JPH04179065A - Ion conductive visco-elastic substance and secondary battery - Google Patents
Ion conductive visco-elastic substance and secondary batteryInfo
- Publication number
- JPH04179065A JPH04179065A JP2302578A JP30257890A JPH04179065A JP H04179065 A JPH04179065 A JP H04179065A JP 2302578 A JP2302578 A JP 2302578A JP 30257890 A JP30257890 A JP 30257890A JP H04179065 A JPH04179065 A JP H04179065A
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- solid electrolyte
- solid
- meth
- acrylate
- 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
- 239000003190 viscoelastic substance Substances 0.000 title abstract description 3
- 229940006076 viscoelastic substance Drugs 0.000 title abstract 2
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 22
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 4
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims 1
- 239000007784 solid electrolyte Substances 0.000 abstract description 52
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 239000007787 solid Substances 0.000 abstract description 14
- 150000003839 salts Chemical class 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000008151 electrolyte solution Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- -1 [N(BLI)4] Chemical class 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- 239000003792 electrolyte Substances 0.000 description 20
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000956 alloy Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- 150000004291 polyenes Chemical class 0.000 description 8
- 229920006295 polythiol Polymers 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 238000012719 thermal polymerization Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
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- 229920002635 polyurethane Polymers 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 230000008018 melting Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 2
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000713 I alloy Inorganic materials 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 229920001079 Thiokol (polymer) Polymers 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 125000001153 fluoro group Chemical class F* 0.000 description 2
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- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 1
- 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 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 229910052960 marcasite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SNWKNPMDQONHKK-UHFFFAOYSA-N methyl 2-sulfanylpropanoate Chemical compound COC(=O)C(C)S SNWKNPMDQONHKK-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000323 polyazulene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、イオン伝導体及び二次電池に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to an ion conductor and a secondary battery.
［従来の技術］
電気化学反応を利用した電気化学素子の固体化（固形化
）が強く望まれている。従来より電気化学素子は電解液
を使用しているため、電解液の漏れ、溶媒の揮発による
容器内の乾燥があるばかりでなく、容器内では電解液の
かたよりにより隔膜が部分的に乾燥状態になり、このこ
とが内部インピーダンスの上昇あるいは内部短絡の原因
になる。これらの欠点を解決するための方法として高分
子固体電解質を用いることが提案されている。その具体
的例として、オキシエチレン鎖、オキシプロピレン鎖を
含有するマトリックスポリマーと無機塩の固溶体が挙げ
られるが、このものは完全固体であり、加工性にも優れ
るものの、そのイオン伝導度は室温で１０″’ Ｓ／ｃ
−と通常の非水電解液に比べて３桁はど低い。この低い
伝導度を改良する方法として、高分子固体電解質の薄膜
化も提案されているが、ミクロンオーダーの薄膜を電池
内部の電界が均一になるようにコントロールすることは
難しくかつ信頼性も低い。[Prior Art] There is a strong desire to solidify (solidify) electrochemical elements using electrochemical reactions. Conventionally, electrochemical devices use electrolyte, so not only can the container dry out due to electrolyte leakage or solvent volatilization, but also the diaphragm can become partially dry inside the container due to the electrolyte being biased. This causes an increase in internal impedance or an internal short circuit. The use of solid polymer electrolytes has been proposed as a method to solve these drawbacks. A specific example is a solid solution of a matrix polymer containing oxyethylene chains or oxypropylene chains and an inorganic salt. Although this material is completely solid and has excellent processability, its ionic conductivity is low at room temperature. 10'' S/c
-, which is three orders of magnitude lower than normal non-aqueous electrolytes. As a way to improve this low conductivity, making a solid polymer electrolyte into a thin film has been proposed, but it is difficult and unreliable to control a micron-order thin film so that the electric field inside the battery is uniform.
高分子固体電解質のイオン伝導度を向上させるために、
高分子に有機電解液を溶解させて半固形状のものにする
方法（特開昭５４−１０４５４１号公報）や、電解質を
加えた液状モノマーを重合反応させて電解質を含む架橋
重合体とする方法（特開昭６３−９４５０１号公報）が
提案されている。To improve the ionic conductivity of polymer solid electrolytes,
A method of dissolving an organic electrolyte in a polymer to form a semi-solid product (Japanese Unexamined Patent Publication No. 104541/1982), and a method of polymerizing a liquid monomer to which an electrolyte has been added to form a crosslinked polymer containing an electrolyte. (Japanese Unexamined Patent Publication No. 63-94501) has been proposed.
しかし、前者の方法で得られる固体電解質はその固体強
度が十分でないという問題を含み、また、後者の方法で
得られる固体電解質は、十分な固体強度を有するものの
、イオン伝導度の点で未だ不満足であるという問題を含
んでいる。However, the solid electrolyte obtained by the former method has a problem of insufficient solid strength, and the solid electrolyte obtained by the latter method, although it has sufficient solid strength, is still unsatisfactory in terms of ionic conductivity. It includes the problem that.
また、固体電解質を用いるリチウム二次電池の提案も盛
んに行われている。しかしながら、負極活物質にはほと
んどの場合がＬｉを用いるため、モス状リチウム、デン
ドライトのためサイクル寿命が十分でない。Ｌｉ−Ａ１
合金の使用も考えられるが、一般にＬｉ−Ａ１合金はも
ろく、粉末となりやすいため、やはりサイクル寿命が十
分ではない。Furthermore, proposals for lithium secondary batteries using solid electrolytes are also being actively made. However, since Li is used as the negative electrode active material in most cases, the cycle life is not sufficient due to moss-like lithium and dendrite. Li-A1
The use of alloys is also considered, but generally Li-A1 alloys are brittle and easily turn into powder, so the cycle life is still insufficient.
［発明が解決しようとする課題］
本発明は従来の高分子を基材とする固体電解質に見られ
る前記問題点を解決し、イオン伝導度及び均一性にすぐ
れるとともに、各種素子用固体電解質としての使用に十
分な固体強度を有する高分子を基材とする固体電解質を
提供することをその目的とする。[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems found in conventional solid electrolytes based on polymers, has excellent ionic conductivity and uniformity, and can be used as a solid electrolyte for various devices. The object is to provide a solid electrolyte based on a polymer having sufficient solid strength for use in.
さらに、それを用いる長サイクル寿命の二次電池を提供
することをその目的とする。Furthermore, it is an object of the present invention to provide a secondary battery with a long cycle life using the same.
［課題を解決するための手段］
本発明者らは、前記課題を解決すべく鋭意検討を重ねた
結果、重合性化合物を非水電解液に溶解させて重合反応
を行わせることによりイオン伝導性粘弾性体が得られる
ことを見出し、その際に非水電解液中に含有している電
解質塩、特にカチオンの種類により固体強度が大きく変
化することを見出した。そして、さらに鋭意検討を重ね
た結果、非水電解液中に多価カチオンを含有した非水電
解液に重合性化合物を溶解させて重合反応を行わせるこ
とにより、多量の非水電解液を固体化することが可能で
、得られる重合反応物も十分な固体強度とイオン伝導度
を有する粘弾性体となることを見出し、本発明に至った
。[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors have discovered that ion conductivity can be achieved by dissolving a polymerizable compound in a non-aqueous electrolyte and causing a polymerization reaction. It has been found that a viscoelastic body can be obtained, and that the solid strength varies greatly depending on the type of electrolyte salt, especially the cation, contained in the non-aqueous electrolyte. As a result of further intensive studies, we discovered that by dissolving a polymerizable compound in a non-aqueous electrolyte containing polyvalent cations and causing a polymerization reaction, a large amount of the non-aqueous electrolyte can be solidified. It has been found that the resulting polymerization reaction product becomes a viscoelastic body having sufficient solid strength and ionic conductivity, leading to the present invention.
即ち、本発明は高分子量重合体に非水電解液を含有する
構造の粘弾性体であって、該非水電解液中に多価カチオ
ンを含有することを特徴とするイオン伝導性粘弾性体で
ある。That is, the present invention relates to an ion-conducting viscoelastic body having a structure in which a high molecular weight polymer contains a non-aqueous electrolyte, and the non-aqueous electrolyte contains polyvalent cations. be.
さらに、上記イオン伝導性粘弾性体を二次電池、特にＡ
ｌ集電体上にＬ ｉ −Ａ Ｉ合金層を有する負極を用
いる二次電池に使用した場合、負極のサイクル寿命の上
昇による二次電池の性能の向上を見出し、本発明に至っ
た。Furthermore, the ion conductive viscoelastic body is used in a secondary battery, especially A
When used in a secondary battery using a negative electrode having a Li-AI alloy layer on a current collector, the inventors discovered that the performance of the secondary battery is improved due to an increase in the cycle life of the negative electrode, leading to the present invention.
