JPH02230667A - Lithium battery - Google Patents
Lithium batteryInfo
- Publication number
- JPH02230667A JPH02230667A JP1051288A JP5128889A JPH02230667A JP H02230667 A JPH02230667 A JP H02230667A JP 1051288 A JP1051288 A JP 1051288A JP 5128889 A JP5128889 A JP 5128889A JP H02230667 A JPH02230667 A JP H02230667A
- Authority
- JP
- Japan
- Prior art keywords
- group
- block
- electrolyte
- lithium
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 30
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 2
- -1 acryl group Chemical group 0.000 abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 2
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000005518 polymer electrolyte Substances 0.000 description 11
- 239000007784 solid electrolyte Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229920001400 block copolymer Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000002093 peripheral effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910000733 Li alloy Inorganic materials 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001989 lithium alloy Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Chemical group 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004831 Hot glue Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KHQBJTWCNHYZPW-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.C(C)(C)(C)O[K] Chemical compound C1=CC=CC2=CC=CC=C12.C(C)(C)(C)O[K] KHQBJTWCNHYZPW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical group CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- WGWWKACBPIVNDI-UHFFFAOYSA-N potassium;stilbene Chemical group [K].C=1C=CC=CC=1C=CC1=CC=CC=C1 WGWWKACBPIVNDI-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はリチウムまたはリチウム合金を負極とするリチ
ウム電池、とくにはその電池要素である正極集電板と負
極集電板との間に介在する電解質として、ブロックーグ
ラフト共重合体のリチウムイオン塩との複合物を使用し
たリチウム電池に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a lithium battery using lithium or a lithium alloy as a negative electrode, and particularly to a lithium battery interposed between a positive electrode current collector plate and a negative electrode current collector plate, which are battery elements thereof. The present invention relates to a lithium battery using a complex of a block-graft copolymer with a lithium ion salt as an electrolyte.
（従来の技術）
従来、リチウム電池に利用される電解貿としてはリチウ
ム塩を非水系溶媒Ｃこ溶解させてなる高流動性の液体の
ほか，この液にゲル化剤を加えてゲル状とした液体電解
質が知られている。(Prior art) Conventionally, electrolytic products used in lithium batteries include a highly fluid liquid made by dissolving a lithium salt in a non-aqueous solvent, and a gelling agent added to this liquid to form a gel. Liquid electrolytes are known.
しかし、最近のマイクロエレクトロニクス化の進展はメ
モリーバックアップ電源に代表されるように、電池の機
器内収納、素子、回路との一体化に伴って電池の小型化
、薄型化，軽量化が望まれてきている．このような要望
に対して液体電解質（電解液）を使用する電池では電極
と電極との接触を防止するため電極間にセパレー夕が必
要で、電池の小型化．薄型化に制約があるほか、液漏れ
の心配や使用温度範囲が狭いなどの問題がある。However, recent advances in microelectronics, as typified by memory backup power supplies, have led to the desire for batteries to be smaller, thinner, and lighter as batteries are housed inside devices and integrated with elements and circuits. ing. In response to these demands, batteries that use a liquid electrolyte (electrolyte) require a separator between the electrodes to prevent contact between the electrodes, making the battery smaller. In addition to being limited in their ability to be made thinner, there are other issues such as concerns about liquid leakage and a narrow operating temperature range.
これらの問題に対して電解液を固体化する方法として高
分子固体電解質を用いる試みがなされている。これまで
に、このような高分子固体電解質としてポリエチレンオ
キサイド，ポリエチレンイミン、ボリフオスファゼンな
どのボリマーとリチウム塩との組合せを用いた系が報告
されている．（発明が解決しようとする課題）
しかし，これらの高分子固体電解質には、】−）イオン
伝導率が十分でない、２）強度に欠ける、３）成形性が
悪い、４）電極に対して不安定であるなどの欠点がある
ために、放電特性面で満足できず，また経時的に性能低
下が大きく寿命面でも難があることから呪段階では実用
化には至っていない。To solve these problems, attempts have been made to use solid polymer electrolytes as a method of solidifying electrolytes. So far, systems using combinations of polymers such as polyethylene oxide, polyethyleneimine, and borifosphazene with lithium salts have been reported as such solid polymer electrolytes. (Problems to be Solved by the Invention) However, these solid polymer electrolytes have problems such as -) insufficient ionic conductivity, 2) lack of strength, 3) poor formability, and 4) poor electrode resistance. Due to shortcomings such as stability, the discharge characteristics are not satisfactory, and the performance deteriorates significantly over time, causing problems in terms of lifespan, so it has not been put into practical use at the curse stage.
したがって、本発明はイオン伝導度が高く，成．形性の
よい高分子固体電解貿を用いて上記の高性能化および長
寿命化の要望に十分に対応できるリチウム電池を提供す
ることを目的とする．（課題を解決するための手段）
本発明によるリチウム電池は、一般式（１）（ここに，
Ｒ１は水素原子、メチル基、またはエチル基．Ｒ２は水
素原子またはメチル基 Ｒ３はアルキル基，アリール基
、アシル基、またはシリル基、ｍは１〜４５の整数であ
り，Ｐは整数、式中の
ロ
数平均分子景は４５以上２，０００未満である）で表さ
れる繰返し単位からなる少なくとも１種の重合体のブロ
ック鎖Ａと、一般式（１１）Ｍ
（ここに Ｒ４は水素原子、メチル基、またはエチル基
，Ｍは式 一ＣＨ＝ＣＨ２．
−Ｃ（ＣＨ．）＝ＣＩ｛２．−ＣＯＯＣＲ，，または−
Ｃ Ｏ Ｏ Ｃ２Ｈ，で表される基、フエニル基、も
しくは置換フエニル基、ｎは整数である）で表される繰
返し単位からなる少なくとも１種の重合体のブロック鎖
Ｂ，とから構成されるプロツクーグラフト共重合体のリ
チウムイオン塩との複合物を，電解質として内蔵してな
るものとしたことを要旨とするものである。Therefore, the present invention has high ionic conductivity and a high ionic conductivity. The purpose of this project is to provide a lithium battery that satisfactorily meets the above requirements for higher performance and longer life by using a polymer solid electrolyte with good shape. (Means for Solving the Problems) The lithium battery according to the present invention has the general formula (1) (where,
R1 is a hydrogen atom, a methyl group, or an ethyl group. R2 is a hydrogen atom or a methyl group, R3 is an alkyl group, aryl group, acyl group, or silyl group, m is an integer from 1 to 45, P is an integer, and the rhonumber average molecular size in the formula is 45 or more and 2,000 at least one polymer block chain A consisting of repeating units represented by the general formula (11) M (where R4 is a hydrogen atom, methyl group, or ethyl group, M is a formula =CH2.-C(CH.)=CI{2.-COOCR, or-
C O O C H, a phenyl group or a substituted phenyl group, n is an integer), and at least one polymer block chain B consisting of a repeating unit represented by The gist is that a composite of Tsukuu graft copolymer and lithium ion salt is incorporated as an electrolyte.
