+3-Benzanthracene) 1,2-Benzanthracene (1+2-Benzanthracene)
) 9-Phenylfluorene (9-Phenylfluorene)
rene) 9-phenylanthracene (9-I'hen
Perylene
e) Pentacene Triphenylene Benzo (
a) Pyrene (Benzo Ca 3 pyrene) 9
．． 10-diphenylanthracene (9,10-Diph
enylanthracene) Coronene 1,4.5.8-Naphthalenetetracarboxylic dianhydride (1,4+5+8-Naphthalene)
ne tetracarboxylic dianhy
1,4-Naphthoquinone (1,4-Naphthoqui)
none) 6,13-pentacenequinone (6,13-P
entacenequinone) xanthene (Xan
thene) Xanthone Acenaphthinquinone
none) acenaphthylene
ne) Benzo (gh) perylene
i) perylene) 5,12-naphthacenequinone (5+ 12-Naphthacenequinone
) 1.2.3.4-Dibenzanthracene (1,2,3
,4-ro1benzanthracene)9,9°-
Bifluorene (9+ 9'-Bif 1uorene)
Chrysene Fluorenone 1,3-Benzodioxo!e
1.4-Chrysenquinone (1+4-Chrysenqu
inone) 1.2.3,6,7,8.11.12-octahydrobenzo(e)pyren-9(IOH)-one (1,2,3,6,7+8.11.12-OcLahy
drobenzo (e) pyren-9 (Lo
ll)-one) 1,2-naphthoquinone (1,2-Na
phthoquinone) 3.4,9.10-perylenetetrapowerlupoxylinocdianhydride (3+ 4
+9+10-1'eryleneLetracar
boxyl icdianhydride) Decacyclene 9.10
Dihydrohendz[α]pyrene-7(8H)-one (9
,1O-Dihydrobenzo (α]pyren
-7(811) -one) Dihydrocoumarin (Di
hydrocoumarin) 1.4.4a,9a-tetrahydranthraquinone (1,4,4a,9a-T
(a) Anthracene-7,12-dione (Ilenz)
[a ] ] anthracen-7+12-
Dione) Benzan thr
one) and derivatives of the aromatic compounds exemplified above,
Bitumens, humic acids, etc. can also be used.
特にイオウを含有する芳香族化合物、とりわけヘンゼン
環とイオウを環内に含む複素環とが結合したイオウを含
有する芳香族化合物や、それらの塩素化物（それら芳香
族化合物の水素原子の一部または全部が塩素原子で置換
した塩素化物）、酸素を含有する芳香族化合物や、それ
らの塩素化物、ヘンゼン環を２個以上含む同素環式芳香
族化合物や、それらの塩素化物などが、放電初期の電圧
効果を防止する効果が優れていることから好ましい。な
お、イオウを含有する芳香族化合物や酸素を含有する芳
香族化合物では、ヘンゼン環が１個の場合でも好ましい
効果が発揮される。また、いずれの芳香族化合物におい
ても、ヘンゼン環の個数が多くなると電解液への？′８
解度が低下するので、いずれの芳香族化合物もヘンゼン
環を７個以下の範囲で含むものが好ましい。In particular, sulfur-containing aromatic compounds, in particular sulfur-containing aromatic compounds in which a Hensen ring and a heterocycle containing sulfur in the ring are bonded, and their chlorinated products (some of the hydrogen atoms of these aromatic compounds or At the initial stage of discharge, aromatic compounds containing oxygen, chlorinated products thereof, homocyclic aromatic compounds containing two or more Hensen rings, and chlorinated products thereof, etc. It is preferable because it has an excellent effect of preventing the voltage effect. Note that in the case of aromatic compounds containing sulfur and aromatic compounds containing oxygen, favorable effects are exhibited even when there is only one Hensen ring. Also, in any aromatic compound, if the number of Hensen rings increases, will it affect the electrolyte? '8
Since the solubility decreases, any aromatic compound preferably contains 7 or less Hensen rings.