即ち、本発明は、Ａｌ集電体上にＬ ｉ −Ａ １合金
層を有する負極を用いる二次電池において、上記イオン
伝導性粘弾性体を用いることを特徴とする二次電池であ
る。That is, the present invention is a secondary battery using a negative electrode having a Li-A 1 alloy layer on an Al current collector, characterized in that the above-mentioned ion-conductive viscoelastic body is used.
本発明の固体電解質は高分子量重合体基材と、非水電解
液とから構成される全体が均質な粘弾性体からなるもの
である。また本発明の固体電解質は高いイオン伝導度、
低弾性串、低いガラス転移温度（Ｔｇ） 、高温安定性
、８加工性、低いクリープ特性および粘着性を有し、さ
らに多量の電解液を含みながら保液性に優れたものであ
る。その上、保形性の優れたものである。本発明の固体
電解質の交流インピーダンス法による２５℃のイオン伝
導度は本電解質の構成要素である非水電解液の伝導率に
大きく影響を受けるとともに、それを超えるものではな
いが、固体化によってその伝導率の低下はほとんどなく
、通常１０−４〜１Ｏ−２Ｓ／ｃｍを有する。動的粘弾
性試験機（Ｊ？）ＩＥＯＭＥＴＲＩＣ，ＩＮＣ■ＲＤＳ
−７７００）による弾性率は通常１０ ｄｙｎｅ／ｃ
ｄ以下、好ましくは１０３〜１０５ｄｙｎｅ／ｃｄであ
り、Ｔｇは一３０℃以下であり、１００℃においても溶
解することはない。クリープはクリープメーター（山型
ＩＩＲＥ−１３０５．プランジャー断面積２０−２荷重
３０ｇ）を使用して歪量の時間変化を測定したところ、
歪量は時間で変化せず低いクリープ特性を有する。クリ
ープメーターを使用して荷重２５ＪｒノＣ−で本固体電
解質を圧縮しても内部に含まれる電解液が流出すること
はない。さらに、この粘弾性体は高い粘着性密着を示し
、粘弾性体同士を張り合わせた後、剥離しようとしても
容易に剥がれることはない。The solid electrolyte of the present invention is entirely made of a homogeneous viscoelastic body composed of a high molecular weight polymer base material and a non-aqueous electrolyte. In addition, the solid electrolyte of the present invention has high ionic conductivity,
It has a low elasticity skewer, a low glass transition temperature (Tg), high temperature stability, 8 processability, low creep properties and tackiness, and also has excellent liquid retention properties even though it contains a large amount of electrolyte. Moreover, it has excellent shape retention. The ionic conductivity at 25°C measured by the AC impedance method of the solid electrolyte of the present invention is greatly influenced by the conductivity of the non-aqueous electrolyte that is a component of the present electrolyte, and although it does not exceed the conductivity of the non-aqueous electrolyte, it is There is almost no decrease in conductivity, and the conductivity is usually 10-4 to 10-2S/cm. Dynamic viscoelasticity tester (J?) IEOMETRIC, INC ■RDS
-7700) is usually 10 dyne/c
d or less, preferably 103 to 105 dyne/cd, Tg is -30°C or less, and does not dissolve even at 100°C. Creep was determined by measuring the change in strain over time using a creep meter (IIRE-1305, plunger cross-sectional area: 20-2, load: 30 g).
The amount of strain does not change over time and has low creep characteristics. Even when this solid electrolyte is compressed using a creep meter under a load of 25 Jr., the electrolyte contained therein will not flow out. Furthermore, this viscoelastic body exhibits high adhesive adhesion, and even if the viscoelastic bodies are pasted together and an attempt is made to peel them off, they will not peel off easily.
本発明のイオン伝導性粘弾性体中に含有している非水電
解液中にはＭｇ 、Ｚｎ 、Ｐｂ２”、２＋
２＋
２＋ ２＋ ２＋ 、’
ｌ＋ ３＋Ｍｎ 、Ｃｄ 、Ｆｅ
、Ｎｌ 、Ａｌ 。The non-aqueous electrolyte contained in the ion-conducting viscoelastic body of the present invention contains Mg, Zn, Pb2'', 2+
2+ 2+ 2+ 2+ ,'
l+ 3+Mn, Cd, Fe
, Nl, Al.
３＋ ３＋
Ｇａ 、Ｉｎ 、Ｆｅ”＋のごとき多価カチオンを
含有している。非水電解液中のカチオンは粘弾性体を製
造する際の重合反応に関与し、重合体の架橋に寄与して
いると考えられている。そのためＬｉ 、 Ｎａ
、 Ｋ ％ ［Ｎ（ＢＬＩ）４］ のごとき−価の
カチオンに比べ、多価カチオンの方が架橋に寄与する効
果が高く、低濃度においても十分な固体強度を持つイオ
ン伝導性粘弾性体が得られるものと考えられる。具体的
に多価カチオンを供給する電解質としては、カチオン２
＋ ２＋ ２＋
２＋として、Ｍ ｇ ｓ Ｚ ｎ ＳＰ ｂ ｓ
Ｍ ｎ ｓ’ｌ＋ ２＋ 、 ２＋
３＋ ：ＤＣｄ 、Ｆｅ 、Ｎ１ 、Ａ
ｌ 、Ｇａ 。3+ 3+ Contains polyvalent cations such as Ga, In, and Fe"+. The cations in the nonaqueous electrolyte participate in the polymerization reaction when producing the viscoelastic body and contribute to crosslinking of the polymer. Therefore, Li, Na
, K % Compared to -valent cations such as [N(BLI)4], polyvalent cations are more effective in contributing to crosslinking, and an ion-conducting viscoelastic material with sufficient solid strength even at low concentrations can be obtained. This is considered to be what can be obtained. Specifically, as an electrolyte that supplies polyvalent cations, cation 2
+ 2+ 2+
As 2+, M g s Z n SP b s
M n s'l+ 2+ , 2+
3+: DCd, Fe, N1, A
l, Ga.
３＋
Ｉｎ 、Ｆｅ３＋を例示することができ、対アニオン
としてはＢＦ４−１Ｃ１０４−１ＰＦｓ−１ＡｓＦｉ−
，５ｂＦｉ−、ＣＦ３ＳＯ３−″ 、５ＣＮ−１ＣＩ−
１Ｂｒ−１■−等を例示することができる。3+ In, Fe3+ can be exemplified, and the counter anion is BF4-1C104-1PFs-1AsFi-
, 5bFi-, CF3SO3-'', 5CN-1CI-
1Br-1■-, etc. can be exemplified.
また粘弾性体のイオン伝導度の向上、及びリチウム電池
への応用を目的として、ＬｉＢＦ４、ＬｉＣ１０＋、Ｌ
ｉＰＦ５、ＬｉＡｓＦｉ、Ｌｉ５ｂＦｉ、ＬｉＣＦ３Ｓ
Ｏ３等の電解質を混合させてもかまわない。In addition, for the purpose of improving the ionic conductivity of viscoelastic bodies and applying them to lithium batteries, LiBF4, LiC10+, L
iPF5, LiAsFi, Li5bFi, LiCF3S
An electrolyte such as O3 may be mixed.
非水溶媒としてはプロピレンカーボネート、γ−ブチロ
ラクトン、エチレンカーボネート、スルホラン、ジオキ
ソラン、テトラヒドロフラン、２−メチルテトラヒドロ
フラン、ジメチルスルホキシド、１．２−ジメトキシエ
タン、１．２−エトキシメトキシエタンの他、メチルジ
グライム、メチルトリグライム、メチルテトラグライム
、エチルグライム、エチルジグライム、ブチルジグライ
ム等のグライム類が挙げられる。Examples of non-aqueous solvents include propylene carbonate, γ-butyrolactone, ethylene carbonate, sulfolane, dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1.2-dimethoxyethane, 1.2-ethoxymethoxyethane, methyl diglyme, Examples include glymes such as methyl triglyme, methyltetraglyme, ethyl glyme, ethyl diglyme, and butyl diglyme.
これらのうちグライム類とプロピレンカーボネート及び
／又はγ−ブチロラクトンとの組み合わせがイオン伝導
度、電解質塩の溶解性の点で特に好ましい。Among these, combinations of glymes and propylene carbonate and/or γ-butyrolactone are particularly preferred in terms of ionic conductivity and electrolyte salt solubility.