本発明のリチウム電池で用いられる上記ブロツクーグラ
フト共重合体のリチウムイオン塩との複合物は高分子固
体電解質であって、後述する実施例の結果から明らかな
ようレこ従来のものに比べてイオン伝導度が高いため、
これを用いたリチウム電池は内部抵抗が低く、その放電
特性を改善する．また、この高分子固体電解質では高い
イオン伝導度に加えて成形性がよく，強度が大きく、正
極および負極との密着性がよく、またこの両極との反応
性がないために経時変化による内部抵抗の増大および漏
液が防止される結果、長時間の使用によっても性能低下
が少なく従来のものに比べて寿命が長いという利点が与
えられる。The composite of the block graft copolymer and lithium ion salt used in the lithium battery of the present invention is a solid polymer electrolyte, and as is clear from the results of the examples described later, it is more effective than conventional ones. Due to its high ionic conductivity,
Lithium batteries using this material have low internal resistance and improve their discharge characteristics. In addition to high ionic conductivity, this polymer solid electrolyte has good formability, high strength, and good adhesion with the positive and negative electrodes.Also, because it has no reactivity with these two electrodes, it has internal resistance due to changes over time. As a result, an increase in the amount of water and liquid leakage are prevented, resulting in less deterioration in performance even after long-term use and an advantage of a longer lifespan than conventional ones.
ここで用いられるブロックーグラフト共重合体は、それ
ぞれ一般式（１）および（ＩＩ）で表される同種または
異種の繰返し単位からなる、少なくとも１種の重合体の
ブロック鎖Ａ，Ｂが，例えばＡ″ーＢ１、 ｓ １ Ａ
１ ． Ｂ １ Ａ１ ｓ １、 Ｂ工Ａ”Ｂス、Ｂ
工Ａ１＃３本一Ａ１Ｂ″というように、任意に配列され
てなるものである．
重合体のブロックｆｉＡの重合度は１０以上、同じ＜Ｈ
の重合度は３００以上であることが好ましく、またこの
両ブロック鎖Ａ．Ｈの成分比は１：３０〜３０：１であ
ることが好ましい，これは１：３０以下ではグラフト成
分が少なすぎて高分子電解質としての機能を保つことが
難しくなり，また３０：１以上ではブロック鎖の幹分子
としての機械的強度が保持しにくくなるからである．
高分子電解質に用いられる他方のリチウムイオン塩には
、これまでリチウム電池用電解質成分として知られてい
る種々のものを選択使用することができるが、とくに好
適なものとしてはＬｉＰ Ｆ，、Ｌｉｅｕ ○い Ｌ
ｉ Ｂ ｌ’ い ＬｉＢ φ い Ｌｉ
ｅ Ｆ， Ｓ ，ＬｉＡｓ．などが挙げられ、こ
れらはその１種または２種以上の組合せで使用される。In the block-graft copolymer used here, block chains A and B of at least one polymer each consisting of the same or different repeating units represented by general formulas (1) and (II), for example, A″-B1, s 1 A
1. B 1 A1 s 1, B engineering A” B s, B
The polymer blocks fiA have a polymerization degree of 10 or more, with the same <H
It is preferable that the degree of polymerization of A. The component ratio of H is preferably 1:30 to 30:1. If it is less than 1:30, there will be too little graft component and it will be difficult to maintain the function as a polymer electrolyte, and if it is more than 30:1, it will be difficult to maintain the function as a polymer electrolyte. This is because it becomes difficult to maintain mechanical strength as the backbone molecule of the block chain. For the other lithium ion salt used in the polymer electrolyte, various salts known as electrolyte components for lithium batteries can be selected, but particularly preferred are LiP F, Lieu ○ Yes L
i B l' i LiB φ i Li
e F, S, LiAs. These may be used alone or in combination of two or more.