なお、上記した芳香族化合物で塩素化されていないもの
は、電解液への添加により、オキンハロゲン化物によっ
て塩素化され、電解液中ではそれらの水素原子の一部ま
たは全部が塩素原子で置換した状態で存在するものと考
えられる。In addition, the above-mentioned aromatic compounds that are not chlorinated are chlorinated by oquine halides when added to the electrolyte, and in the electrolyte, some or all of their hydrogen atoms are replaced with chlorine atoms. It is thought that it exists in
これら芳香族化合物のＴＬ電解液の添加量としては、Ｉ
Ｘｌ０−’ ｍｏｌ／ ｊ！ 〜Ｉ Ｘｌ０−” ｍ
ｏｌ／ ｌの範囲、特にＩ Ｘｌ０−” ｍｏｌ／ １
．〜Ｉ Ｘｌ０−” ｍｏｌ／ ｌの範囲にするのが好
ましい。つまり、芳香族化合物の電解液への添加量が上
記範囲より少なくなると、負極表面上に形成する塩化リ
チウム被膜を粗にする効果が充分に発揮されず、また芳
香族化合物の電解液への添加量が上記範囲より多くなる
と、最初の放電時、つまり電池を製造してからまったく
放電をしていない未放電電池の放電をした時に、添加し
た芳香族化合物が放電特性に悪影啓を与え、放電初期の
電圧降下が生じたり、放電容量の低下が生じ、また芳香
族化合物の添加量の増加に応じて電池内に充填できる正
極活物質量が低下し、放電容量が低下するからである。The amount of these aromatic compounds added to the TL electrolyte is I
Xl0-' mol/j! 〜I Xl0−” m
ol/l range, especially I Xl0−” mol/1
．． It is preferable to set the amount in the range of ~IXl0-" mol/l. In other words, if the amount of the aromatic compound added to the electrolytic solution is less than the above range, the effect of roughening the lithium chloride film formed on the negative electrode surface will be reduced. If the amount of aromatic compound added to the electrolyte solution exceeds the above range, it will cause damage during the first discharge, that is, when discharging an undischarged battery that has not been discharged at all since the battery was manufactured. However, the added aromatic compounds adversely affect the discharge characteristics, resulting in a voltage drop at the beginning of discharge and a decrease in discharge capacity.Also, as the amount of aromatic compounds added increases, the positive electrode can be filled into the battery. This is because the amount of active material decreases and the discharge capacity decreases.
また、より大きな放電容量を得るには、正極の炭素多孔
質成形体の構成材料（正極材料）として、高比表面積品
、例えば１５（１０）ｎｆ／ｇ程度の炭素を用いること
が望ましい。このようにすれば結果的に正極の炭素多孔
質成形体の体積を減少させることが可能になり、正極活
物質としての塩化チオニルなどを電池内に多量に充填す
ることができるので、放電容量の増大を期することがで
きる。また、不純物を多量に含む炭素材料で成形した炭
素多孔質成形体を正極に用いる場合には、あらかしめ塩
化チオニルなどでｆｃ浄し、不純物を除去してから使用
することが好ましい。Furthermore, in order to obtain a larger discharge capacity, it is desirable to use a product with a high specific surface area, for example, carbon having a surface area of about 15 (10) nf/g, as the constituent material (positive electrode material) of the carbon porous molded body of the positive electrode. In this way, it becomes possible to reduce the volume of the carbon porous molded body of the positive electrode, and a large amount of thionyl chloride, etc., as the positive electrode active material can be filled into the battery, thereby increasing the discharge capacity. It can be expected to increase. In addition, when using a carbon porous molded body formed from a carbon material containing a large amount of impurities as a positive electrode, it is preferable to use it after fc cleaning with thionyl chloride or the like to remove impurities.
本発明の電池においで、工種活物質としては、例えば塩
化チオニル、塩化ホスホリル、塩化スルフリルなどの常
温で液体のオキシハロゲン化物が用いられる。これらオ
キシハロゲン化物は正極活物質であるとともに電解液の
溶媒として用いられ、電解液はこれらのオキシハロゲン
化物にＬｉＡｌＣｌ４ 、ＬｉＡｌＢｒ４、ＬｉＧａＣ
１４、ＬｉＢ、。ＣＩ、。などの支持電解質を溶解させ
ることによって調製される。なお、電解液の調製にあた
って、Ｌ ｒ Ａ Ｉ Ｃｌ ａなどの支持電解質はＬ
ｉＣ１とＡ Ｉ ＣＩ ３をオキシハロゲン化物に添加
しで電解液でＬ ｉ Ａ Ｉ Ｃｌ ａの形で存在（た
だし、イオン化してＬｉ＋とＡｌＣ１，−で存在）する
ようにしてもよいし、また芳香族化合物も電解液調製に
支持電解質とともに、あるいは支持電解質より先に添加
してもよい。In the battery of the present invention, the active material used is, for example, an oxyhalide that is liquid at room temperature, such as thionyl chloride, phosphoryl chloride, or sulfuryl chloride. These oxyhalides are used as positive electrode active materials and as solvents for the electrolyte, and the electrolyte contains these oxyhalides as well as LiAlCl4, LiAlBr4, LiGaC
14. LiB. C.I. prepared by dissolving a supporting electrolyte such as In addition, when preparing the electrolytic solution, the supporting electrolyte such as L r AI Cl a is
iC1 and AICI3 may be added to the oxyhalide so that they exist in the electrolyte in the form of LiAICla (however, they are ionized and exist as Li+ and AlCl,-), or The aromatic compound may also be added to the electrolyte preparation together with the supporting electrolyte or before the supporting electrolyte.
そして、本発明の電池において、負極活物質としては、
例えばリチウム、ナトリウム、カリウムなどのアルカリ
金属が用いられる。In the battery of the present invention, the negative electrode active material is
For example, alkali metals such as lithium, sodium, and potassium are used.