非水電解液中の電解質塩の濃度は非水溶媒１０００重量
部に対し、通常０．５〜７モル、好ましくは１〜５モル
の割合である。０．５モル未満では充分な固体強度を有
する固体電解液が得られない。また、７モルを超えると
無機塩の溶解が難しくなる。電解液はマトリックスを形
成する高分子量重合体に対し、通常、２００重量％以上
、好ましくは２５０〜１０００重量％である。２００重
量％未満ではイオン伝導度が低く、１０００重量％を超
えると固形化が困難になる。The concentration of the electrolyte salt in the nonaqueous electrolyte is usually 0.5 to 7 mol, preferably 1 to 5 mol, per 1000 parts by weight of the nonaqueous solvent. If the amount is less than 0.5 mol, a solid electrolyte having sufficient solid strength cannot be obtained. Moreover, if it exceeds 7 mol, it becomes difficult to dissolve the inorganic salt. The amount of the electrolytic solution is usually 200% by weight or more, preferably 250 to 1000% by weight, based on the high molecular weight polymer forming the matrix. If it is less than 200% by weight, the ionic conductivity is low, and if it exceeds 1000% by weight, solidification becomes difficult.
本発明で用いる重合性化合物は、その分子内に酸素原子
、窒素原子、イオウ原子等の炭素以外の原子を含むもの
である。これらの原子を含有する重合性化合物を非水電
解液に溶解させ、重合反応させて得られる固体電解質（
粘弾性体）においては、その炭素以外の原子は電解質塩
のイオン化を促進させ、固体電解質のイオン伝導性、強
度を向上させる働きもあると考えられる。The polymerizable compound used in the present invention contains atoms other than carbon, such as oxygen atoms, nitrogen atoms, and sulfur atoms, in its molecules. A solid electrolyte (
In viscoelastic bodies), atoms other than carbon are thought to promote the ionization of the electrolyte salt and also have the function of improving the ionic conductivity and strength of the solid electrolyte.
また、本発明で用いる重合性化合物の種類は、特に制約
されず、熱重合及び活性光線重合などの重合反応を生起
して得るものが包含されるが、特に活性光線による光重
合が好ましい。熱重合性の重合反応としてはウレタン化
反応、エポキシ、アクリレート基による重合反応等が挙
げられるがウレタン化反応が好ましい。また活性光線重
合反応としてはアクリレート、ポリエン／ポリチオール
及び架橋性マクロマー（有機シラン、ポリイソチアナフ
テン等）による重合反応が挙げられるが、好ましくはア
クリレート、ポリエン／ポリチオールによる反応である
。Further, the type of polymerizable compound used in the present invention is not particularly limited, and includes those obtained by causing polymerization reactions such as thermal polymerization and active light polymerization, but photopolymerization using active light is particularly preferred. Examples of thermally polymerizable polymerization reactions include urethanization reactions, polymerization reactions using epoxy and acrylate groups, and urethanization reactions are preferred. Examples of the actinic light polymerization reaction include polymerization reactions using acrylates, polyenes/polythiols, and crosslinkable macromers (organosilane, polyisothianaphthene, etc.), but reactions using acrylates and polyenes/polythiols are preferred.
以下、熱重合におけるウレタン化反応、活性光線重合に
おけるアクリレート、ポリエン／ポリチオール反応につ
いて詳述する。The urethanization reaction in thermal polymerization, the acrylate and polyene/polythiol reactions in active light polymerization will be described in detail below.
（熱重合反応）
熱重合反応を生起する重合性化合物として、ポリウレタ
ンを形成するポリイソシアネートとポリオールとの組合
せ及びその予備重合物を挙げることができる。ポリオー
ルとしては、「最新ポリウレタン応用技術Ｊ （■シー
エムシー発行）２２頁〜２５頁記載のポリオールが挙げ
られ、そのうちアルキレンオキサイド（エチレンオキサ
イド、プロピレンオキサイド、テトラヒドロフランなど
）を重合して形成した融点が１０℃以下のポリオキシア
ルキレンポリオールが好ましい。この場合、オキシアル
キレン基、単独であっても２種以上であっても良い。ま
た２種以上のオキシアルキル基は混合して用いても共重
合して用いても良いが、特にエチレンオキシドとプロピ
レンオキシドを共重合したポリオールが好ましい。ポリ
オキシアルキレンポリオールの融点は通常１０℃以下、
好ましくは０℃〜６０℃である。融点が１０℃をこえる
とその結晶性のためイオン伝導度が低下する。ポリオキ
シアルキレンポリオールの水酸基価は通常８４以下、好
ましくはＢＯ以下である。水酸基価が８４を超えると固
体電解質のイオン伝導度が低くなる。ポリイソシアネー
トとしては、前述記載の書籍１３頁〜２１頁記載のポリ
イソシアネートのうち、トリレンジイソシアネート、４
，４°−メタフェニレンジイソシアネート、イソホロン
ジイソシアネート及びこれらのプレポリマーが好ましい
。ＮＣＯ基の含有割合は、通常、４８％（重量％）以下
、好ましくは４０％以下である。ＮＣＯ基含有割合が４
８％を超えると固体電解質のイオン伝導度が低くなる。(Thermal Polymerization Reaction) Examples of polymerizable compounds that cause a thermal polymerization reaction include combinations of polyisocyanates and polyols that form polyurethane, and prepolymerized products thereof. Examples of polyols include polyols described in "Latest Polyurethane Application Technology J (published by CMC), pages 22 to 25, among which polyols with a melting point of 10 A polyoxyalkylene polyol having a temperature of ℃ or less is preferable.In this case, the oxyalkylene group may be used alone or in combination of two or more types.Also, two or more types of oxyalkyl groups may be used in combination or copolymerized. Although it may be used, polyols made by copolymerizing ethylene oxide and propylene oxide are particularly preferred.The melting point of polyoxyalkylene polyols is usually 10°C or less,
Preferably it is 0°C to 60°C. When the melting point exceeds 10°C, the ionic conductivity decreases due to its crystallinity. The hydroxyl value of the polyoxyalkylene polyol is usually 84 or less, preferably BO or less. When the hydroxyl value exceeds 84, the ionic conductivity of the solid electrolyte becomes low. Examples of the polyisocyanate include tolylene diisocyanate, 4 among the polyisocyanates described on pages 13 to 21 of the book described above.
, 4°-metaphenylene diisocyanate, isophorone diisocyanate and prepolymers thereof are preferred. The content of NCO groups is usually 48% (wt%) or less, preferably 40% or less. NCO group content ratio is 4
If it exceeds 8%, the ionic conductivity of the solid electrolyte will decrease.
ポリオールとポリイソシアネートは触媒の存在下での加
熱により重付加反応を起こしてポリウレタンを与える。Polyol and polyisocyanate undergo a polyaddition reaction by heating in the presence of a catalyst to yield polyurethane.
この場合、触媒としてはポリウレタンに慣用されている
ものが挙げられ、具体例としては、トリエチレンジアミ
ン、スタナスオクトエート等である。In this case, catalysts that are commonly used for polyurethane may be used, and specific examples include triethylenediamine and stannous octoate.
