CN109952673A - 用于锂硫电池的电极 - Google Patents
用于锂硫电池的电极 Download PDFInfo
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- CN109952673A CN109952673A CN201780066044.6A CN201780066044A CN109952673A CN 109952673 A CN109952673 A CN 109952673A CN 201780066044 A CN201780066044 A CN 201780066044A CN 109952673 A CN109952673 A CN 109952673A
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- polymer
- electrode
- lithium
- collector
- electrode according
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000004020 conductor Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 7
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- 235000011852 gelatine desserts Nutrition 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
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- 102000004196 processed proteins & peptides Human genes 0.000 claims description 8
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- 102000008186 Collagen Human genes 0.000 claims description 4
- 108010035532 Collagen Proteins 0.000 claims description 4
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- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
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- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000816 peptidomimetic Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims 2
- 229910000733 Li alloy Inorganic materials 0.000 claims 1
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- 239000001989 lithium alloy Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 125000004354 sulfur functional group Chemical group 0.000 claims 1
- 238000005192 partition Methods 0.000 description 15
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- 239000011230 binding agent Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- -1 pentanedione Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical compound ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 102100030089 ATP-dependent RNA helicase DHX8 Human genes 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 101000864666 Homo sapiens ATP-dependent RNA helicase DHX8 Proteins 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