つぎに実施例をあげて本発明をさらに詳細に説明する。 Next, the present invention will be explained in more detail by giving examples.
実施例１
正極活物質として塩化チオニルを用い、負極活物質とし
てリチウムを用いて単３形の塩化チオニル−リチウム電
池を作製した。電解液は上記の塩化チオニルに支持電解
質としてのＬ ｉ Ａ Ｉ Ｃｌ ＜（ただし、塩化チ
オニルへの添加時はＬｉＣ１とＡｌＣ１，とを添加）を
１．２ ｍｏｌ／ ｌ ’（８Ｍしたものであり、本実
施例においては、この電解液にヘンジチオフェンを７
Ｘ １０−’ ｍｏｌ ／ ｌ添加している。Example 1 A AA-sized thionyl chloride-lithium battery was produced using thionyl chloride as a positive electrode active material and lithium as a negative electrode active material. The electrolytic solution was prepared by adding 1.2 mol/l' (8 M) of Li A I Cl < (however, when adding to thionyl chloride, LiC1 and AlC1 were added) as a supporting electrolyte to the above thionyl chloride. In this example, 7 hendithiophene was added to this electrolyte.
X 10-' mol/l is added.
第１［Ｄは上記電池を示すもので、図中、ｌはリチウム
からなる負極であり、この負極１はリチウムシートを有
底円筒状の電池容器２の内周面に圧着することによって
形成されている。３は正極で、この正極３はアセチレン
ブラ、りを主成分とする円柱状の炭素多孔質成形体より
なるものである。The first [D] indicates the above-mentioned battery, and in the figure, l is a negative electrode made of lithium. ing. 3 is a positive electrode, and this positive electrode 3 is made of a cylindrical carbon porous molded body containing acetylene oxide as a main component.
４は電解液で、この電解液４は前記のように塩化チオニ
ルにＬ ｉ Ａ Ｉ Ｃｌ ａを７容解させたものであ
り、本実施例においては、この電解液４にヘンジチオフ
ェンが７ ｘｔｏ−’ ｍｏｌ／ ｌ添加され、電池内
には３．９ｍｊ２注入されている。そして、この電池に
おいては、塩化チオニルは上記のように電解液の溶媒で
あるとともに正極活物質でもある。５はガラス繊維不織
布よりなるセパレータで、円筒状をしていて、前記円筒
状の負極１と円柱状の正極３とを隔離している。６は正
極集電体で、ステンレス鋼棒よりなる。７は電池蓋で、
この電池蓋７はステンレス鋼で形成されていて、その立
ら上がった外周部が前記電池容器２の開口端部と溶接に
より接合されている。そして電池蓋７の内ｊ１−１側に
は正極端子９との間にガラス層が設けられていて、ガラ
ス層８は電池Ｍ７と正極端子９とを絶縁するとともに、
外周面でその構成ガラスが電池蓋７の内周面に融着し、
その内周面でその構成ガラスが正極端子９の外周面に融
着して、電池蓋７と正極端子９との間をシールし、電池
容器２の開口部はいわゆるハーメチックシールにより１
・１０されている。正極端子９はステンレス鋼製で電池
組立時はパイプ状をしていて電解液注入口として使用さ
れ、その上端部を電解液注入後にその中空部内に挿入さ
れた正極集電体６の上部と溶接して封止したものである
。そして、１０および１１はそれぞれガラス繊維不織布
からなる底部隔離材および上部隔離材であり、１２は電
池内の上部に設けられた空気室である。Reference numeral 4 denotes an electrolytic solution, and this electrolytic solution 4 is made by dissolving 7 x of Li A I Cla in thionyl chloride as described above. -' mol/l was added, and 3.9 mj2 was injected into the battery. In this battery, thionyl chloride is not only the solvent of the electrolytic solution as described above, but also the positive electrode active material. Reference numeral 5 denotes a separator made of glass fiber nonwoven fabric, which has a cylindrical shape and separates the cylindrical negative electrode 1 and the cylindrical positive electrode 3. 6 is a positive electrode current collector, which is made of a stainless steel rod. 7 is the battery cover,
This battery lid 7 is made of stainless steel, and its raised outer peripheral portion is joined to the open end of the battery container 2 by welding. A glass layer is provided on the j1-1 side of the battery lid 7 between it and the positive terminal 9, and the glass layer 8 insulates the battery M7 and the positive terminal 9.
The constituent glass is fused to the inner peripheral surface of the battery lid 7 on the outer peripheral surface,
The constituent glass is fused to the outer circumferential surface of the positive terminal 9 on its inner circumferential surface, sealing between the battery lid 7 and the positive terminal 9, and the opening of the battery container 2 is sealed by a so-called hermetic seal.