（光重合反応）
本発明の固体電解質を得るための非水電解液中における
重合反応は電解質の熱分解を避けるために低温プロセス
である活性光線重合反応が好ましい。活性光線重合性化
合物としては（メタ）アクリレートや、ポリエンとポリ
チオールとの組合せ等が挙げられる。ここで（メタ）ア
クリレートとはアクリレート、又はメタアクリレートを
指す。（メタ）アクリレートとしては単官能、多官能（
メタ）アクリレートが挙げられる。単官能アクリレート
としてはアルキル（メタ）アクリレート［メチル（メタ
）アクリレート、ブチル（メタ）アクリレート、トリフ
ルオロエチル（メタ）アクリレート等］、脂環式（メタ
）アクリレート［テトラヒドロフルフリル（メタ）アク
リレート等］、ヒドロキシアルキル（メタ）アクリレー
ト ［ヒドロキシエチルアクリレート、ヒドロキシプロ
ピルアクリレート等］、ヒドロキシポリオキシアルキレ
ン（オキシアルキレン基の炭素数は好ましくは１〜４）
（メタ）アクリレート ［ヒドロキシポリオ牛ジエチレ
ン（メタ）アクリレート、ヒドロキシポリオキシプロピ
レン（メタ）アクリレート等〕及びアルコキシ（アルコ
キシ基の炭素数は好ましくは１〜４）（メタ）アクリレ
ート［メトキシエチルアクリレート、エトキシエチルア
クリレート、フェノキシエチルアクリレート等コがあげ
られる。多官能（メタ）アクリレートの例としてはＵＶ
、ＥＢ硬化技術（［総合技術センター発行）Ｉ４２頁〜
１５２頁記載の光重合性上ツマ−及び光重合性プレポリ
マーのうち３官能以上のモノマー、プレポリマー（トリ
メチロールプロパントリ（メタ）アクリレート、ベタエ
リスリトール（トル）ペンタ（メタ）アクリレート、ジ
ペンタエリスリトールヘキサ（メタ）アクリレート等）
が好ましい。単官能（メタ）アクリレートに多官能（メ
タ）アクリレートを混合して使用しても良い。（メタ）
アクリレートのうち好ましいものは単官能（メタ）アク
リレートのアルキル（メタ）アクリレート、脂環式（メ
タ）アクリレート及びアルコキシ（メタ）アクリレート
である。（メタ）アクリレートによる重合反応において
は特に単官能（メタ）アクリレート及び（メタ）アクリ
レートと多官能（メタ）アクリレートの混合物が好まし
い。次式で示されるアルコキシポリオキシアルキレン（
メタ）アクリレートの光重合反応による固体化は電池用
固体電解質を作製する上で優れたものである。(Photopolymerization Reaction) The polymerization reaction in the non-aqueous electrolyte for obtaining the solid electrolyte of the present invention is preferably an active light polymerization reaction, which is a low temperature process, in order to avoid thermal decomposition of the electrolyte. Examples of the actinic light polymerizable compound include (meth)acrylate and a combination of polyene and polythiol. Here, (meth)acrylate refers to acrylate or methacrylate. (Meth)acrylates include monofunctional and polyfunctional (
Examples include meth)acrylates. Monofunctional acrylates include alkyl (meth)acrylates [methyl (meth)acrylate, butyl (meth)acrylate, trifluoroethyl (meth)acrylate, etc.], alicyclic (meth)acrylates [tetrahydrofurfuryl (meth)acrylate, etc.] , hydroxyalkyl (meth)acrylate [hydroxyethyl acrylate, hydroxypropyl acrylate, etc.], hydroxypolyoxyalkylene (the number of carbon atoms in the oxyalkylene group is preferably 1 to 4)
(Meth)acrylates [Hydroxypoliobovine diethylene (meth)acrylate, hydroxypolyoxypropylene (meth)acrylate, etc.] and alkoxy (the number of carbon atoms in the alkoxy group is preferably 1 to 4) (meth)acrylates [methoxyethyl acrylate, ethoxyethyl Examples include acrylate and phenoxyethyl acrylate. An example of polyfunctional (meth)acrylate is UV
, EB curing technology ([Published by General Technology Center) I42 pages ~
Among the photopolymerizable polymers and photopolymerizable prepolymers described on page 152, trifunctional or higher functional monomers, prepolymers (trimethylolpropane tri(meth)acrylate, betaerythritol (tor)penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.)
is preferred. A mixture of monofunctional (meth)acrylate and polyfunctional (meth)acrylate may be used. (meta)
Among the acrylates, preferred are monofunctional (meth)acrylates such as alkyl (meth)acrylates, alicyclic (meth)acrylates, and alkoxy (meth)acrylates. In the polymerization reaction using (meth)acrylates, monofunctional (meth)acrylates and mixtures of (meth)acrylates and polyfunctional (meth)acrylates are particularly preferred. Alkoxypolyoxyalkylene represented by the following formula (
Solidification of meth)acrylate by photopolymerization reaction is excellent for producing solid electrolytes for batteries.
「
Ｒ：ＨまたはＣｖ Ｈ２又＋１（５Ｉは１〜３の整数）
ｎ：２以上の整数、特に好ましくは２〜５の整数
ｍ：１以上の整数、特に好ましくは１〜３の整数
Ｘ：０、ＮＳＳから選ばれる元素、特に好ましくは０
（メタ）アクリレート系モノマーの添加量は電解液に対
して５０％以下、好ましくは１０〜４０％、さらに好ま
しくは１０〜３０％がよい。"R: H or Cv H2 or +1 (5I is an integer of 1 to 3) n: an integer of 2 or more, particularly preferably an integer of 2 to 5 m: an integer of 1 or more, particularly preferably an integer of 1 to 3 X: The amount of the (meth)acrylate monomer added is preferably 50% or less, preferably 10 to 40%, more preferably 10 to 30%, based on the electrolytic solution.
ポリエン／ポリチオール反応は基本的には次式の通りで
ある。The polyene/polythiol reaction is basically as shown in the following formula.
Ｒ５Ｈ−Ｒ５・十Ｈψ
ＲＳ・＋ＣＨ２−ＣＨ−ＣＨ２Ｒ−
凹Ｒ５−ＣＨ２−ＣＨ２−ＣＨ２Ｒ−＋Ｒ５（前記式中
、Ｒ及びＲ゛はアルキル基等の有機基である）
ポリエンとしては、（ポリ）アリルエーテル化合物、（
ポリ）アリルエステル化合物が挙げられる。（ポリ）ア
リルエーテル化合物の例としては、置換、末置換のアリ
ルアルコールにエポキシ化合物［エチレンオキサイド、
プロピレンオキサイド、ブチレンオキサイド、スチレン
オキサイド、シクロヘキセンオキサイド、エビハロヒド
リン、アリルグリシジルエーテル等］を付加した化合物
が挙げられる。このうち好ましいものは置換、末置換の
アリルアルコールにエチレンオキサイド、プロピレンオ
キサイドを付加した化合物である。（ポリ）アリルエス
テル化合物としてはアリルアルコール又は上記の（ポリ
）アリルエーテル化合物とカルボン酸との反応生成物が
挙げられる。カルボン酸の例としては脂肪族、脂環式及
び芳香族の、飽和及び不飽和の、モノ及びポリカルボン
酸、［酢酸、プロピオン酸、酪酸、オクタン酸、ラウリ
ン酸、ステアリン酸、オレイン酸、安息香酸等のモノカ
ルボン酸（炭素数１−２０） ；アジピン酸、フタル酸
などのジカルボン酸等］が挙げられる。このうち好まし
いものは（ポリ）アリルエーテル化合物とポリカルボン
酸の反応生成物である。R5H-R5・10Hψ RS・+CH2-CH-CH2R- Concave R5-CH2-CH2-CH2R-+R5 (In the above formula, R and R' are organic groups such as alkyl groups) As the polyene, (poly) Allyl ether compound, (
Examples include poly)allyl ester compounds. Examples of (poly)allyl ether compounds include substituted and terminally substituted allyl alcohols and epoxy compounds [ethylene oxide,
Examples include compounds to which propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, shrimp halohydrin, allyl glycidyl ether, etc. are added. Among these, preferred are compounds obtained by adding ethylene oxide or propylene oxide to substituted or terminally substituted allyl alcohol. Examples of the (poly)allyl ester compound include allyl alcohol or a reaction product of the above-mentioned (poly)allyl ether compound and carboxylic acid. Examples of carboxylic acids include aliphatic, cycloaliphatic and aromatic, saturated and unsaturated, mono- and polycarboxylic acids, [acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, stearic acid, oleic acid, benzoic acid] Examples include monocarboxylic acids (having 1 to 20 carbon atoms) such as acids; dicarboxylic acids such as adipic acid and phthalic acid. Among these, a reaction product of a (poly)allyl ether compound and a polycarboxylic acid is preferred.
ポリチオールとしては液状ポリサルファイド：脂肪族、
脂環式及び芳香族（ポリ）チオール化合物；メルカプト
カルボン酸エステルがあげられる。液状ポリサルファイ
ドとしてはチオコールＬＰシリーズ（東しチオコール鰭
）があげられる。このうち好ましいものは平均分子量が
４００以下のものである。脂肪族、脂環式及び芳香族（
ポリ）チオール化合物の例としてはメタン（ジ）チオー
ル、エタン（ジ）チオールが挙げられる。メルカプトカ
ルボン酸エステルとしてはメルカプトカルボン酸と多価
アルコールのエステル化反応又はメルカプトカルボン酸
アルキルエステルと多価アルコールとのエステル交換反
応により得られる化合物が挙げられる。メルカプトカル
ボン酸の例としては２−メルカプト酢酸、３−メルカプ
トプロピオン酸が挙げられる。Polythiols include liquid polysulfide: aliphatic,
Examples include alicyclic and aromatic (poly)thiol compounds; mercaptocarboxylic acid esters. Examples of liquid polysulfides include Thiokol LP series (Eastern Thiokol fin). Among these, preferred are those having an average molecular weight of 400 or less. Aliphatic, cycloaliphatic and aromatic (
Examples of poly)thiol compounds include methane(di)thiol and ethane(di)thiol. Examples of the mercaptocarboxylic acid ester include compounds obtained by an esterification reaction between a mercaptocarboxylic acid and a polyhydric alcohol, or a transesterification reaction between a mercaptocarboxylic acid alkyl ester and a polyhydric alcohol. Examples of mercaptocarboxylic acids include 2-mercaptoacetic acid and 3-mercaptopropionic acid.