また、これのブロックーグラフト共重合体に対する割合
は，この共重合体のアルキレンオキサイドユニットに対
して０．０５〜８０モル％、好ましくはＯ。１〜５０モ
ル％が適当である．
このブロツクーグラフト共重合体は、例えば一般式（Ｉ
ｌｌ）
（式中、Ｒ１．ｍは前記に同じ）で表される繰返し単位
からなる少なくとも１種の重合体のブロック鎖Ｃと、前
記一般式（Ｕ）で表される繰返し単位からなる少なくと
も１種の重合体のブロック＃ＩＢとから構成されている
、幹分子鎖となるブロック共重合体Ｔを合成し、次にこ
のブロック共重合体が持つ側鎖のヒドロキシル基に，一
般弐ＲＭｅ（ここにＲはｔ−ブチルエーテル、ジフェニ
ルエチレン、ベンジル、ナフタレン、またはクミル基、
Ｍｅはナトリウム、カリウム、またはセシウム原子であ
る）で表される有機アルカリ金属を反応させてカルバニ
オン化し，これに一般式（ＩＶ）で表されるアルキレン
オキサイドを加えてグラフト鎖を成長させることによっ
て製造することができる．
この際、出発原料として用いられるブロック鎖Ｃ，Ｂか
らなる幹分子鎖としてのブロック共重合体７１’は，ま
ず４−ヒドロキシスチレン、４−（１−メチルエテニル
）フェノールなどで例示される、一般式（Ｉｌｌ）で示
される残基を含有するモノマー化合物について、そのフ
ェノール性水酸基をトリアルキル基やトリアルキルシリ
ル基で保護しておき，これと，スチレン、α−メチルス
チレン等のビニル化合物；ブタジエン、イソブレン等の
ジエン化合物；メチルアクリレート、エチルアクリレー
ト、メチルメタクリレート、エチルメタクリレート等の
アクリル酸エステル、メタクリル酸エステル；等で例示
される七ノマー化合物より合成された、一般式（■）で
表される繰返し単位を有するプロック重合体を，リビン
グアニオン重合法により重合し、次に酸などで加水分解
することによって得ることができる．
この重合に用いられる開始剤には，ｎ−ブチルリチウム
、ｓｅｅ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム
、２−メチルブチルリチウム等の有機金属化合物系のも
のが例示されるが，これらの内では特にｎ−ブチルリチ
ウムが好ましい．この使用量は仕込み化合物量と共に、
得られる重合体の分子量を決定するので、所望の分子量
に応じて選択される。得られたブロック共重合体Ｔを構
成するブロック鎖Ｃの重合度は１０以上あるものが好ま
しいので．通常は反応溶液中でｔｏ−’〜１０−４■ｏ
ｆ／ Ｑのオーダーの濃度になるようにする．
重合は一般に有機溶媒中で行なわれるが、これに使用で
きる有機溶媒の例としては，ベンゼン、トルエン，ｎ−
へキサン．テトラヒド口フラン等のア二オン重合用の溶
媒が好ましい．重合に供するモノマー化合物の反応溶液
中の濃度は１〜１０重量％が適切であり、重合反応は圧
力１０−’Ｔｏｒｒ以下の高真空下、または精製して水
分等の反応に対する有害物質を除去したアルゴン、窒素
等の不活性ガス雰囲気中で、室温において攪拌下に行な
うのが好ましい。The proportion of this in the block-graft copolymer is 0.05 to 80 mol%, preferably O, based on the alkylene oxide unit of the copolymer. A suitable amount is 1 to 50 mol%. This block graft copolymer can be produced by, for example, the general formula (I
ll) (wherein R1.m is the same as above) at least one polymer block chain C consisting of a repeating unit and at least one polymer block chain C consisting of a repeating unit expressed by the general formula (U) A block copolymer T as a backbone molecular chain composed of seed polymer block #IB is synthesized, and then general 2RMe (here R is t-butyl ether, diphenylethylene, benzyl, naphthalene, or cumyl group,
Produced by reacting an organic alkali metal represented by (Me is a sodium, potassium, or cesium atom) to carbanion, and adding an alkylene oxide represented by general formula (IV) to this to grow a graft chain. can do. At this time, the block copolymer 71' as a backbone molecular chain consisting of block chains C and B used as a starting material is first prepared by a general formula such as 4-hydroxystyrene, 4-(1-methylethenyl)phenol, etc. Regarding the monomer compound containing the residue represented by (Ill), the phenolic hydroxyl group is protected with a trialkyl group or trialkylsilyl group, and this and a vinyl compound such as styrene or α-methylstyrene; butadiene, Diene compounds such as isobrene; acrylic esters and methacrylic esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; It can be obtained by polymerizing a block polymer having units by a living anionic polymerization method and then hydrolyzing it with an acid or the like. Examples of initiators used in this polymerization include organometallic compound-based initiators such as n-butyllithium, see-butyllithium, tert-butyllithium, and 2-methylbutyllithium. -Butyllithium is preferred. This usage amount, together with the amount of compound used,
Since it determines the molecular weight of the resulting polymer, it is selected depending on the desired molecular weight. The degree of polymerization of the block chains C constituting the obtained block copolymer T is preferably 10 or more. Usually to-' to 10-4■o in the reaction solution
The concentration should be on the order of f/Q. Polymerization is generally carried out in an organic solvent, and examples of organic solvents that can be used include benzene, toluene, n-
Hexane. Solvents for anionic polymerization such as tetrahydrofuran are preferred. The appropriate concentration of the monomer compound to be subjected to polymerization in the reaction solution is 1 to 10% by weight, and the polymerization reaction is performed under a high vacuum at a pressure of 10-'Torr or less, or by purification to remove harmful substances such as moisture. It is preferable to carry out the reaction under stirring at room temperature in an inert gas atmosphere such as argon or nitrogen.
保護基の脱離反応はジオキザン、アセトン、メチルエチ
ルケトン，アセＩ−二１−リル等の溶媒中で加熱下、塩
酸またはよう化水索酸等の酸を滴下することによって容
易に行なうことができる。The elimination reaction of the protecting group can be easily carried out in a solvent such as dioxane, acetone, methyl ethyl ketone, acetyl-21-lyl, etc. by adding dropwise an acid such as hydrochloric acid or iodide acid while heating.
このようにして得られたブロック共重合体Ｔのヒドロキ
シル基のカルバニオン化は、これを濃度１〜３０重量％
、好ましくは１〜１０重量％のテトラヒド口フラン等の
ア二オン重合用溶媒に溶解し，これに有機アルカリ金屈
をテトラヒド口フラン等の適当な溶媒に溶かして加え，
０〜２５″Ｃで３０分〜４時間攪拌することにより行わ
れる。Carbanionization of the hydroxyl groups of the block copolymer T obtained in this way is carried out at a concentration of 1 to 30% by weight.
, preferably 1 to 10% by weight of an anionic polymerization solvent such as tetrahydrofuran, and to this, an organic alkali metal is dissolved in a suitable solvent such as tetrahydrofuran and added,
This is done by stirring at 0-25''C for 30 minutes to 4 hours.
この反応に用いられる有機アルカリ金属としては、例え
ばｔ−ブトキシカリウム、ナフタレンカリウム、ジフェ
ニルエチレンカリウム，ベンジルカリウム，クミルカリ
ウム、ナフタレンナトリウム、クミルセシウム等が挙げ
られるが，これらの内ではどくにｔ−ブトキシカリウム
が好ましい。Examples of organic alkali metals used in this reaction include potassium t-butoxy, potassium naphthalene, potassium diphenylethylene, potassium benzyl, potassium cumyl, sodium naphthalene, and cumyl cesium. preferable.