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- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- WCDDVEOXEIYWFB-VXORFPGASA-N (2s,3s,4r,5r,6r)-3-[(2s,3r,5s,6r)-3-acetamido-5-hydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-4,5,6-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@@H]1C[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](O)[C@H](O)[C@H]1O WCDDVEOXEIYWFB-VXORFPGASA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 108060008539 Transglutaminase Proteins 0.000 description 1
- IYDWBHJEYMDOBU-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC(=O)C(O)=O.OC(=O)C(O)=O Chemical class [Li+].[Li+].[Li+].[O-]B([O-])[O-].OC(=O)C(O)=O.OC(=O)C(O)=O IYDWBHJEYMDOBU-UHFFFAOYSA-N 0.000 description 1
- SROPKFOGVUYJCW-UHFFFAOYSA-N [Li].[SH2]=N.C(F)(F)F Chemical compound [Li].[SH2]=N.C(F)(F)F SROPKFOGVUYJCW-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005526 alkyl sulfate group Chemical group 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229940014041 hyaluronate Drugs 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 102000003601 transglutaminase Human genes 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
根据本公开，存在一种用于锂硫电池的电极。该电极包含沉积于集电器上的基质，其中该基质包含导电材料、电活性硫材料和包含聚合物的粘合剂，该聚合物经交联形成交联的聚合物网络。
Description
技术领域
本发明涉及用于锂硫电池的电极。本发明还涉及生产这种电极的方法，以及包括这种电极的锂硫电池。
背景技术
典型的锂-硫电池包括由锂金属或锂金属合金形成的负极(负电极)，和由单质硫或其他电活性硫材料形成的正极(正电极)。硫或其他电活性含硫材料可以与导电材料如碳混合而改进其导电性。碳和硫可以碾磨并随后与溶剂和粘合剂混合而形成浆料。浆料可以施加于集电器上，并随后干燥而除去溶剂。获得的结构压延而形成复合结构，将其切割成期望的形状而形成正极。隔板可以放置于正极上，且电解质则可以施加于隔板上以润湿正极和隔板。锂负极可以放置于隔板上而形成电池堆。
附图说明
本公开的各方面仅通过举例的方式示意性地显示于附图中，其中：
图1显示了实施例1的电池的放电容量如何随循环次数而变化。
具体实施方式
在描述本发明的具体实施例之前，应该理解的是，本公开不限于本文公开的具体电池、方法或材料。还应该理解的是，本文使用的术语仅用于描述具体实施例，而非旨在成为限制性的，因为保护范围将由权利要求书及其等同物限定。
术语“蛋白质”或“多肽”或“肽”可以互换使用，并且是指由氨基酸的链构成的分子，而不涉及特定的作用模式、尺寸、三维结构或来源。
如本文使用的“明胶”和“明胶样蛋白”是指任何明胶，无论是通过传统方法提取的还是源自重组或生物合成的，或是指任何具有明胶的至少一种结构和/或功能特征的分子。术语涵盖了明胶产品中包含的多于一种多肽的组合物，以及组成明胶材料的各种多肽。因此，涉及本发明使用的术语明胶既包括含有明胶多肽的明胶材料，也涵盖了各自的明胶多肽。
如本文描述的“交联剂”是指包含交联剂的组合物。如本文使用的“交联剂”是指可以在有机分子中引入共价的分子内和分子间桥的反应性化学化合物。
在描述和要求保护本发明的电池和方法中，将会使用以下术语：单数形式“一个”、“一种”和“该”除非上下文另有明确说明，包括复数形式。因此，例如，提及“一个负极”包括提及一个或多个这种元件。
根据本发明，有一种用于锂硫电池的电极。电极包含沉积于集电器上的基质，其中基质包含导电材料、电活性硫材料和包含经交联而形成交联的聚合物网络的聚合物的粘合剂。