多価アルコールの例としてはエチレングリコール、トリ
メチロールプロパン、グリセリン、ペンタエリスリトー
ル、ショ糖及びこれらのアルキレンオキサイド付加物（
エチレンオキサイド、ブチレンオキサイド等）が挙げら
れる。多価アルコールとして好ましいものは３価以上の
多価アルコールでアルキレンオキサイド付加物を含まな
いものである。メルカプトカルボン酸アルキルエステル
の例としては２−メルカプト酢酸エチルエステル、３−
メルカプトプロピオン酸メチルエステル等が挙げられる
。ポリチオールのうちで好ましいものは液状ポリサルフ
ァイド及びメルカプトカルボン酸エステルである。Examples of polyhydric alcohols include ethylene glycol, trimethylolpropane, glycerin, pentaerythritol, sucrose, and their alkylene oxide adducts (
(ethylene oxide, butylene oxide, etc.). Preferred polyhydric alcohols are trivalent or higher polyhydric alcohols that do not contain alkylene oxide adducts. Examples of mercaptocarboxylic acid alkyl esters include 2-mercaptoacetic acid ethyl ester, 3-mercaptoacetic acid ethyl ester,
Examples include mercaptopropionic acid methyl ester. Among the polythiols, preferred are liquid polysulfides and mercaptocarboxylic acid esters.
以上述べてきたアクリレート、ポリエン／ポリチオール
等の活性光線重合性化合物の重合開始剤としては光重合
開始剤が使用できる。光重合開始剤としては、カルボニ
ル化合物（ベンゾイン類［ベンゾイン、ベンゾインメチ
ルエーテル、ベンゾインエチルエーテル、ベンゾインイ
ソプロピルエーテル、ペンゾインイソブチルエ−チル、
α−メチルベンゾイン、α−フェニルベンゾイン等コ、
アントラキノン類［アントラキノン、メチルアントラキ
ノン、クロルアントラキノン等コ、その他の化合物［ベ
ンジル、ジアセチル、アセトフェノン、ベンゾフェノン
、メチルベンゾイルフォーメート等］）、硫黄化合物（
ジフェニルサルファイド、ジフェニルスルフィド、ジチ
オカーバメート等）、多縮合環系灰化水素のハロゲン化
物（α−クロルメチルナフタリン等）、色素類（アクリ
ルフラビン、フルオレセン等）、金属塩類（塩化鉄、塩
化銀等）、オニウム塩類（Ｐ−メトキシベンゼンジアゾ
ニウム、ヘキサフルオロフォスフェート、ジフェニルア
イオドニウム、トリフェニルスルフオニウム等）などが
挙げられる。これらは単独でも、あるいは２種以上の混
合物としても使用できる。好ましい光重合開始剤はカル
ボニル化合物、硫黄化合物及びオニウム塩類である。必
要により熱重合開始剤［アゾビスイソブチロニトリル、
ベンゾイルパーオキサイド等］も併用できる。増感剤、
貯蔵安定剤も必要により併用できる。その具体例として
はｒＵＶ、 ＥＢ硬化技術（−総合技術センター発行’
） Ｊ １５８頁〜１５６９頁記載の増感剤、貯蔵安定
剤のうち前者として尿素、ニトリル化合物［Ｎ、Ｎ−ジ
置換−Ｐ−アミノベンジニトリル等］、燐化合物［トリ
ーｎ−ブチルホスフィン等］が好ましく、後者として第
４級アンモニウムクロライド、ベンゾチアゾール及びハ
イドロキノンが好ましい。A photopolymerization initiator can be used as the polymerization initiator for the actinic light polymerizable compounds such as acrylates and polyenes/polythiols described above. As a photopolymerization initiator, carbonyl compounds (benzoins [benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, penzoin isobutyl ethyl,
α-methylbenzoin, α-phenylbenzoin, etc.
Anthraquinones [anthraquinone, methylanthraquinone, chloroanthraquinone, etc., other compounds [benzyl, diacetyl, acetophenone, benzophenone, methylbenzoyl formate, etc.]), sulfur compounds (
diphenyl sulfide, diphenyl sulfide, dithiocarbamate, etc.), polycondensed ring hydrogen ash halides (α-chloromethylnaphthalene, etc.), pigments (acrylic flavin, fluorescene, etc.), metal salts (iron chloride, silver chloride, etc.) , onium salts (P-methoxybenzenediazonium, hexafluorophosphate, diphenyliodonium, triphenylsulfonium, etc.). These can be used alone or as a mixture of two or more. Preferred photoinitiators are carbonyl compounds, sulfur compounds and onium salts. A thermal polymerization initiator [azobisisobutyronitrile,
benzoyl peroxide, etc.] can also be used in combination. sensitizer,
A storage stabilizer can also be used in combination if necessary. Specific examples include rUV and EB curing technologies (published by the General Technology Center).
) J Among the sensitizers and storage stabilizers described on pages 158 to 1569, the former include urea, nitrile compounds [N,N-disubstituted-P-aminobenzinitrile, etc.], phosphorus compounds [tri-n-butylphosphine, etc.] is preferred, with quaternary ammonium chloride, benzothiazole and hydroquinone being preferred as the latter.
重合開始剤は活性光線重合性化合物に対し通常０．１〜
１０重量％、好ましくは０．５〜７重量％である。この
範囲外では適度な反応性が得られない。増感剤及び貯蔵
安定剤は活性光線重合性化合物１００部に対し通常０．
１〜５部である。The polymerization initiator is usually 0.1 to
10% by weight, preferably 0.5-7% by weight. Outside this range, appropriate reactivity cannot be obtained. The amount of the sensitizer and storage stabilizer is usually 0.00 parts per 100 parts of the active light polymerizable compound.
1 to 5 parts.
本発明の固体電解質は重合性化合物及び重合開始剤を含
む非水電解液を容器に入れるか、あるいは支持体（例え
ばフィルム、金属、ガラス）にコーティングして、熱ま
たは活性光線で重合することにより得られる。活性光線
としては通常、光、紫外線、電子線、Ｘ線が使用できる
。The solid electrolyte of the present invention is produced by placing a non-aqueous electrolyte containing a polymerizable compound and a polymerization initiator in a container or coating it on a support (e.g., film, metal, glass) and polymerizing it with heat or actinic rays. can get. As the actinic ray, light, ultraviolet rays, electron beams, and X-rays can usually be used.
これらのうち、好ましくは、１００〜８００ｎｍの波長
の活性光線である。Among these, active rays with a wavelength of 100 to 800 nm are preferred.
本発明の所定の固体電解質を得るためには電解質塩濃度
と重合性化合物量との適切な配合が必要であり両者の間
には密接な関係がある。特に（１）式のアクリレートを
用いた固体化においては、塩濃度が１．０モル１５Ｉで
は固体化のための重合性化合物濃度は３０〜５０％程度
必要となり、３モル／９以上の高濃度ではｌＯ〜２０％
程度の添加量で充分な特性を有する固体電解質が作製で
きる。In order to obtain the predetermined solid electrolyte of the present invention, it is necessary to appropriately mix the electrolyte salt concentration and the amount of polymerizable compound, and there is a close relationship between the two. In particular, in solidification using the acrylate of formula (1), when the salt concentration is 1.0 mol 15I, the concentration of the polymerizable compound for solidification needs to be about 30 to 50%, and a high concentration of 3 mol/9 or more is required. Then lO~20%
A solid electrolyte with sufficient properties can be produced with a moderate amount of addition.