この反応の確認は、生成物を１−リメチルシリルクロラ
イドと反応させた後、メタノール中で沈殿、精製後，乾
燥して単離して得られた試料を，１Ｈ−ＮＭＲによって
ヒドロキシル基の消滅，トリメチルシリル基の増加量を
測定することにより行うことができ、有機アルカリ金属
のヒドロキシル基への反応を定量的に把握できる。また
ＧＰＣによってブロック鎖が架橋や分解反応を受けてい
ないことも確認できる．
カルバニオン化したブロック共重合体゛ｌ゛は、次に一
般式（１ｖ）で示されるアルキレンオキサイド、例えば
エチレンオキサイド、プロピレンオキサイドなどを蒸気
状あるいは液状で加え、量にもＪ；るがＯ〜８０℃で１
−〜４８時間攪拌すると、ブロックーグラフト共重合体
にすることができる。This reaction was confirmed by reacting the product with 1-limethylsilyl chloride, precipitating it in methanol, purifying it, drying it, and isolating the resulting sample. This can be done by measuring the amount of increase in trimethylsilyl groups, and the reaction of organic alkali metals to hydroxyl groups can be quantitatively understood. It was also confirmed by GPC that the block chains were not subjected to cross-linking or decomposition reactions. Next, to the carbanionized block copolymer "l", an alkylene oxide represented by the general formula (1v), such as ethylene oxide, propylene oxide, etc., is added in vapor or liquid form, and the amount is J; 1 in °C
- After stirring for ~48 hours, a block-graft copolymer can be obtained.
アルキレンオキサイドを加えた重合溶液はｎ −ヘキサ
ン中に注ぐと沈殿し，それをろ過して乾燥すると単離で
きる。キャラクタリゼーションは膜浸透圧計で数平均分
子量を測定し、赤外吸収スペクトル、’ Ｈ − Ｎ
Ｍ Ｒで構造や組成を決定し，その結果からグラフト鎖
の長さ．数を決定できる。またＧ Ｐ Ｃで目的物が単
離できているか否かの判断と分子量分布を推測すること
ができる。The polymerization solution to which alkylene oxide has been added is poured into n-hexane to precipitate it, which can be isolated by filtering and drying. Characterization was carried out by measuring the number average molecular weight with a membrane osmometer, infrared absorption spectrum, 'H-N
The structure and composition are determined by MR, and the length of the graft chain is determined from the results. can determine the number. Furthermore, it is possible to determine whether the target substance has been isolated by GPC and to estimate the molecular weight distribution.
この幹分子鎖となるブロック共重合体Ｔの重合およびこ
れの枝分子鎖成長のための反応は通常有機溶媒中で行わ
れるが、これに使用できる有機溶媒の例としては、テト
ラヒド口フラン、ジオキサン、テトラヒドロビラン，ベ
ンゼン等の、アニオン重合または開環重合用の溶媒が好
ましい．重合の停止に用いられる化合物には、例えば酢
酸等の酸類；メチルブロマイド、ペンジルクロライド等
のハロゲン化物；トリメチルシリルクロライド，ｔ−ブ
チルジメチルシリルクロライド等のシリル化合物；等が
挙げられる．
グラフト鎖の長さの制御は、ブロックーグラフト共重合
体に含まれるブロックｆｌＡＣのモル数と，カルバニオ
ン化するときの有機アルカリ金属の量と、アルキレンオ
キサイドの址とで決定される．すなわち有機アルカリ金
属の量はブロック鎖Ｃのモル数を超えてはならず、また
グラフト鎖の長さは
で表される．
例えば，グラフト鎖の長さが数平均分子量で２，０００
のブロックーグラフト共重合体を製造するには、ブロッ
ク鎖Ｃを７Ｘ１０−３モル含むブロックーグラフト共重
合体に、有機アルカリ金属を５×１０−３モル加えてカ
ルバニオン化した後、アルキレンオキサイドＬｏｇを加
えればよい。また数平均分子量が４５のブロックーグラ
フト共重合体を製造するには，上記の各成分をすべて等
モルにすればよい．さらに数平均分子量が４５〜２，０
００のものでは、その中間のモル数を任意に選択するこ
とにより達成される．
このようにして得られたブロックーグラフト共重合体は
、次にリチウムイオン塩を添加複合させて高分子固体電
解質とするのであるが、この方法には特にシＪ限はなく
、例えばブロックーグラフト共重合体にリチウムイオン
塩を必要に応じメチルエチルケトンなどの溶媒に溶かし
て均一に混合する方法、ブロックーグラフト共重合体に
リチウムイオン塩を添加して常温または加熱下に機械的
に混練する方法，リチウムイオン塩を溶解したメタノー
ルなどの溶媒に、ブロックーグラフト共重合体の膜を含
浸して膜を膨潤させ、これにリチウムイオン塩を均一に
複合させる方法など、任意に選択することができる．
本発明によるリチウム電池は，正極集電板と負極集電板
との間に５リチウムまたはリチウム合金からなる負極と
両極間に介在する上記固体電解質を収容したものであり
．種々の大きさ，形状のものとすることができるが，特
に簿型構造の電池として好適である．
以下、この簿型構造のリチウム電池の詳細を、その一実
施態様を示した第１，図により説明する。The polymerization of the block copolymer T that will become the main molecular chain and the reaction for the growth of its branch molecular chains are usually carried out in an organic solvent. Examples of organic solvents that can be used for this are tetrahydrofuran, dioxane, etc. Solvents for anionic polymerization or ring-opening polymerization, such as , tetrahydrobilane, and benzene, are preferred. Compounds used to terminate polymerization include, for example, acids such as acetic acid; halides such as methyl bromide and penzyl chloride; silyl compounds such as trimethylsilyl chloride and t-butyldimethylsilyl chloride; and the like. Control of the length of the graft chain is determined by the number of moles of block flAC contained in the block-graft copolymer, the amount of organic alkali metal during carbanionization, and the amount of alkylene oxide. That is, the amount of organic alkali metal must not exceed the number of moles of block chain C, and the length of the graft chain is expressed as. For example, the length of the graft chain is 2,000 in number average molecular weight.