・It is 10. The positive electrode terminal 9 is made of stainless steel and has a pipe shape when the battery is assembled, and is used as an electrolyte injection port, and its upper end is welded to the upper part of the positive electrode current collector 6 inserted into the hollow part after the electrolyte is injected. It was then sealed. Reference numerals 10 and 11 are a bottom isolation member and an upper isolation member respectively made of glass fiber nonwoven fabric, and 12 is an air chamber provided at the upper part of the battery.
実施例２
ベンゾチオフェンに代えてジベンゾチオフェンを７ Ｘ
ｌ０−’ ｍｏｌ／ ｌ添加した電解液を用いたほかは
実施例１と同様の構成からなる塩化チオニル−リチウム
電池を作製した。Example 2 Dibenzothiophene was replaced with benzothiophene 7X
A thionyl chloride-lithium battery having the same structure as in Example 1 was prepared except that an electrolytic solution containing 10-' mol/l was used.
実施例３
ベンゾチオフェンに代えて４−フェニルチオフェンを７
Ｘ ＩＰ’ ｍｏｌ ／ ｊ２添加した電解液を用い
たほかは実施例１と同様の構成からなる塩化チオニル−
リチウム電池を作製した。Example 3 4-phenylthiophene was used instead of benzothiophene.
Thionyl chloride having the same structure as in Example 1 except that an electrolytic solution containing
A lithium battery was created.
実ｈｉｎｉ例４
ベンゾチオフェンに代えてチオクロマン−４−オンを７
Ｘｌ０−’ ｍｏｌ／ １添加した電解液を用いたほ
かは実施例１と同様の構成からなる塩化チオニル−リチ
ウム電池を作製した。Practical hini example 4: replacing benzothiophene with thiochroman-4-one
A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that an electrolytic solution to which Xl0-' mol/1 was added was used.
実施例５
ベンゾチオフェンに代えてチオキサンセン−９−オンを
７ Ｘ １０”” ｍｏｌ／ ｌ添加した電解液を用い
たほかは実施例１と同様の構成からなる塩化チオニル−
リチウム電池を作製した。Example 5 Thionyl chloride having the same structure as Example 1 except that an electrolyte containing 7×10" mol/l of thioxansen-9-one was used instead of benzothiophene.
A lithium battery was created.
実施例６
ベンゾチオフェンに代えて２，４．６− トリクロロベ
ンゾチオフェンをＩ Ｘｌ０−” ｍｏｌ／ ｌ添加し
た電解液を用いたほかは実施例１と同様の構成からなる
塩化チオニル−リチウム電池を作製した。Example 6 A thionyl chloride-lithium battery was produced with the same structure as in Example 1, except that an electrolytic solution to which 2,4.6-trichlorobenzothiophene was added at IXl0-'' mol/l instead of benzothiophene was used. did.
実施例７
ベンゾチオフェンに代えて２，４．７− トリクロロジ
ベンゾチオフェンをＩ Ｘ １０−’ ｍｏｌ ／ Ｉ
！、添加した電解液を用いたほかは実施例１と同様の構
成からなる塩化チオニル−リチウム電池を作製した。Example 7 2,4.7-trichlorodibenzothiophene was used in place of benzothiophene at I X 10-' mol/I
! A thionyl chloride-lithium battery was fabricated having the same structure as in Example 1 except that the added electrolyte was used.
実施例８
ベンゾチオフェンの添、別置を７ Ｘ １０−’ ＴＩ
Ｏ＋ ／ １に変えた電解液を用いたほかは実施例１と
同様の構成からなる塩化チオニル−リチウム電池を作製
した。Example 8 Addition and separation of benzothiophene to 7 x 10-' TI
A thionyl chloride-lithium battery having the same structure as in Example 1 was produced, except that an electrolyte solution of O+/1 was used.
実施例９
ベンゾチオフェンの添加量を７ Ｘ １０−’ ｍｏｌ
／ １に変えた電解液を用いたほかは実施例■と同様
の構成からなる塩化チオニル−リチウム電池を作製した
。Example 9 The amount of benzothiophene added was 7 x 10-' mol
A thionyl chloride-lithium battery having the same structure as in Example 2 was produced except that an electrolyte solution different from 1 was used.
実施例１Ｏ
ベンゾチオフェンに代えて２，６−ジ−ターシャリーブ
チル−１，４−ベンゾキノンを７ Ｘｌ０−’ ｍｏｌ
／２添加した電解液を用いたほかは実施例１と同様の構
成からなる塩化チオニル−リチウム電池を作製した。Example 1O 7 Xl0-' mol of 2,6-di-tert-butyl-1,4-benzoquinone in place of benzothiophene
A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that an electrolyte solution with a concentration of 1/2 was used.
実施例１１
ベンゾチオフェンに代えて１．８−ナツタリックアンハ
イドライドをＩ Ｘ １０−’ ｍｏｌ／ ｌ添加した
電解液を用いたほかは実施例１と同様の構成からなる塩
化チオニル−リチウム電池を作製した。Example 11 A thionyl chloride-lithium battery having the same structure as in Example 1 was produced, except that an electrolyte containing I x 10-' mol/l of 1.8-natalic anhydride was used instead of benzothiophene. did.