また、本発明の非水電解液には、非水電解液の表面張力
を下げて、隔膜あるいは活物質への浸透を向上させる浸
漬助剤を添加することが好ましい。このような浸漬助剤
としては、シリコンオイル、シリコン−アルキレンオキ
サイド付加物等のシリコン誘導体；ポリプロピレンオキ
シド誘導体；パーフルオロアルキルスルホン酸塩；パー
フルオロアルキルカルボン酸塩；パーフルオロアルキル
第４級アンモニウムヨウ化物、パーフルオロアルキルポ
リオキシエチレンエタノール、フッ素化アルキルエステ
ル等のフッ素誘導体が挙げられる。これらのうち好まし
いものはシリコン誘導体及びフッ素誘導体である。Further, it is preferable to add an immersion aid to the non-aqueous electrolyte of the present invention, which lowers the surface tension of the non-aqueous electrolyte and improves its penetration into the diaphragm or active material. Such immersion aids include silicone oil, silicone derivatives such as silicone-alkylene oxide adducts; polypropylene oxide derivatives; perfluoroalkyl sulfonates; perfluoroalkyl carboxylates; perfluoroalkyl quaternary ammonium iodides. , perfluoroalkyl polyoxyethylene ethanol, and fluorine derivatives such as fluorinated alkyl esters. Among these, silicon derivatives and fluorine derivatives are preferred.
この浸漬助剤は、固体電解質中、通常、０．１〜１０重
量％、好ましくは、０．５〜５重量％である。This immersion aid is generally 0.1 to 10% by weight, preferably 0.5 to 5% by weight in the solid electrolyte.
この範囲外では経済的な浸漬効果が得られない。Outside this range, economical immersion effects cannot be obtained.
次に本発明の二次電池について説明する。本発明の二次
電池の負極にはＡｌ上にＬ ｉ −Ａ Ｉ合金を設けて
なる負極を用いる。本発明の二次電池の負極にはＡ１層
を有するため、フレキシブルでシート化が可能である。Next, the secondary battery of the present invention will be explained. As the negative electrode of the secondary battery of the present invention, a negative electrode formed by providing a Li-A I alloy on Al is used. Since the negative electrode of the secondary battery of the present invention has the A1 layer, it is flexible and can be formed into a sheet.
Ｌ ｉ −Ａ １合金は前述したように崩壊、脱落が生
じやすいものであるが、本発明の二次電池では多価カチ
オンを含有するイオン伝導性粘弾性体を固体電解質とし
て用いるため、多価カチオンがＬ ｉ −Ａ Ｉあるい
はＡｌ中に拡散することにより、負極の機械的強度の改
善、充放電による合金層の変形の防止、及び充放電効率
の向上と負極の性能を飛躍的に向上させることが出来る
。本発明の二次電池の負極は、
（１）リチウム塩を含む非水電解液中でＡｌにリチウム
を電着して合金化する電気化学的製造方法、
（２） Ａ １基板上にリチウムを積層した後、加熱処
理をおこない、Ａｌ基板表面を合金化する方法、
（３） （２）の積層体を電解液中で電気化学的処理に
より合金化する方法、
（４）リチウムとＡｌを電解液を介在させて接触させる
ことによりＡ１表面を合金化させる方法、
等により作製することができる。As mentioned above, the L i -A 1 alloy is prone to collapse and fall off, but since the secondary battery of the present invention uses an ion-conducting viscoelastic body containing polyvalent cations as a solid electrolyte, Diffusion of cations into Li-A I or Al improves the mechanical strength of the negative electrode, prevents deformation of the alloy layer due to charging and discharging, improves charging and discharging efficiency, and dramatically improves the performance of the negative electrode. I can do it. The negative electrode of the secondary battery of the present invention is produced by: (1) an electrochemical manufacturing method in which lithium is electrodeposited and alloyed with Al in a non-aqueous electrolyte containing a lithium salt; (2) lithium is deposited on an A1 substrate; (3) A method of alloying the laminate of (2) by electrochemical treatment in an electrolytic solution; (4) Electrolyzing lithium and Al It can be produced by a method in which the A1 surface is alloyed by contacting with a liquid.
本発明の二次電池の負極のＡｌは２０〜３００μ閣、好
ましくは３０−１００μｍである。２０μ厘以下ではＡ
ｌの集電効率、負極の機械的強度に問題があり、３００
μｍ以上では負極はフレキシブルでなくなる。Ａ１は表
面の結晶性が主に（１００）面を有することが好ましい
。この様なＡ１を使用することにより、負極製造時の合
金化が均一に行うのみでなく、負極のサイクル寿命も向
上する。Ｌｉ−Ａ１合金は４〜１５０μ１１好ましくは
１０〜１００μ−である。４μｇ以下では負極の放電容
量が十分でなく、１５０μｍ以上では負極の機械的強度
が低下する。また、Ｌｉ−Ａ１合金はＡｌよりも薄いこ
とが好ましい。Al of the negative electrode of the secondary battery of the present invention has a thickness of 20 to 300 μm, preferably 30 to 100 μm. A below 20 μm
There are problems with the current collection efficiency of l and the mechanical strength of the negative electrode.
Above μm, the negative electrode is no longer flexible. It is preferable that the surface crystallinity of A1 mainly has a (100) plane. By using such A1, not only is alloying performed uniformly during production of the negative electrode, but also the cycle life of the negative electrode is improved. The Li-A1 alloy has a particle diameter of 4 to 150μ, preferably 10 to 100μ. If it is less than 4 μg, the discharge capacity of the negative electrode will not be sufficient, and if it is more than 150 μm, the mechanical strength of the negative electrode will decrease. Moreover, it is preferable that the Li-A1 alloy is thinner than Al.
本発明の二次電池の負極にはＡｌあるいはＬｉ−Ａ１合
金にＭｇ、Ｚｎ、Ｍｎ％Ｐｂを０．０１〜１５％含有し
ていることが好ましい。The negative electrode of the secondary battery of the present invention preferably contains 0.01 to 15% of Mg, Zn, and Mn%Pb in Al or Li-A1 alloy.
さらに、ＡｌあるいはＬ ｉ −Ａ １合金は研磨材、
電解エツチング等により粗面化されていることが好まし
い。特に電解エツチングにより無数のビットを設けるこ
とにより電極反応をスムーズに行うことができ、充放電
効率の向上、負極のサイクル寿命の向上となり好ましい
。Furthermore, Al or Li-A 1 alloy is an abrasive,
It is preferable that the surface be roughened by electrolytic etching or the like. In particular, it is preferable to provide a countless number of bits by electrolytic etching, as this enables smooth electrode reactions, improves charging and discharging efficiency, and improves the cycle life of the negative electrode.
本発明の二次電池は基本的には正極活物質からなる正極
、負極活物質からなる負極及び隔膜の電池要素と、固体
電解質より構成される。本発明の固体電解質そのものに
隔膜としての機能を兼用させることも可能であるが、極
間の電界を均一にし、信頼性向上のために隔膜と一体化
することが好ましい。The secondary battery of the present invention basically comprises battery elements including a positive electrode made of a positive electrode active material, a negative electrode made of a negative electrode active material, and a diaphragm, and a solid electrolyte. Although it is possible for the solid electrolyte of the present invention itself to function as a diaphragm, it is preferable to integrate it with a diaphragm in order to make the electric field between the electrodes uniform and improve reliability.
本発明の場合、この隔膜と固体電解質との一体化は容易
で、前記したように隔膜を有する電池容器内において直
接固体電解質を形成することにより、あるいは隔膜中に
固体電解質形成用組成物を含浸させ、重合反応を行うこ
とにより達成することができる。この場合、固体電解質
形成用組成物には、浸漬助剤を添加するのが好ましい。In the case of the present invention, the diaphragm and the solid electrolyte can be easily integrated by forming the solid electrolyte directly in the battery container having the diaphragm as described above, or by impregnating the diaphragm with a composition for forming a solid electrolyte. This can be achieved by carrying out a polymerization reaction. In this case, it is preferable to add a dipping aid to the solid electrolyte forming composition.
正極活物質としては、カルコゲナイド化合物［ＴｉＳ２
、Ｎｂｉ Ｓ４ 、ＭＯ８２、Ｃ０８２、ＦｅＳ２、Ｖ
２０Ｓ 、Ｃｒ２０ｓ ｓ ＭｎＯ２、ＣＯＯ２等］や
、正極電気活性高分子［ポリアニリン、ポリピロール、
ポリ−３−メチルチオフェン、ポリジフェニルベンジジ
ン、ポリアズレン等の導電性高分子や、メタロセンポリ
マー等］を挙げることができる。これらのうち好ましい
ものは、正極電気活性高分子であり、より好ましくは導
電性高分子である。As the positive electrode active material, a chalcogenide compound [TiS2
, Nbi S4, MO82, C082, FeS2, V
20S, Cr20s MnO2, COO2, etc.], positive electrode electroactive polymers [polyaniline, polypyrrole,
conductive polymers such as poly-3-methylthiophene, polydiphenylbenzidine, polyazulene, metallocene polymers, etc.). Preferred among these are positive electrode electroactive polymers, more preferably conductive polymers.