在另一方面中，本发明还提供了一种锂硫电池，其包含如上描述的电极。电极优选是电池的正极。负极可以是包含锂金属的负极，例如纯锂金属或锂金属合金。其他合适的负极材料包括适用于锂离子电池的负极，例如硅或石墨负极。
在另一方面中，本发明提供了一种生产用于锂硫电池的电极的方法。方法包括将包含导电材料、电活性硫材料和包含聚合物的粘合剂的电极混合物沉积在集电器上，由此使聚合物交联而在集电器上形成交联的聚合物网络。
聚合物可以在沉积于集电器上之前交联，或可以在沉积于集电器上之后通过例如暴露于交联剂而聚合。
通过交联聚合物，导电材料和电活性硫材料可以通过交联的聚合物网络保持就位。这种交联的聚合物网络可以改进电极的结构完整性，帮助锂硫电池的充电和放电循环期间形成的带电物质在电池充电和放电时与集电器保持电接触。有利地，这可以导致锂硫电池的循环寿命的改进。
粘结剂
粘结剂包含经交联而形成聚合物网络的聚合物。聚合物可以是任何可交联的聚合物。例如，聚合物可以包含可以交联的官能团。合适的官能团的实例包括胺、酰胺、羰基、羧基、醚、硫醚和羟基基团。在一个实施方式中，聚合物通过选自胺、酰胺、羰基、羧基、醚、硫醚和羟基中的至少一种官能团交联。在优选的实施方式中，聚合物包含氨基酸残基。交联可以通过这些残基中的一种或多种发生。
优选地，聚合物是生物聚合物。生物聚合物选自多肽和多糖。合适的多肽包括明胶、胶原和胶原模拟肽。合适的多糖包括壳聚糖、透明质酸盐(酯)和透明质酸。在优选的实施方式中，聚合物是明胶。
在一个实施方式中，聚合物是聚丙烯酰胺。
聚合物可以构成沉积于集电器上的基质的0.01至50重量％。优选地，聚合物构成沉积于集电器上的基质的0.01至20重量％。更优选地，聚合物可以构成沉积于集电器上的基质的0.1至15重量％，例如，1至10重量％。
聚合物的重量与导电材料(例如，碳)和电活性硫材料(例如，硫)的重量的比率可以为0.01-10:30-60，优选0.1-5:35-55，更优选1-3:40-50。在一个实施方式中，聚合物与导电材料(例如，碳)的重量比可以为0.01-15:5-35，优选0.1-10:8-25，更优选1-5:10-15。在一个实施方式中，聚合物与电活性材料(例如，硫)的重量比可以为0.01-20:20-50，优选0.1-15:25-45，更优选1-10:30-40。
交联剂
聚合物可以使用任何合适的方法，例如，通过加热或通过暴露于辐射例如UV辐射来行交联。例如，在使用生物聚合物如明胶的情况下，聚合物可以通过加热交联。
在一些实施例中，聚合物通过交联剂与聚合物反应而交联。可以使用任何合适的交联剂。
合适的交联剂包括醛。合适的醛的实例包括甲醛，二醛，戊二醛，甘油醛和糠醛。在一些实施方式中，酮用作交联剂。合适的酮包括丙酮，二缩醛和其他二酮，例如戊二酮，例如氯代戊烷二酮。
交联剂的其他实例包括碳二亚胺、脲、乙二醛、聚甲醛、亚胺、二环氧化合物和二异氰酸酯。也可以使用酶，例如反式谷氨酰胺酶。在进一步的实施方式中，交联剂选自双(2-氯乙基脲)；2-羟基-4,6-二氯-1,3,5-三嗪；US 3,288,775中公开的反应性含卤素化合物；氨基甲酰基吡啶鎓化合物，其中吡啶环带有硫酸盐或烷基硫酸盐基团，公开于US 4,063,952和US 5,529,892中；二乙烯基砜和S-三嗪衍生物如2-羟基-4,6-二氯-s-三嗪。合适的交联剂的其他实例包括1-乙基-3-[3-二甲基氨基丙基]碳二亚胺盐酸盐(EDC或EDAC)。
交联剂可以以任何合适的量添加。例如，粘结剂中的交联剂与聚合物的重量比可以为0.01-20:10-200，优选0.1-10:20-100，更优选1-5:10-50。
聚合物可以通过任何合适的方法交联。例如，在一个实施方式中，包含导电材料、电活性硫材料和粘合剂的电极混合物可以分散于溶剂(例如，水或有机溶剂)中而形成施加于集电器上的浆料。可以将浆料干燥并将获得的结构压缩而形成沉积于集电器上的基质。交联剂可以施加于基质上而使基质中的聚合物交联。交联剂可以作为单独的溶液施加或与随后在电池组装期间与电极接触的电解质溶液混合。
在可替换的实施方式中，交联剂可以在将浆料沉积于集电器上之前或之后添加到浆料中。
在另一个可替换方案中，聚合物可以在引入电极混合物之前交联。包含导电材料、电活性硫材料和交联的聚合物粘合剂的得到的混合物可以分散于溶剂(例如，水或有机溶剂)中而形成施加于集电器上的浆料。可以将浆料干燥并压缩得到的结构而形成沉积于集电器上的基质。
交联反应可以通过添加水分，用例如UV辐照或通过升高的温度而增强。
电活性硫材料和导电材料
基质包括电活性硫材料和导电材料的混合物。这种混合物形成电活性层，其与集电器接触放置。
电活性硫材料可以包括单质硫、基于硫的有机化合物、基于硫的无机化合物和含硫聚合物。优选使用单质硫。
导电材料可以是任何合适的固体导电材料。优选地，固体导电材料可以由碳构成。实例包括碳黑、碳纤维、石墨烯和碳纳米管。其他合适的材料包括金属(例如，薄片，锉屑和粉末)和导电聚合物。优选使用碳黑。