To produce a block-graft copolymer containing 7 x 10-3 mol of block chain C, 5 x 10-3 mol of an organic alkali metal is added to carbanionize the block-graft copolymer, and then alkylene oxide Log Just add. Furthermore, in order to produce a block-graft copolymer with a number average molecular weight of 45, all of the above components should be made equal in mole. Furthermore, the number average molecular weight is 45 to 2,0
00, this can be achieved by arbitrarily selecting an intermediate number of moles. The block-graft copolymer thus obtained is then combined with a lithium ion salt to form a solid polymer electrolyte, but there is no particular limit to this method; for example, block-graft copolymer A method in which a lithium ion salt is dissolved in a solvent such as methyl ethyl ketone as necessary to the copolymer and mixed uniformly, a method in which a lithium ion salt is added to a block-graft copolymer and mechanically kneaded at room temperature or under heating, Any method can be selected, such as impregnating a block-graft copolymer membrane in a solvent such as methanol in which a lithium ion salt is dissolved, allowing the membrane to swell, and then uniformly compounding the lithium ion salt. The lithium battery according to the present invention contains a negative electrode made of 5 lithium or a lithium alloy between a positive current collector plate and a negative current collector plate, and the solid electrolyte interposed between the two electrodes. Although it can be made into various sizes and shapes, it is particularly suitable for batteries with a book-shaped structure. Hereinafter, details of this book-shaped lithium battery will be explained with reference to Figure 1, which shows one embodiment thereof.
図において、１はステン１ノス鋼からなる方形平板状の
正極集電板，２は同様にステンレス鋼からなる方形皿状
の負極集電板で、この周縁部は段状に折り曲げられてツ
バ状の平坦部２ａを形成している。３は両極集電板１、
２をそれぞれの相対する周縁部】ａ、２ａにおいて結合
・封止するための接着剤層、４は両極集電板１、２によ
って包囲形成される空隙である．この空隙４内には正極
集電板１側に正極５が、負極集電板２側にリチウムまた
はリチウム合金からなる負極６が、それぞれ高分子固体
電解質７を介して配設されている。８は正極５の周りに
設けられたポリブロビレンなどからなる方形状の枠体で
ある．
上記構成のリチウム電池において，接着剤層３の形成に
は汎用の塗料溶液型接着剤を利用してもよいが、熱融着
性材料からなる環状シートを用いた方が好ましい。すな
わち、両極集電板１、２の周縁部１ａ．２ａの幅に対応
する幅を有する環状の熱融着性材料からなるシートを予
め準備し、これを周縁部１ａ、２ａ間に挿着し、両周縁
部を圧接した後，このままの状態で所定温度に加熱する
ことによって両周縁部を結合させることができる。In the figure, 1 is a rectangular plate-shaped positive electrode current collector plate made of stainless steel, and 2 is a rectangular dish-shaped negative electrode current collector plate also made of stainless steel. A flat portion 2a is formed. 3 is a bipolar current collector plate 1;
[2] A, an adhesive layer for bonding and sealing 2a at the opposing peripheral edges; 4 is a gap surrounded by the bipolar current collector plates 1 and 2; In this gap 4, a positive electrode 5 is disposed on the positive electrode current collector plate 1 side, and a negative electrode 6 made of lithium or a lithium alloy is disposed on the negative electrode current collector plate 2 side, with a solid polymer electrolyte 7 in between. Reference numeral 8 denotes a rectangular frame made of polypropylene, etc., provided around the positive electrode 5. In the lithium battery having the above structure, a general-purpose paint solution type adhesive may be used to form the adhesive layer 3, but it is preferable to use an annular sheet made of a heat-fusible material. That is, the peripheral edges 1a of the bipolar current collector plates 1 and 2. A sheet made of an annular heat-fusible material having a width corresponding to the width of 2a is prepared in advance, and this is inserted between the peripheral edges 1a and 2a, and after pressing the two peripheral edges together, the sheet is held in a predetermined position in this state. Both peripheral edges can be bonded together by heating to a temperature.
この方法では固体の熱融着性材料を用いるので取扱いお
よび取付け操作が極めて容易になることのほか、塗料溶
液型接着剤のように空隙４内に流入して電解質、電極と
混じり合う恐れがない．なお，この熱融着性材料にはホ
ットメルト型接着剤、ハーメチックシールの可能なセラ
ミックスを始め種々のものを適用することができる。Since this method uses a solid heat-fusible material, it is extremely easy to handle and install, and there is no risk of it flowing into the cavity 4 and mixing with the electrolyte and electrodes, unlike paint solution adhesives. ．． Note that various materials can be used as the heat-fusible material, including hot-melt adhesives and ceramics capable of hermetic sealing.
正極５としては，従来リチウム電池用の正極活物質とし
て適用された種々のもの髪使用することができるが．特
に好適なものとしてはＭ ｎ Ｏ．、Ｔｉｅ．、Ｍ ｏ
Ｓ ，、ｖ．ｏ，．．ｖ．ｏ，、ＮｉＰＳ，などのほ
か、ボリアニリン、ポリアセチレンなどの導電性高分子
が挙げられ，これらは２種以上を併用してもよい。As the positive electrode 5, various materials that have been conventionally used as positive electrode active materials for lithium batteries can be used. Particularly preferred are M n O. , Tie. , M o
S,,v. o,. ．． v. In addition to NiPS, etc., conductive polymers such as polyaniline and polyacetylene may be used, and two or more of these may be used in combination.
負極６としては、リチウムまたはリチウム合金のいずれ
でも使用可能であるが，リチウム単独では長期の使用の
間に劣化する恐れがあるので，アルミニウムなどとの合
金化を図ることが望ましい．なお、本発明によるリチウ
ム電池では両極集電板】．、２の構造を．前記図示のも
の以外に、両方を皿状にしたもの，両方を平板状として
それぞれの周縁部間にセラミックス製などのスペーサを
介在させたものなどとすることもできる。As the negative electrode 6, either lithium or a lithium alloy can be used, but since lithium alone may deteriorate during long-term use, it is preferable to alloy it with aluminum or the like. In addition, in the lithium battery according to the present invention, the bipolar current collector plate]. , the structure of 2. In addition to the illustrated structure, both may be plate-shaped, or both may be plate-shaped and a spacer made of ceramic or the like may be interposed between the peripheral edges of each.