実施例１２
ベンゾチオフェンに代えて９，１０−アントラキノンを
１ ｘｔｏ−３ｍｏｌ／ ｌ添加した電解液を用いたほ
かは実施例１と同様の構成からなる塩化チオニル−リチ
ウム電池を作製した。Example 12 A thionyl chloride-lithium battery having the same structure as in Example 1 was produced, except that an electrolytic solution to which 1 x to 3 mol/l of 9,10-anthraquinone was added instead of benzothiophene was used.
実施例１３
ベンゾチオフェンに代えてテトラクロロフタリックアン
ハイドライドをｌ ＸＩＯ”’ ｍｏｌ／ ｌ添加した
電解液を用いたほかは実施例１と同様の構成からなる塩
化チオニル−リチウム電池を作製した。Example 13 A thionyl chloride-lithium battery having the same structure as in Example 1 was produced, except that an electrolytic solution to which 1 XIO"' mol/l of tetrachlorophthalic anhydride was added instead of benzothiophene was used.
実施例１４
ベンゾチオフェンに代えて２，３．６．７−チトラクロ
ロアントラキノンをＩ Ｘ ＩＯ−３ｍｏｌ ／ ｌ添
加した電解液を用いたほかは実施例１と同様の構成から
なる塩化チオニル−リチウム電池を作製した。Example 14 A thionyl chloride-lithium battery having the same structure as Example 1 except that an electrolytic solution containing IXIO-3 mol/l of 2,3,6,7-titrachloroanthraquinone instead of benzothiophene was used. was created.
実施例１５
ベンゾチオフェンに代えてナフタレンを５ＸＩＯ−”ｍ
ｏｌ／ｊ！添加した電解液を用いたほかは実施例１と同
様の構成からなる塩化チオニル−リチウム電池を作製し
た。Example 15 5XIO-”m of naphthalene in place of benzothiophene
ol/j! A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that the added electrolyte was used.
実施例１６
ベンゾチオフェンに代えてアントラセンを５×１０−’
ｍｏｌ／ １添加した電解液を用いたほかは実施例１
と同様の構成からなる塩化チオニル−リチウム電池を作
製した。Example 16 5×10-' anthracene instead of benzothiophene
Example 1 except that an electrolyte solution containing mol/1 was used.
A thionyl chloride-lithium battery having the same configuration as above was fabricated.
実施例１７
ベンゾチオフェンに代えてピレンをＩ Ｘｌ０−３ｖａ
ｏｌ／ｌ添加した電解液を用いたほかは実施例１と同様
の構成からなる塩化チオニル−リチウム電池を作製した
。Example 17 Pyrene in place of benzothiophene I Xl0-3va
A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that an electrolyte solution containing ol/l was used.
実施例１８
ベンゾチオフェンに代えて２．３−ベンズアントラセン
を７ Ｘｌ０−’ ｍｏｌ／ ｌ添加した電解液を用い
たほかは実施例１と同様の構成からなる塩化チオニル−
リチウム電池を作製した。Example 18 Thionyl chloride having the same structure as Example 1 except that an electrolyte containing 7 Xl0-' mol/l of 2,3-benzanthracene was used instead of benzothiophene.
A lithium battery was created.
実施例１９
ベンゾチオフェンに代えてペンタセンをＩＸＩＯ−３ｍ
ｏｌ／ｆ添加した電解液を用いたほかは実施例１と同様
の構成からなる塩化チオニル−リチウム電池を作製した
。Example 19 IXIO-3m with pentacene instead of benzothiophene
A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that an electrolyte solution containing ol/f was used.
実施例２０
ベンゾチオフェンに代えて１．２，３．４−ジベンゾア
ントラセンを５ Ｘ １０−’ ｍｏｌ ／ ｌ添加し
た電解液を用いたほかは実施例１と同様の構成からなる
塩化チオニル−リチウム電池を作製した。Example 20 Thionyl chloride-lithium battery having the same structure as Example 1 except that an electrolyte containing 5 x 10-' mol/l of 1,2,3,4-dibenzanthracene was used instead of benzothiophene. was created.
実施例２１
ベンゾチオフェンに代えてコローネンを５Ｘ１０−’１
Ｉｌｏｌ／ｌ添加した電解液を用いたほかは実施例１と
同様の構成からなる塩化チオニル−リチウム電池を作製
した。Example 21 5X10-'1 coronene in place of benzothiophene
A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that an electrolytic solution to which Ilol/l was added was used.
実施例２２
ベンゾチオフェンに代えて２，４．７−ドリクロロフル
オレンをＩ ＸＩＯ”” ｍｏｌ／ Ｉ！ｌ添加た電解
液を用いたほかは実施例１と同様の構成からなる塩化チ
オニル−リチウム電池を作製した。Example 22 2,4.7-dolichlorofluorene was used instead of benzothiophene. A thionyl chloride-lithium battery was produced having the same structure as in Example 1, except that an electrolytic solution containing 1.1% was used.