电活性硫材料可以以60至90重量％，优选65至85重量％，更优选70至80重量％的量存在于沉积于集电器上的基质中。
导电材料可以以10至45重量％，优选15至35重量％，更优选20至25重量％的量存在于沉积于集电器上的基质中。
电活性硫材料与导电材料的重量比可以为0.01-10:10-50，优选0.1-5:15-45，更优选1-5:20-35。
锂硫电池
本发明的电化学电池可以是任何合适的锂-硫电池。电池通常包括负极、由本文描述的电极形成的正极和电解质。负极可以由锂金属或锂金属合金构成。优选地，负极是金属箔电极，如锂箔电极。锂箔可以由锂金属或锂金属合金形成。
隔板可以置于负极和正极之间。电解质可以引入电池中而润湿正极和隔板。在一个实施方式中，隔板置于正极上并用电解质润湿，之后将负极置于隔板上方。电解质可以通过例如涂覆或喷涂施加于隔板上。
电解质允许电荷在负极和正极之间传递。优选地，电解质润湿正极的孔隙以及隔板的孔隙。在一个实施方式中，用于组装电池的电解质包含可以使粘结剂中存在的聚合物反应和交联的交联剂。合适的交联剂如上所述。当存在时，交联剂可以以0.01至10重量％，优选0.1至1重量％的浓度存在于电解质中。
可以使用任何合适的电解质。电解质可以包含有机溶剂和盐，例如锂盐。合适的有机溶剂包括醚，酯，酰胺，胺，亚砜，磺酰胺，有机磷酸酯和砜。实例包括四氢呋喃，2-甲基四氢呋喃，丙酸甲基丙酯，丙酸乙基丙酯，乙酸甲酯，1,2-二甲氧基乙烷，1,3-二氧戊环，二甘醇二甲醚(2-甲氧基乙基醚)，三甘醇二甲醚，四甘醇二甲醚，丁内酯，1,4-二噁烷，1,3-二噁烷，六甲基磷酰胺，吡啶，二甲基亚砜，磷酸三丁酯，磷酸三甲酯，N,N,N,N-四乙基磺酰胺和砜及它们的混合物。
合适的电解质盐包括锂盐。合适的锂盐包括六氟磷酸锂，六氟砷酸锂，硝酸锂，高氯酸锂，三氟甲磺酰亚胺锂，双(草酸)硼酸锂和三氟甲磺酸锂。优选的锂盐是三氟甲磺酸锂(lithium trifluoromethanesulphonate)(也称为三氟甲磺酸锂(lithium triflate))。可以使用盐的组合。例如，三氟甲磺酸锂可以与硝酸锂组合使用。锂盐可以以0.1至5M，优选0.5至3M的浓度存在于电解质中。
隔板可以置于负极和正极之间。在本发明的电池中存在隔板的情况下，隔板可以包括允许离子在电池的电极之间移动的任何合适的多孔基材。隔板应该位于电极之间以防止电极之间的直接接触。基材的孔隙率应为至少30％，优选至少50％，例如，高于60％。合适的隔板包括由聚合物材料形成的网。合适的聚合物包括聚丙烯、尼龙和聚乙烯。非编织聚丙烯是特别优选的。可以使用多层的隔板。
结合本发明的具体方面、实施方式或实施例描述的特征、整体、特性、化合物、化学部分或基团应该理解为，除非与其不相容，可以适用于本文描述的任何其他方面、实施方式或实施例。本说明书中公开的所有特征(包括任何所附权利要求，摘要和附图)和/或如此公开的任何方法或过程的所有步骤，除了至少一些这样的特征和/或步骤的组合是相互排斥的情况之外，可以以任何组合进行组合。本发明不限于任何前述实施方式的细节。本发明会拓展至本说明书中公开的特征(包括任何所附权利要求，摘要和附图)中的任何新颖的特征，或任何新颖组合，或拓展至如此公开的任何方法或过程的步骤的任何新颖的特征，或任何新颖的组合。
读者的注意力会导向连同本申请一起与本说明书同时或在本说明书之前提交的以及与本说明书一起对公众公开的所有论文和文件，并且所有这些论文和文件的内容都通过引证结合于本文中。
实施例1
在这个实施例中，将碳和硫研磨并与聚合物粘结剂和水混合而形成浆料，其中硫含量为75wt％，碳为23wt％，且明胶粘结剂为2wt％(40-50wt％，在H2O中)。将含有丙酮作为交联剂的溶液(水:交联剂(2:1比率))作为溶剂加入到分散体中，以形成固体含量为20wt％的分散体。然后将浆料施加于集电器上并在35℃下干燥以从涂覆的正极上除去溶剂，获得5.0mAh·cm-2的表面容量。正极用于组装填充有基于醚的电解质的6S/5Li电池。
以下图1显示了在0.2C和0.1C(分别为放电-充电)速率下循环的电池的放电性能，并与其中未添加交联剂的电池比较。可以观察到，即使两种电池都显示出相似的初始放电容量值，使用交联剂生产的电池随着时间的在约1100mAh·g(S) -1的硫利用率下保持稳定。在另一方面，使用未交联的粘结剂组装的电池在第三次循环后开始退化。
使用交联的粘结剂观察到的改进可以归因于由聚合物粘结剂与交联剂反应而导致的正极结构的完整性增强。还认为这种交联反应会改进涂层与集电器的粘附性，降低可能导致电池过早退化的脱离的风险。
实施例2
正极通过在集电器上沉积硫、碳和明胶的混合物而形成。从正极切割两个正方形(2×2cm)。
在手套箱中，将5滴福尔马林(37％甲醛的H2O溶液，具有10％甲醇作为稳定剂)施加于一个正极样品上并放置过夜。然后用棉签进行刮擦测试，并且显示福尔马林处理的样品具有比未处理样品好得多的正极完整性和对集电器的粘附性。
实施例3
进行一系列实验以研究明胶是否与甲醛发生交联。