隔膜としては、イオン移動に対して低抵抗であり、かつ
、溶液保持性に優れたものが用いられる。例えば、ガラ
ス繊維フィルター；ポリエステル、テフロン、ポリエチ
レン、ポリプロピレン等の高分子ボアフィルター−ある
いは不織布；ガラス繊維と高分子繊維からなる混抄紙等
を用いることができる。中でも０．１〜０．０１μ■の
ミクロボア径を有するポリプロピレン製不織布と固体電
解質との複合体は性能面において特に有用である。As the diaphragm, one that has low resistance to ion movement and excellent solution retention is used. For example, glass fiber filters; polymeric bore filters such as polyester, Teflon, polyethylene, and polypropylene; or nonwoven fabrics; mixed paper made of glass fibers and polymeric fibers, etc. can be used. Among these, a composite of a polypropylene nonwoven fabric having a micropore diameter of 0.1 to 0.01 .mu.m and a solid electrolyte is particularly useful in terms of performance.
本発明の二次電池は、一般式（１）で示されるアクリレ
ートを含む重合性化合物と非水電解液からなる粘弾性体
を従来の固体電解質の代わりに用いて製造することがで
きる。本発明の固体電解質は、非水電解液中に溶解させ
た重合性化合物を重合させ、反応液を柔軟性に富む粘弾
性体に変換させることにより形成されるので、電極、隔
膜あるいは電池内において直接重合反応を行って形成す
るのが好ましい。即ち、電極あるいは隔膜に固体電解質
形成用組成物を含浸させ、加熱あるいは活性光線の照射
等の前述した重合手段により粘弾性体とし、固体電解質
と電池要素の一体化を行うことが好ましい。各電池要素
の固体電解質との一体化は、各電池要素と別個に一体化
させてもよいが、正極と隔膜、負極と隔膜あるいは正極
と隔膜と負極とを積層後固体電解質との一体化を行って
もよい。The secondary battery of the present invention can be manufactured by using a viscoelastic body made of a polymerizable compound containing an acrylate represented by general formula (1) and a nonaqueous electrolyte instead of a conventional solid electrolyte. The solid electrolyte of the present invention is formed by polymerizing a polymerizable compound dissolved in a nonaqueous electrolyte and converting the reaction liquid into a highly flexible viscoelastic body, so it can be used in electrodes, diaphragms, or batteries. Preferably, it is formed by direct polymerization reaction. That is, it is preferable to impregnate the electrode or diaphragm with a composition for forming a solid electrolyte, make it into a viscoelastic body by the above-mentioned polymerization means such as heating or irradiation with actinic rays, and integrate the solid electrolyte and the battery element. Although each battery element may be integrated with the solid electrolyte separately, it is possible to integrate the solid electrolyte after laminating the positive electrode and the diaphragm, the negative electrode and the diaphragm, or the positive electrode and the diaphragm and the negative electrode. You may go.
このように各電池要素と前記固体電解質が一体化してい
れば、正極、負極での電極反応及びイオンの移動がスム
ーズに進行させることができ、電池の内部抵抗を大幅に
低減することができる。If each battery element and the solid electrolyte are integrated in this way, the electrode reaction at the positive electrode and the negative electrode and the movement of ions can proceed smoothly, and the internal resistance of the battery can be significantly reduced.
本発明の二次電池は正極、負極を固体電解質と一体化さ
せて、隔膜を介し、積層した積層体をそのまま、あるい
はスパイラル状にし、コイン型、円筒型、角型、ガム型
、シート型等の各種電池容器に実装し、電池を製造する
ことができる。The secondary battery of the present invention has a positive electrode and a negative electrode integrated with a solid electrolyte and is laminated with a diaphragm in between, either as it is or in a spiral shape, such as a coin shape, a cylinder shape, a square shape, a gum shape, a sheet shape, etc. It can be mounted in various battery containers to manufacture batteries.
［実施例コ
以下、実施例により本発明を更に詳細に説明するが、本
発明はこれらに限定されるものではない。以下において
、部及び％はそれぞれ重量部及び重量％を示す。[Examples] The present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In the following, parts and % indicate parts by weight and % by weight, respectively.
また、実施例、比較例において使用した材料は次の通り
である。なお、非水溶媒及び電解質塩は十分に精製を行
い、水分２０ｐｐｍ以下としたもので更に脱酸素及び脱
窒素を行った電池グレードのものを使用し、すべての操
作はアルゴンガス雰囲気で行った。また、イオン伝導度
、弾性率の測定温度は２０℃で行った。Further, the materials used in the Examples and Comparative Examples are as follows. Note that the non-aqueous solvent and electrolyte salt were sufficiently purified to have a water content of 20 ppm or less, and were of battery grade that had been further deoxidized and denitrified, and all operations were performed in an argon gas atmosphere. Further, the measurement temperature for ionic conductivity and elastic modulus was 20°C.
実施例１
プロピレンカーボネート及び１．２−ジメトキシエタン
を各々重量比６：４の割合で混合した非水溶媒１０００
部に２モルのＭｇ（Ｃ１０４） ２を溶解せしめた電解
液を７９．２％、エトキシジエチレングリコールアクリ
レートを１９，５％、メチルベンゾイルフォーメートを
０．８％混合した。Example 1 Non-aqueous solvent 1000 in which propylene carbonate and 1,2-dimethoxyethane were mixed at a weight ratio of 6:4, respectively.
79.2% of an electrolytic solution in which 2 mol of Mg(C104) 2 was dissolved, 19.5% of ethoxydiethylene glycol acrylate, and 0.8% of methyl benzoyl formate were mixed.
これに高圧水銀灯により活性光を３０分照射して固体電
解質を得た。イオン伝導度は２．４×１０−’Ｓ／ｃｍ
、弾性率２ ｘ １０’ ｄｙｎ／ｃｍであった。This was irradiated with active light for 30 minutes using a high-pressure mercury lamp to obtain a solid electrolyte. Ionic conductivity is 2.4 x 10-'S/cm
, the elastic modulus was 2 x 10' dyn/cm.
実施例２
プロピレンカーボネート１０００部に１モルのＭｇ（Ｂ
Ｆ４）２．１モルのＬｉ ＢＦ４を溶解せしめた電解液
を７９．２％、エトキシジエチレングリコールアクリレ
ートを１９．５％、メチルベンゾイルフォーメートを０
．８％混合した。これに高圧水銀灯により活性光を３０
分照射して固体電解質を得た。Example 2 1 mol of Mg(B
F4) 79.2% electrolyte in which 2.1 mol of Li BF4 was dissolved, 19.5% ethoxydiethylene glycol acrylate, and 0 methylbenzoyl formate.
．． 8% mixed. This is then exposed to active light for 30 minutes using a high-pressure mercury lamp.
A solid electrolyte was obtained by irradiation for 30 minutes.
イオン伝導度２Ｊ ｘ １Ｏ−３Ｓ／Ｃｓ、弾性率１．
５ Ｘ１０’ ｄｙｎ／Ｃｓであった。Ionic conductivity 2J x 1O-3S/Cs, elastic modulus 1.
It was 5×10′ dyn/Cs.
実施例３
プロピレンカーボネート、γ−ブチロラクトンを各々重
量比８：２の割合で混合した非水溶媒１０００部に０．
７モルのＭｇ（ＣＩＯｎ ） ２を溶解せしめ電解液と
し、この電解液８９．１％に、ポリエン（分子量４００
のポリオキシエチレングリコール４００部にアリルグリ
シジルエーテル３４２部を反応させたもの）６．４％、
ペンタエリスリトールテトラキスチオグリコレート３．
６％、メチルベンゾイルフォーメート０．４％及びシリ
コンアルキレンオキサイド付加物０．５％の割合で混合
した。Example 3 0.00 parts of a non-aqueous solvent prepared by mixing propylene carbonate and γ-butyrolactone at a weight ratio of 8:2 was added.
7 mol of Mg(CIOn) 2 was dissolved to prepare an electrolyte, and 89.1% of this electrolyte was added with polyene (molecular weight 400
400 parts of polyoxyethylene glycol reacted with 342 parts of allyl glycidyl ether) 6.4%,
Pentaerythritol tetrakisthioglycolate 3.
6%, methyl benzoyl formate 0.4% and silicon alkylene oxide adduct 0.5%.