比較例１
ベンゾチオフェンなどの芳香族化合物をまった（添加し
ていない電解液、つまり塩化チオニルにＬｉＡｌＣ１，
を１．２ ｍｏｌ／ ｊ２溶解しただけの電解液を用い
たほかは実施例１と同様の構成からなる塩化チオニル−
リチウム電池を作製した。Comparative Example 1 An aromatic compound such as benzothiophene was added to the electrolyte (without the addition of LiAlC1, thionyl chloride, etc.).
Thionyl chloride-
A lithium battery was created.
比較例２
ベンゾチオフェンに代えて塩素化ポリエチレンを０．１
ｇ＃！添加した電解液を用いたほかは実施例１と同様の
構成からなる塩化チオニル−リチウム電池を作製した。Comparative Example 2 Chlorinated polyethylene was used in place of benzothiophene at 0.1
g#! A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that the added electrolyte was used.
なお、上記塩素化ポリエチレンの電解液への添加量は実
施例１におけるベンゾチオフェンの添加量とほぼ同ダラ
ム数である。つまり、実施例１の電池における電解液へ
のベンゾチオフェンの添加槽は７ＸＩＰ’ ｍｏｌ／ｌ
であるが、これをｇ／ｌで表示すると０．０９４ ｇ
／ ｆｆｉである。このように塩素化ポリエチレンの電
解液への添加量をｇ／ｆｆｉ基準にしたのは、塩素化ポ
リエチレンが高分子化合物で分子量が非常に大きいため
、実施例１のベンゾチオフェンと同モル（ｍｏｌ／ １
） ６２度で電解液に添加すると添加量が非常に多く
なりすぎ、かえって性能低下を招くためである。The amount of the chlorinated polyethylene added to the electrolytic solution was approximately the same Durham number as the amount of benzothiophene added in Example 1. In other words, the tank for adding benzothiophene to the electrolyte in the battery of Example 1 was 7XIP' mol/l.
However, when expressed in g/l, it is 0.094 g
/ffi. The reason why the amount of chlorinated polyethylene added to the electrolytic solution was based on g/ffi is because chlorinated polyethylene is a high molecular compound and has a very large molecular weight, so it has the same mole (mol/ffi) as the benzothiophene in Example 1. 1
) This is because if added to the electrolyte at 62 degrees, the amount added would be too large, which would actually lead to a decline in performance.
比較例３
ベンゾチオフェンに代えてポリエチレンオキサイドを０
．１ｇ／ｅ添加した電解液を用いたほかは実施例１と同
様の構成からなる塩化チオニル−リチウム電池を作製し
た。Comparative Example 3 0 polyethylene oxide was used instead of benzothiophene
．． A thionyl chloride-lithium battery having the same structure as in Example 1 was produced except that an electrolytic solution to which 1 g/e was added was used.
このように、この比較例３においてもポリエチレンオキ
サイドの電解液への添加針をｇ ／ ｌ ｊｌ、 １鯉
にしたのは、比較例２の塩素化ポリエチレンの場合と同
様の観点からである。As described above, the reason why the addition needle of polyethylene oxide to the electrolytic solution was set to g/l jl, 1 carp in Comparative Example 3 is from the same viewpoint as in the case of chlorinated polyethylene in Comparative Example 2.
上記実施例１〜２２の電池および比較例１〜３の電池を
６０°Ｃで２０日間貯蔵した後、２０°Ｃ１負荷１（１
０）Ωで連続放電させ、その放電特性を調べた。After storing the batteries of Examples 1 to 22 and the batteries of Comparative Examples 1 to 3 at 60°C for 20 days, 20°C1 load 1 (1
A continuous discharge was performed at 0)Ω, and the discharge characteristics were investigated.
実施例１〜２２の電池は、いずれも放電特性が平坦で、
かつ、それらの間に大きな差は認められなかった。した
がって、これら実施例１〜２２の放電特性を同一図面上
に回示すると、いずれも同じような放電カーブになり、
その識別が困難になるので、それらを代表して、実施例
１の電池の放電特性のみを第２図に示した。また、第２
図には、上記実施例１の電池の放電特性と対比するため
、電解液に添加物をまったく添加していない比較例１の
電池の放電特性も図示した。The batteries of Examples 1 to 22 all had flat discharge characteristics;
Moreover, no major difference was observed between them. Therefore, when the discharge characteristics of Examples 1 to 22 are shown on the same drawing, they all have similar discharge curves,
Since it would be difficult to identify them, only the discharge characteristics of the battery of Example 1 are shown in FIG. 2 to represent them. Also, the second
In order to compare with the discharge characteristics of the battery of Example 1, the figure also shows the discharge characteristics of a battery of Comparative Example 1 in which no additives were added to the electrolytic solution.