使用TA Instruments DHR2流变仪以振荡时间扫描模式测量存储/损耗模量和相角。
明胶原液的制备：
将来自冷水鱼皮的15g明胶@45％(ex Sigma Aldrich G7765)称入100cm-3玻璃烧杯中，向其中加入15g去离子水，然后在IKA磁力搅拌器上混合5分钟。
明胶/甲醛溶液的制备
将3g制备的明胶溶液称入玻璃小瓶中，向其中加入0.036g甲醛溶液(ex SigmaAldrich 252549)并在IKA磁力搅拌器上混合而得到2％溶液。
流变测定
使用TA Instruments DHR 2流变仪测量明胶/甲醛溶液以及作为基线的明胶原液的粘弹性。以下列出了流变仪参数和测试条件：
流变仪参数：
流变仪：TA Instruments DHR2流变仪
几何结构：平行板直径40mm
2％应变，1Hz频率下振荡时间2小时
珀耳帖板温度：40℃
结果：
由振荡时间扫描，明胶原液的损耗模量和相角几乎没有偏差。因此，没有交联的证据。
然而，加入2％甲醛则存在明胶交联的证据。用3841秒处的交叉点观察到模量的明显变化。相角从约90°下降到2°，证实了凝胶结构的增加。
Claims (18)
1.一种用于锂硫电池的电极，所述电极包括沉积于集电器上的基质，其中所述基质包含导电材料、电活性硫材料和包含聚合物的粘合剂，所述聚合物交联以在所述基质中形成交联的聚合物网络。
2.根据权利要求1所述的电极，其中，所述聚合物经由选自胺、酰胺、羰基、羧基、醚、硫醚和羟基中的至少一种的官能团交联。
3.根据权利要求1或2所述的电极，其中，所述聚合物是生物聚合物。
4.根据前述权利要求中任一项所述的电极，其中，生物聚合物选自多肽和多糖。
5.根据权利要求4所述的电极，其中，所述生物聚合物是选自明胶、胶原和胶原模拟肽的多肽。
6.根据权利要求3所述的电极，其中，所述生物聚合物是壳聚糖。
7.根据权利要求1或2所述的电极，其中，所述聚合物是聚丙烯酰胺。
8.根据前述权利要求中任一项所述的电极，其中，所述聚合物经由交联剂交联。
9.根据权利要求8所述的电极，其中，所述交联剂选自环氧交联剂、二乙烯基砜、二硫化碳、醛、酮、碳二亚胺和二异氰酸酯。
10.根据权利要求9所述的电极，其中，所述交联剂是甲醛或二异氰酸酯。
11.根据前述权利要求中任一项所述的电极，其中，所述基质包含0.01至50重量％的交联的聚合物。
12.根据前述权利要求中任一项所述的电极，其中，所述导电材料包括颗粒碳材料，并且所述电活性硫材料包括单质硫。
13.根据前述权利要求中任一项所述的电极，其中，所述导电材料和所述电活性硫材料分散在所述基质中的交联的聚合物网络中。
14.一种锂硫电池，包括前述权利要求中任一项所述的正极和由锂金属或锂合金形成的负极。
15.一种生产用于锂硫电池的电极的方法，所述方法包括：
将电极混合物沉积在集电器上以涂覆所述集电器，其中所述电极混合物包含导电材料、电活性硫材料和包含聚合物的粘合剂；以及
使所述聚合物交联，从而将包含交联的聚合物网络的基质沉积在所述集电器上。
16.根据权利要求15所述的方法，其中，将包含所述电极混合物和溶剂的浆料沉积在所述集电器上。
17.根据权利要求16所述的方法，其中，将交联剂添加至涂覆的所述集电器以使所述聚合物交联。
18.根据权利要求15所述的方法，其中，将交联剂添加至电解质，随后使所述电解质与涂覆的所述集电器接触。
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| CN110518244A (zh) * | 2019-07-16 | 2019-11-29 | 南方科技大学 | 锂硫电池粘结剂及其制备、使用方法和锂硫电池 |
| JP7477147B2 (ja) * | 2020-04-14 | 2024-05-01 | 学校法人 関西大学 | リチウム硫黄二次電池の正極用バインダ |
| KR102681603B1 (ko) * | 2021-07-30 | 2024-07-03 | 경상국립대학교 산학협력단 | 바이오고분자 바인더를 포함하는 리튬-황 배터리용 양극재와 이의 제조 방법 |
| WO2024177450A1 (ko) * | 2023-02-20 | 2024-08-29 | 경상국립대학교산학협력단 | 하이드록시기 또는 카르복실산 기반 황전지용 고분자 바인더 및 이를 포함하는 황전지 |
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| TWI787212B (zh) | 2022-12-21 |
| BR112019006408A8 (pt) | 2023-02-07 |
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| KR20190077320A (ko) | 2019-07-03 |
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