また、電池の外形は方形以外の多角形，円形など用途に
応じて種々の形状とすることができる。Further, the external shape of the battery can be made into various shapes depending on the purpose, such as a polygon other than a rectangular shape, or a circular shape.
さらに電池の総厚は１．０＋ａ以下．とくにはＯ。３〜
０．７ａｍ程度にするのが好ましく、これにより本発明
の適用効果が大となる。Furthermore, the total thickness of the battery is 1.0+a or less. Especially O. 3~
It is preferable to set it to about 0.7 am, which increases the application effect of the present invention.
（実施例）
以下、本発明の具体的実施態様を実施例および比較例に
基づいてさらに詳細に説明するが，本発明はこの実施例
の記載に限定されるものではない。(Examples) Hereinafter, specific embodiments of the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the description of these Examples.
なお，例中のブロック共重合体は，各成分をｒ−ｂ−Ｊ
でつないで，例えば「ボリスチレン、ポリーｐ−ヒドロ
キシスチレン、ボリスチレンの三成分三元ブロック共重
合体」を，「ポリ（スチレンーｂｐ−ヒドロキシスチレ
ンーｂ−スチレン）」と表記し，グラフト共重合体は，
各成分をｒ−ｇ−Ｊでつないで，例えば『ボリスチレン
，ボリーｐ−ヒドロキシスチレン，ポリスチレンの三成
分三元ブロック共重合体とポリエチレンオキサイドとの
ブロックーグラフト共重合体」を．「ポリ〔スチレンー
ｂ−（ｐ−ヒド口キシスチレンーｇ一エチレンオキサイ
ド）−ｂ−スチレン〕」と表記する。In addition, in the block copolymer in the example, each component is r-b-J
For example, "a ternary block copolymer of boristyrene, poly p-hydroxystyrene, and boristyrene" is written as "poly(styrene-bp-hydroxystyrene-b-styrene)," and a graft copolymer is ，
Each component is connected with r-g-j to form, for example, a block-graft copolymer of a ternary block copolymer of polystyrene, poly-p-hydroxystyrene, and polystyrene and polyethylene oxide. It is written as "poly[styrene-b-(p-hydroxystyrene-g-ethylene oxide)-b-styrene]".
また，各例中の電池のサイクル特性は２５℃の温度下で
１００μＡの定電流による充放電サイクル特性を充電終
止電圧： ３．５Ｖ、放電終止電圧： ｌ．５Ｖとして
測定したものである。In addition, the cycle characteristics of the battery in each example are the charge/discharge cycle characteristics at a constant current of 100 μA at a temperature of 25° C., end-of-charge voltage: 3.5V, end-of-discharge voltage: l. It was measured at 5V.
実施例 １
ポリエチレンオキサイド成分が重量比で４４％、分子量
が５００であるポリ〔スチレンーｂ−（ｐ−ヒドロキシ
スチレンーｇ一エチレンオキサイド）−ｂ−スチレン）
２ｇとＬｉＣ１０．０．５ｇとを５０ｍｌの酢酸エチル
に溶解し、テフロン板上に流延した．この膜を室温で２
４時間放置して過剰の溶媒を除去した後、さらに６０℃
で２４時間減圧乾燥して均一な固体電解質を得た。この
電解質のイオン伝導率は４．０×１０″３であった．
一方、厚さが０．１ａｍで一片の長さが１５ｍの正方形
のステンレス製平板からなる正極集電板１上に、ボリプ
ロビレン製の方形の枠体８を置き、ＴｉＳ，がその中に
充満するようにスキージ塗布法により塗布して、厚さが
０．１一で一片の長さが１０ｍの正方形の正極５を作製
した．
この上に厚さが１００μ層の上記の固体電解質７を置き
、さらにこの上に厚さが８０４で一片の長さが４＋ｍの
正方形のりチウムーアルミニウム合金の箔からなる負極
６を重ねて積層した．
次に、正極集電板１の周縁部ｌａ上に、厚さが６０４、
外郭の一片の長さが１５−、幅２ｍの正方形環状のシ一
ト３からなる変性ポリオレフイン系ホットメルト接着剤
を置き、その上に厚さが０．１ｍ、一片の長さが１５ｍ
、深さが０．４ｍの正方形皿状のステンレス製板からな
る負極集電板２を被せ、両極集電板の周縁部１ａ、２ａ
を圧接した後、 １８５℃に加熱し上記シ一ト３により
熱融着封止して、第１図に示したのと同様の構造の、一
片の長さが２５曙の正方形で，総厚が０．５一の簿型の
リチウム電池を製作した。Example 1 Poly[styrene-b-(p-hydroxystyrene-g-ethylene oxide)-b-styrene] with a polyethylene oxide component of 44% by weight and a molecular weight of 500
2 g and 10.0.5 g of LiC were dissolved in 50 ml of ethyl acetate and cast on a Teflon plate. This film was heated for 2 hours at room temperature.
After leaving for 4 hours to remove excess solvent, further heat to 60°C.
The solid electrolyte was dried under reduced pressure for 24 hours to obtain a uniform solid electrolyte. The ionic conductivity of this electrolyte was 4.0×10″3. On the other hand, polypropylene A square positive electrode 5 having a thickness of 0.1 m and a piece length of 10 m was prepared by applying TiS using a squeegee coating method so that it was filled with TiS. . On top of this, the solid electrolyte 7 with a thickness of 100 μm was placed, and on top of this, a negative electrode 6 made of a square lithium-aluminum alloy foil with a thickness of 804 mm and a piece of length 4+ m was laminated. Next, on the peripheral edge la of the positive electrode current collector plate 1, a layer with a thickness of 604 mm,
A modified polyolefin hot-melt adhesive consisting of a square annular sheet 3 with one piece of the outer shell having a length of 15 m and a width of 2 m was placed, and on top of it a modified polyolefin hot melt adhesive with a thickness of 0.1 m and a length of one piece of 15 m.