この第２図から、明らかなように、比較例１の電池では
放電初期に電圧降下が見られるが、本発明の実施例１の
電池では、そのような電圧降下がなく、放電特性が平坦
であった。なお、電解液に塩素化ポリエチレンを添加し
た比較例２の電池や電解液にポリエチレンオキサイドを
添加した比較例３の電池では、１（１０）Ωという中負
荷放電では電流密度が約３．４ｍＡ／ｃ−とかなり高く
なるので、放電初期の電圧降下を防止する効果が少なく
、添加物をまったく添加していない比較例１の電池に近
い放電特性であづた。As is clear from FIG. 2, the battery of Comparative Example 1 shows a voltage drop at the beginning of discharge, but the battery of Example 1 of the present invention has no such voltage drop and has a flat discharge characteristic. there were. In addition, in the battery of Comparative Example 2 in which chlorinated polyethylene was added to the electrolyte and the battery in Comparative Example 3 in which polyethylene oxide was added to the electrolyte, the current density was approximately 3.4 mA/ c-, which had little effect on preventing a voltage drop at the beginning of discharge, and the discharge characteristics were close to those of the battery of Comparative Example 1 to which no additives were added.
また、実施例１〜２２の電池および比較例１〜３の電池
を６０°Ｃで２０日曲藏した後、２Ｑ’Ｃ１１０Ωで５
０ｍ５間の放電をしたときの５０ｍ５後の電池電圧を？
Ｊ１１１定した。その結果を第１表に示す。In addition, after the batteries of Examples 1 to 22 and the batteries of Comparative Examples 1 to 3 were stored at 60°C for 20 days,
What is the battery voltage after 50m5 when discharged for 0m5?
J111 was established. The results are shown in Table 1.
第１表に示すように、６０°Ｃで２０日間貯蔵後に、１
０Ωで５０ｍ５放電させた場合は、電ａｉ密度が約１０
〜２０ｍＡ／ｃ＋ｆｉと太き（なるため（なお、電流密
度に幅があるのは、各電池によって電圧が異なるためで
ある）、添加物の効果がさらに明瞭になり、添加物をま
ったく添加していない比較例１の電池では、電池電圧が
１．１８９Ｖまで低下して大きな電圧降下が認められた
のに対し、実施例１〜２２の電池では、添加物の相違や
添加量の相違で若干の差異はあるものの、電池電圧が１
．５０２ Ｖ 〜２．１４９Ｖの範囲内にあって、いず
れも大きな電圧降下はｐｊめられなかった。また、電解
液に塩素化ポリエチレンを添加した比較例２の電池や電
解液にポリエチレンオキサイドを添加した比較例３の電
池は、電池電圧がそれぞれ１．２０３Ｖと１．２（１０
）Ｖと比較例１の電池に近く、このような大電流放電で
は、電圧降下を防止する効果がほとんど認められなかっ
た。As shown in Table 1, after storage at 60°C for 20 days, 1
When discharging 50m5 at 0Ω, the electric density is approximately 10
~20mA/c+fi (note that the current density varies because the voltage differs depending on the battery), the effect of additives becomes even clearer, and no additives are added at all. In the battery of Comparative Example 1, the battery voltage decreased to 1.189V and a large voltage drop was observed, whereas in the batteries of Examples 1 to 22, there was a slight voltage drop due to the difference in additives and the difference in the amount added. Although there are differences, the battery voltage is 1
．． Within the range of 502 V to 2.149 V, no large voltage drop was observed in either case. In addition, the battery of Comparative Example 2, in which chlorinated polyethylene was added to the electrolyte, and the battery of Comparative Example 3, in which polyethylene oxide was added to the electrolyte, had battery voltages of 1.203 V and 1.2 (10
)V was close to that of the battery of Comparative Example 1, and in such a large current discharge, almost no effect of preventing voltage drop was observed.
以上説明したように、本発明では、電解液に芳香族化合
物を添加することにより、貯蔵後の大電流放電において
も、放電初期の電圧降下を防止することができた。As explained above, in the present invention, by adding an aromatic compound to the electrolytic solution, it was possible to prevent voltage drop at the initial stage of discharge even in large current discharge after storage.
第１１ＥＩは本発明の無機非水電解液電池の一実施例を
示す断面図である。第２関は実施例１の電池と比較例１
の電池の放電特性図である。
■・・・負極、 ３・・・正極、 ４・・・電解液
１：ｐ：＋パ゛力
第 １ 図
第２図
□実１１１テ１１
一−−−比較勺Ｉ
放 電 時 間 （ｈ）11th EI is a sectional view showing one embodiment of the inorganic non-aqueous electrolyte battery of the present invention. The second test is the battery of Example 1 and Comparative Example 1.