これに高圧水銀灯により活性光を３０分照射して固体電
解質を得た。イオン伝導度は４ Ｘ １０−’３／ｃｍ
、弾性率５ Ｘ １０−’ｄｙｍ／ｃｍであった。This was irradiated with active light for 30 minutes using a high-pressure mercury lamp to obtain a solid electrolyte. Ionic conductivity is 4 x 10-'3/cm
, the elastic modulus was 5 x 10-' dym/cm.
比較例１
実施例１において過塩素酸テトラブチルアンモニウムを
用いる以外は同様にして固体電解質の作製を試みたが溶
液の粘度は高くなるものの液状であった。Comparative Example 1 An attempt was made to produce a solid electrolyte in the same manner as in Example 1 except that tetrabutylammonium perchlorate was used, but although the viscosity of the solution increased, it remained liquid.
比較例２
実施例２においてＬｉＢＦ４を用いる以外は同様にして
固体電解質の作製を行った。弾性率はＩ Ｘ １０’
ｄｙｎ／ｃｍであった。Comparative Example 2 A solid electrolyte was produced in the same manner as in Example 2 except that LiBF4 was used. The elastic modulus is I x 10'
It was dyn/cm.
実施例４
プロピレンカーボネート及び１．２−ジメトキシエタン
を各々重量比６：４の割合で混合した非水溶媒１０００
部に０．１モルのＭｇ（ＢＦ４） ２．２．８モルのＬ
ｉＢＦ４を溶解せしめた電解液を７９．２％、エトキシ
ジエチレングリコールアクリレートを１９．５％、メチ
ルベンゾイルフォーメートを０．８％混合し、固体電解
質組成物とした。Example 4 Non-aqueous solvent 1000 in which propylene carbonate and 1,2-dimethoxyethane were mixed at a weight ratio of 6:4, respectively.
0.1 mol of Mg (BF4) in parts 2.2.8 mol of L
A solid electrolyte composition was prepared by mixing 79.2% of an electrolytic solution in which iBF4 was dissolved, 19.5% of ethoxydiethylene glycol acrylate, and 0.8% of methyl benzoyl formate.
厚さ７５μ園のアルミニウム箔を電気化学的にエツチン
グして面に対して垂直方向に魚類のピットを形成した。A 75 μm thick aluminum foil was electrochemically etched to form fish pits in a direction perpendicular to the surface.
このアルミニウム箔上にＬｉを２０μｓ８Ｉ層後、１５
０℃で２０秒間加熱処理を行い、負極を製造した。After a 20 μs 8I layer of Li on this aluminum foil, 15
Heat treatment was performed at 0° C. for 20 seconds to produce a negative electrode.
厚さ０．０２■■の粗面化したＳＵＳ基板の片面に１ｓ
ｏｌ／１２のアニリン、３ｍｏｌ／９のＨＢ Ｆ４水溶
液中で３ｍＡ／ｃｊの定電流電解重合法によりポリアニ
リンを５ｍｇ／ｃｊ析出せしめた。還元処理、真空乾燥
を十分に行った後、ＰＥＴ／アルミニウム／ポリプロピ
レン積層体の外装材に貼り付けたポリアニリンに固体電
解質組成物を十分にしみこませてガラス基板に挾み、１
ｋｇで加熱して高圧水銀灯により活性光を照射し、正極
と固体電解質を複合化した。次に、隔膜（セルガード４
５０１）をシート状正極上に配置して固体電解質形成用
組成物を含浸した後、活性光線を照射することにより該
組成物を固化せしめた。一方、ＰＥＴ／アルミニウム／
ポリプロピレン積層体の外装材に負極を貼り付け、Ｌ
ｉ −Ａ Ｉ合金上に固体電解質形成用組成物を塗布し
、ガラス基板に挾んで高圧水銀灯により活性光線を照射
することにより該組成物を固化せしめ、負極と固体電解
質を複合化した。前記の外装材／正極／セパレータ（固
体電解質）と外装材／負極（固体電解質）とを貼り合わ
せ、周辺部を熱融着して、５×７■のカード型電池を作
製した。２．５１＾の定電流で２．０Ｖ〜３，７■で充
放電を行った結果、初期容量１２．５■Ａｈ 、サイク
ル１００回後、１１．２１Ａｈ 。1s on one side of a roughened SUS board with a thickness of 0.02■■
Polyaniline was deposited in an amount of 5 mg/cj using a constant current electrolytic polymerization method at 3 mA/cj in an aqueous solution of aniline at ol/12 and HB F4 at 3 mol/9. After sufficient reduction treatment and vacuum drying, the polyaniline attached to the exterior material of the PET/aluminum/polypropylene laminate was thoroughly impregnated with the solid electrolyte composition and sandwiched between glass substrates.
kg and irradiated with active light using a high-pressure mercury lamp to form a composite of the positive electrode and solid electrolyte. Next, the diaphragm (Celgard 4
501) was placed on a sheet-like positive electrode and impregnated with a composition for forming a solid electrolyte, and then the composition was solidified by irradiation with active light. On the other hand, PET/aluminum/
Attach the negative electrode to the exterior material of the polypropylene laminate, and
A composition for forming a solid electrolyte was applied onto the i-A I alloy, sandwiched between glass substrates, and irradiated with actinic rays from a high-pressure mercury lamp to solidify the composition, thereby forming a composite of the negative electrode and the solid electrolyte. The above-mentioned exterior material/positive electrode/separator (solid electrolyte) and exterior material/negative electrode (solid electrolyte) were bonded together and the peripheral portions were heat-sealed to produce a 5×7 square card-type battery. As a result of charging and discharging at a constant current of 2.51^ from 2.0V to 3.7■, the initial capacity was 12.5Ah, and after 100 cycles, it was 11.21Ah.
３００回後、９．５ｓＡｈが得られた。After 300 cycles, 9.5 sAh was obtained.
［発明の効果コ
以上説明したように、本発明のイオン伝導性、粘弾性体
は、高い固体強度とイオン伝導性を持つため、たとえば
二次電池、エレクトロクロミック素子、センサー等の各
種素子に有用であり、らに本発明の二次電池は高性能で
ある。[Effects of the Invention] As explained above, the ionic conductive, viscoelastic body of the present invention has high solid strength and ionic conductivity, so it is useful for various devices such as secondary batteries, electrochromic devices, and sensors. Moreover, the secondary battery of the present invention has high performance.
Claims (2)
粘弾性体であって、該非水電解液中に多価カチオンを含
有することを特徴とするイオン伝導性粘弾性体。(1) An ion-conducting viscoelastic body having a structure containing a non-aqueous electrolyte in a high molecular weight polymer, characterized in that the non-aqueous electrolyte contains a polyvalent cation.
る二次電池において、第一項記載のイオン伝導性粘弾性
体を用いることを特徴とする二次電池。(2) A secondary battery using a negative electrode formed by providing a Li-Al alloy on Al, characterized in that the ion-conductive viscoelastic body described in item 1 is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2302578A JPH04179065A (en) | 1990-11-09 | 1990-11-09 | Ion conductive visco-elastic substance and secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2302578A JPH04179065A (en) | 1990-11-09 | 1990-11-09 | Ion conductive visco-elastic substance and secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04179065A true JPH04179065A (en) | 1992-06-25 |
Family
ID=17910669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2302578A Pending JPH04179065A (en) | 1990-11-09 | 1990-11-09 | Ion conductive visco-elastic substance and secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04179065A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001091209A1 (en) * | 2000-05-24 | 2001-11-29 | Telcordia Technologies, Inc. | Dual cation rechargeable electrochemical battery cell |
| JP2005108520A (en) * | 2003-09-29 | 2005-04-21 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| WO2013027767A1 (en) * | 2011-08-23 | 2013-02-28 | 株式会社日本触媒 | Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte |
| JP2014029818A (en) * | 2011-08-23 | 2014-02-13 | Nippon Shokubai Co Ltd | Gel electrolyte or negative electrode mixture, and battery using the gel electrolyte or the negative electrode mixture |
-
1990
- 1990-11-09 JP JP2302578A patent/JPH04179065A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001091209A1 (en) * | 2000-05-24 | 2001-11-29 | Telcordia Technologies, Inc. | Dual cation rechargeable electrochemical battery cell |
| JP2005108520A (en) * | 2003-09-29 | 2005-04-21 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| WO2013027767A1 (en) * | 2011-08-23 | 2013-02-28 | 株式会社日本触媒 | Negative electrode mixture or gel electrolyte, and battery using said negative electrode mixture or said gel electrolyte |
| JP2014029818A (en) * | 2011-08-23 | 2014-02-13 | Nippon Shokubai Co Ltd | Gel electrolyte or negative electrode mixture, and battery using the gel electrolyte or the negative electrode mixture |
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