, a negative electrode current collector plate 2 made of a square dish-shaped stainless steel plate with a depth of 0.4 m is covered, and the peripheral edges 1a and 2a of the bipolar current collector plates are covered.
After welding them under pressure, we heated them to 185°C and sealed them by heat sealing with the sheet 3 mentioned above, and made a square piece with a length of 25 mm and a total thickness similar to that shown in Figure 1. A book-shaped lithium battery with a value of 0.51 was manufactured.
このリチウム電池は開路電圧３．Ｏｖであり、そのサイ
クル特性を第２図に、また１００サイクルｌ］の充放電
における電池電圧の経時変化を第３図に示した。This lithium battery has an open circuit voltage of 3. The cycle characteristics are shown in FIG. 2, and the change in battery voltage over time during charging and discharging for 100 cycles is shown in FIG. 3.
実施例 ２
原料としてポリエチレンオキサイド成分が重量比で２８
％、分子量が２８０であるボリ〔スチレンーｂ−（ｐ−
ヒドロキシスチレンーｇ一エチレンオキサイド）一ｂ−
スチレン〕の２ｇとＬｉＢＦ．の０．５ｇとを使用した
ほかは、実施例１と同様にして蒲型のリチウム電池を製
作した。この電池は開路電圧３．Ｏｖであり、そのサイ
クル特性を第２図に，また１００サイクル］１の充放電
における電池電圧の経時変化を第３図にそれぞれ示した
．
なお、ここで用いた固体電解質のイオン伝導率は２．Ｏ
Ｘ １０−’であった。Example 2 Polyethylene oxide component as a raw material has a weight ratio of 28
%, molecular weight is 280, polystyrene-b-(p-
Hydroxystyrene-g-ethylene oxide)-
2 g of styrene] and LiBF. A cap-shaped lithium battery was produced in the same manner as in Example 1, except that 0.5 g of the above was used. This battery has an open circuit voltage of 3. Figure 2 shows its cycle characteristics, and Figure 3 shows the change in battery voltage over time during charging and discharging for 100 cycles. The ionic conductivity of the solid electrolyte used here was 2. O
It was X 10-'.
実施例 ３
原料として実施例１の高分子固体電解質を使用し、正極
材料にＶ，Ｏ，を使用したほかは、実施例１と同様にし
て薄型リチウム電池を製作した．この電池は開路電圧３
。Ｏｖであり、そのサイクル特性を第２図に、また１０
０サイクル］」の充放電における電池電圧の経時変化を
第３図にそれぞれ示した．比較例 １
数平均分子葉が６００ ， ０００のポリエチレンオキ
サイドを１ｇとＬｉＣ Ｆ， Ｓ Ｏ，を０，２３６ｇ
とをアセトニトリル５膳ｌに溶解し、スターラで均一に
攪拌した．次に，この溶液をテフロン基板上に流延し，
常圧下アルゴンガス中で放置した後、温度１３０℃で真
空乾燥してアセトニトリルを蒸発除去し、厚みが２０／
ｊＩｍの高分子固体電解貿を得た。このイオン伝導率は
１．ＯＸ１０−’であった。Example 3 A thin lithium battery was manufactured in the same manner as in Example 1, except that the polymer solid electrolyte of Example 1 was used as the raw material and V, O, was used as the positive electrode material. This battery has an open circuit voltage of 3
. Ov, its cycle characteristics are shown in Figure 2, and 10
Figure 3 shows the changes in battery voltage over time during charging and discharging of 0 cycles. Comparative Example 1 1 g of polyethylene oxide with a number average molecular weight of 600,000 and 0,236 g of LiC F, SO.
was dissolved in 5 liters of acetonitrile and stirred uniformly with a stirrer. Next, this solution was cast onto a Teflon substrate.
After being left in an argon gas atmosphere under normal pressure, the acetonitrile was evaporated off by vacuum drying at a temperature of 130°C.
Obtained polymer solid electrolyte trade from jIm. This ionic conductivity is 1. It was OX10-'.
これを用いて実施例１と同様にしてリチウム電池を製作
した。Using this, a lithium battery was manufactured in the same manner as in Example 1.
比較例 ２
原料として数平均分子量が３００，０００のポリエチレ
ンオキサイドを１ｇとＬｉＣＦ３ＳＯ，を０．７１７
ｇ、正極材料にＶ，Ｏ，を使用したほかは、前例と同様
にして高分子固体電解質を得た。このイオン伝導率は２
．２ Ｘ １０−’であった．
これを用いて実施例１と同様にしてリチウム電池を製作
した．
さらに、以上の各実施例および比較例で得られた高分子
固体電解質について、その放電特性を測定した結果を第
４図に示した．
（発明の効果）
本発明によるリチウム電池はイオン伝導度が高く、成形
性のよい高分子固体電′解質を用いるため，充放電特性
に優れ経時的な性能低下が少なく、高性能化および長寿
命化の要望に十分に対応できる．Comparative Example 2 As raw materials, 1 g of polyethylene oxide with a number average molecular weight of 300,000 and LiCF3SO, 0.717
g. A solid polymer electrolyte was obtained in the same manner as in the previous example except that V and O were used as the positive electrode materials. This ionic conductivity is 2
．． It was 2 x 10-'. Using this, a lithium battery was manufactured in the same manner as in Example 1. Furthermore, the discharge characteristics of the polymer solid electrolytes obtained in each of the above Examples and Comparative Examples were measured, and the results are shown in FIG. (Effects of the Invention) The lithium battery according to the present invention has high ionic conductivity and uses a polymer solid electrolyte with good moldability, so it has excellent charge and discharge characteristics, has little performance deterioration over time, has improved performance, and has a long lifespan. It can fully meet the demands for longer service life.
第１図は本発明によるリチウム電池の一実施態様につい
ての縦断面図、第２図は各実施例で得らｉだリチウム電
池についてサイクル特性を測定した結果を示すグラフ，
第３図は同様のリチウム電池について１００サイクル目
の充放電における電池電圧の経時変化をを測定した結果
を示すグラフ、第４図は各実施例および比較例で得られ
た高分子固体電解質について、その放電特性を測定した
結果を示すグラフである．
第２図
３６ｅＩ
サイクル劃（
第３図
鴫デｊFIG. 1 is a longitudinal cross-sectional view of one embodiment of the lithium battery according to the present invention, and FIG. 2 is a graph showing the results of measuring cycle characteristics of the lithium batteries obtained in each example.