FIG. 3 is a discharge characteristic diagram of the battery. ■... Negative electrode, 3... Positive electrode, 4... Electrolyte 1: p: + power 1 Figure 2 □ Actual 111 Te 11 - Comparison I Discharge time (h )
Claims (12)
媒とし、アルカリ金属を負極活物質とする無機非水電解
液電池において、電解液に芳香族化合物を添加したこと
を特徴とする無機非水電解液電池。(1) An inorganic non-aqueous electrolyte battery using an oxyhalide as a positive electrode active material and an electrolyte solvent and an alkali metal as a negative electrode active material, characterized in that an aromatic compound is added to the electrolyte. liquid battery.
ある特許請求の範囲第１項記載の無機非水電解液電池。(2) The inorganic non-aqueous electrolyte battery according to claim 1, wherein the aromatic compound is an aromatic compound containing sulfur.
オウを環内に含む複素環とが結合した芳香族化合物であ
る特許請求の範囲第２項記載の無機非水電解液電池。(3) The inorganic nonaqueous electrolyte battery according to claim 2, wherein the sulfur-containing aromatic compound is an aromatic compound in which a benzene ring and a heterocycle containing sulfur in the ring are bonded.
した芳香族化合物がベンゾチオフェン、ジベンゾチオフ
ェン、４−フェニルチオフェンチオクロマン−４−オン
またはチオキサンセン−９−オンである特許請求の範囲
第３項記載の無機非水電解液電池。(4) Claims in which the aromatic compound in which a benzene ring and a heterocycle containing sulfur are bonded is benzothiophene, dibenzothiophene, 4-phenylthiophenethiochroman-4-one, or thioxancene-9-one. The inorganic non-aqueous electrolyte battery according to item 3.
または全部が塩素原子で置換されている特許請求の範囲
第２項記載の無機非水電解液電池。(5) The inorganic non-aqueous electrolyte battery according to claim 2, wherein some or all of the hydrogen atoms of the sulfur-containing aromatic compound are replaced with chlorine atoms.
る特許請求の範囲第１項記載の無機非水電解液電池。(6) The inorganic non-aqueous electrolyte battery according to claim 1, wherein the aromatic compound is an aromatic compound containing oxygen.
シャリーブチル−１，４−ベンゾキノン、１，８−ナフ
タリックアンハライドまたは９，１０−アントラキノン
である特許請求の範囲第６項記載の無機非水電解液電池
。(7) Claim 6, wherein the oxygen-containing aromatic compound is 2,6-di-tert-butyl-1,4-benzoquinone, 1,8-naphthalic anhalide, or 9,10-anthraquinone. The inorganic non-aqueous electrolyte battery described above.
たは全部が塩素原子で置換されている特許請求の範囲第
６項記載の無機非水電解液電池。(8) The inorganic non-aqueous electrolyte battery according to claim 6, wherein some or all of the hydrogen atoms of the oxygen-containing aromatic compound are replaced with chlorine atoms.
式芳香族化合物である特許請求の範囲第１項記載の無機
非水電解液電池。(9) The inorganic non-aqueous electrolyte battery according to claim 1, wherein the aromatic compound is a homocyclic aromatic compound containing two or more benzene rings.
物がナフタリン、アントラセン、ピレン、２，３−ベン
ズアントラセン、ペンタセン、１，２，３，４−ジベン
ズアントラセンまたはクローネンである特許請求の範囲
第９項記載の無機非水電解液電池。(10) A patent claim in which the homocyclic aromatic compound containing two or more benzene rings is naphthalene, anthracene, pyrene, 2,3-benzanthracene, pentacene, 1,2,3,4-dibenzanthracene, or clonene. The inorganic non-aqueous electrolyte battery according to item 9.
物の水素原子の一部または全部が塩素原子で置換されて
いる特許請求の範囲第９項記載の無機非水電解液電池。(11) The inorganic non-aqueous electrolyte battery according to claim 9, wherein some or all of the hydrogen atoms of the homocyclic aromatic compound containing two or more benzene rings are replaced with chlorine atoms.
−＾６ｍｏｌ／ｌ〜１×１０＾−＾２ｍｏｌ／ｌである
特許請求の範囲第１項記載の無機非水電解液電池。(12) The amount of aromatic compound added to the electrolyte is 1 x 10^
The inorganic non-aqueous electrolyte battery according to claim 1, wherein the electrolyte is -^6 mol/l to 1 x 10^-^2 mol/l.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-156948A JPH012260A (en) | 1987-06-24 | Inorganic non-aqueous electrolyte battery | |
| EP88110028A EP0296589B1 (en) | 1987-06-24 | 1988-06-23 | Non-aqueous electrochemical cell |
| DE88110028T DE3883630T2 (en) | 1987-06-24 | 1988-06-23 | Non-aqueous electrochemical cell. |
| US07/210,927 US4888255A (en) | 1987-06-24 | 1988-06-24 | Non-aqueous electrochemical cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-156948A JPH012260A (en) | 1987-06-24 | Inorganic non-aqueous electrolyte battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS642260A JPS642260A (en) | 1989-01-06 |
| JPH012260A true JPH012260A (en) | 1989-01-06 |
Family
ID=
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