Figure 3 is a graph showing the results of measuring changes in battery voltage over time at the 100th charge/discharge cycle for similar lithium batteries, and Figure 4 is for the solid polymer electrolytes obtained in each example and comparative example. This is a graph showing the results of measuring the discharge characteristics. Fig. 2 36eI Cycle section ( Fig. 3
Claims (1)
基、Ｒ＾２は水素原子またはメチル基、Ｒ＾３はアルキ
ル基、アリール基、アシル基、またはシリル基、ｍは１
〜４５の整数であり、ｐは整数、式中の▲数式、化学式
、表等があります▼で示されるグラフト鎖の数平均分子
量は４５以上２，０００未満である）で表される繰返し
単位からなる少なくとも１種の重合体のブロック鎖Ａと
、 一般式（II） ▲数式、化学式、表等があります▼……（II） （ここに、Ｒ＾４は水素原子、メチル基、またはエチル
基、Ｍは式−ＣＨ＝ＣＨ＿２、 −Ｃ（ＣＨ＿２）＝ＣＨ＿２−ＣＯＯＣＨ＿３、または
−ＣＯＯＣ＿２Ｈ＿５で表される基、フェニル基、もし
くは置換フェニル基、ｎは整数である） で表される繰返し単位からなる少なくとも１種の重合体
のブロック鎖Ｂ、 とから構成されるブロック−グラフト共重合体のリチウ
ムイオン塩との複合物を、電解質として内蔵してなるリ
チウム電池。[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (Here, R^1 is a hydrogen atom, a methyl group, or an ethyl group, and R^2 is a Hydrogen atom or methyl group, R^3 is an alkyl group, aryl group, acyl group, or silyl group, m is 1
~45 integer, p is an integer, and from the repeating unit represented by ▲ in the formula (there are mathematical formulas, chemical formulas, tables, etc.) the number average molecular weight of the graft chain indicated by ▼ is 45 or more and less than 2,000) At least one polymer block chain A having the general formula (II) ▲Mathematical formula, chemical formula, table, etc.▼...(II) (Here, R^4 is a hydrogen atom, a methyl group, or an ethyl group. , M is a group represented by the formula -CH=CH_2, -C(CH_2)=CH_2-COOCH_3, or -COOC_2H_5, a phenyl group, or a substituted phenyl group, n is an integer). A lithium battery comprising, as an electrolyte, a composite of a block-graft copolymer and a lithium ion salt consisting of at least one type of polymer block chain B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1051288A JPH02230667A (en) | 1989-03-03 | 1989-03-03 | Lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1051288A JPH02230667A (en) | 1989-03-03 | 1989-03-03 | Lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02230667A true JPH02230667A (en) | 1990-09-13 |
| JPH0574195B2 JPH0574195B2 (en) | 1993-10-15 |
Family
ID=12882745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1051288A Granted JPH02230667A (en) | 1989-03-03 | 1989-03-03 | Lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02230667A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04147571A (en) * | 1990-10-11 | 1992-05-21 | Shin Etsu Chem Co Ltd | Lithium battery |
| JP2000021448A (en) * | 1998-06-30 | 2000-01-21 | Sanyo Electric Co Ltd | High polymer electrolyte secondary battery |
| US6025437A (en) * | 1997-03-04 | 2000-02-15 | Shin-Etsu Chemical Co., Ltd. | Block-graft copolymer, self-crosslinked polymer solid electrolyte and composite solid electrolyte manufactured through use of the block-graft copolymer, and solid cell employing the composite solid electrolyte |
| US6096234A (en) * | 1997-01-23 | 2000-08-01 | Shin-Etsu Chemical Co., Ltd. | Cross-linked polymer solid electrolyte, method of manufacturing cross-linked solid polymer electrolyte, composite solid electrolyte, and thin solid cell employing composite solid electrolyte |
| KR100421762B1 (en) * | 1996-01-31 | 2004-06-14 | 에이이에이 테크놀로지 배터리 시스템즈 리미티드 | Electrolyte Containing Polymer Composition |
| JP2011014387A (en) * | 2009-07-02 | 2011-01-20 | Nippon Zeon Co Ltd | All-solid secondary battery |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6322924B1 (en) | 1999-01-29 | 2001-11-27 | Shin-Etsu Chemical Co., Ltd. | Preparation of crosslinked solid polymer electrolyte |
| JP7302476B2 (en) * | 2017-08-31 | 2023-07-04 | 日本ゼオン株式会社 | Composition for electrochemical element functional layer, functional layer for electrochemical element, and electrochemical element |
-
1989
- 1989-03-03 JP JP1051288A patent/JPH02230667A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04147571A (en) * | 1990-10-11 | 1992-05-21 | Shin Etsu Chem Co Ltd | Lithium battery |
| KR100421762B1 (en) * | 1996-01-31 | 2004-06-14 | 에이이에이 테크놀로지 배터리 시스템즈 리미티드 | Electrolyte Containing Polymer Composition |
| US6096234A (en) * | 1997-01-23 | 2000-08-01 | Shin-Etsu Chemical Co., Ltd. | Cross-linked polymer solid electrolyte, method of manufacturing cross-linked solid polymer electrolyte, composite solid electrolyte, and thin solid cell employing composite solid electrolyte |
| US6025437A (en) * | 1997-03-04 | 2000-02-15 | Shin-Etsu Chemical Co., Ltd. | Block-graft copolymer, self-crosslinked polymer solid electrolyte and composite solid electrolyte manufactured through use of the block-graft copolymer, and solid cell employing the composite solid electrolyte |
| JP2000021448A (en) * | 1998-06-30 | 2000-01-21 | Sanyo Electric Co Ltd | High polymer electrolyte secondary battery |
| JP2011014387A (en) * | 2009-07-02 | 2011-01-20 | Nippon Zeon Co Ltd | All-solid secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0574195B2 (en) | 1993-10-15 |
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