CN118589034A - A polymer electrolyte and its preparation method and application - Google Patents
A polymer electrolyte and its preparation method and application Download PDFInfo
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- CN118589034A CN118589034A CN202411067898.4A CN202411067898A CN118589034A CN 118589034 A CN118589034 A CN 118589034A CN 202411067898 A CN202411067898 A CN 202411067898A CN 118589034 A CN118589034 A CN 118589034A
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- polymer electrolyte
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- battery
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 152
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 46
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 19
- -1 tetrafluoroborate Chemical compound 0.000 claims abstract description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 29
- 229920001223 polyethylene glycol Polymers 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 24
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical group FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical group FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 42
- 230000005012 migration Effects 0.000 abstract description 21
- 238000013508 migration Methods 0.000 abstract description 21
- 150000003949 imides Chemical class 0.000 abstract 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract 1
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 18
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 13
- 239000011230 binding agent Substances 0.000 description 11
- 239000006258 conductive agent Substances 0.000 description 11
- 239000004014 plasticizer Substances 0.000 description 11
- 230000010287 polarization Effects 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 239000002608 ionic liquid Substances 0.000 description 8
- 239000007784 solid electrolyte Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000002897 diene group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- ORRRIJVZQZKAKQ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxypropoxy)propoxy]propane Chemical compound CCOCC(C)OCC(C)OCC(C)OCC ORRRIJVZQZKAKQ-UHFFFAOYSA-N 0.000 description 1
- FXAFMVDJGZBDEP-UHFFFAOYSA-N 1-ethoxy-2-[2-[2-(2-ethoxypropoxy)propoxy]propoxy]propane Chemical compound CCOCC(C)OCC(C)OCC(C)OCC(C)OCC FXAFMVDJGZBDEP-UHFFFAOYSA-N 0.000 description 1
- RERATEUBWLKDFE-UHFFFAOYSA-N 1-methoxy-2-[2-(2-methoxypropoxy)propoxy]propane Chemical compound COCC(C)OCC(C)OCC(C)OC RERATEUBWLKDFE-UHFFFAOYSA-N 0.000 description 1
- ROSYHLFNMZTEKZ-UHFFFAOYSA-N 1-methoxy-2-[2-[2-(2-methoxypropoxy)propoxy]propoxy]propane Chemical compound COCC(C)OCC(C)OCC(C)OCC(C)OC ROSYHLFNMZTEKZ-UHFFFAOYSA-N 0.000 description 1
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 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
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
本发明提供一种聚合物电解质及其制备方法和应用，其中，聚合物电解质包括聚合物和锂盐，所述聚合物包括所示化合物和所示化合物共聚后得到的交联体，式I中，m为选自2~20之间的整数；式II中，R选自双三氟甲基磺酰亚胺根、双氟磺酰亚胺根、高氯酸根、四氟硼酸根、二草酸硼酸根、二氟草酸硼酸根或三氟甲基磺酸根，n选自1~10之间的整数。本发明的聚合物电解质兼具优异的离子电导率、锂离子迁移数和力学强度。The present invention provides a polymer electrolyte and a preparation method and application thereof, wherein the polymer electrolyte comprises a polymer and a lithium salt, wherein the polymer comprises The compounds shown and The crosslinked body obtained by copolymerization of the compounds shown in the formula I, m is an integer selected from 2 to 20; in the formula II, R is selected from bistrifluoromethylsulfonyl imide, bisfluorosulfonyl imide, perchlorate, tetrafluoroborate, dioxalate borate, difluorooxalate borate or trifluoromethylsulfonate, and n is an integer selected from 1 to 10. The polymer electrolyte of the present invention has excellent ionic conductivity, lithium ion migration number and mechanical strength.
Description
技术领域Technical Field
本发明属于电池技术领域，涉及一种聚合物电解质及其制备方法和应用。The invention belongs to the technical field of batteries and relates to a polymer electrolyte and a preparation method and application thereof.
背景技术Background Art
电解质是锂二次电池的重要组成部分，其在正负极之间起到输送离子、传导电流的作用。相比于液态电解质，固态电解质具有更高的机械强度和稳定性，能够有效地抑制锂枝晶的生长，降低电池短路的风险，此外，其在较宽的温度范围内都能保持良好的性能，具有较好的温度稳定性，并且固态电解质的化学稳定性好，不易与电极发生反应，有利于延长电池的循环寿命。聚合物固态电解质是一种应用广泛的固态电解质，其具有较好的柔韧性和可加工性，得到了广泛的研究。聚氧化乙烯（PEO）来源广泛，与锂盐的兼容性好，通常作为聚合物固态电解质的主要原料，然而现有的聚氧化乙烯基固态电解质在使用过程中仍存在离子电导率低、锂离子迁移数低、力学强度差等问题，导致电池的倍率性能、循环性能和安全性能较差。Electrolyte is an important component of lithium secondary batteries, which plays the role of transporting ions and conducting current between the positive and negative electrodes. Compared with liquid electrolytes, solid electrolytes have higher mechanical strength and stability, can effectively inhibit the growth of lithium dendrites, and reduce the risk of battery short circuit. In addition, they can maintain good performance in a wide temperature range and have good temperature stability. Solid electrolytes have good chemical stability and are not easy to react with electrodes, which is conducive to extending the cycle life of the battery. Polymer solid electrolytes are a widely used solid electrolyte with good flexibility and processability, and have been widely studied. Polyethylene oxide (PEO) has a wide range of sources and good compatibility with lithium salts. It is usually used as the main raw material for polymer solid electrolytes. However, the existing polyethylene oxide solid electrolytes still have problems such as low ionic conductivity, low lithium ion migration number, and poor mechanical strength during use, resulting in poor rate performance, cycle performance and safety performance of the battery.
发明内容Summary of the invention
本发明提供一种聚合物电解质，该聚合物电解质兼具优异的离子电导率、锂离子迁移数和力学强度。The present invention provides a polymer electrolyte having excellent ion conductivity, lithium ion transference number and mechanical strength.
本发明还提供一种聚合物电解质的制备方法，在式I所示化合物和式II所示化合物聚合之前加入锂盐，使得锂盐均匀分散于聚合形成的交联体中，从而得到上述具有优异离子电导率、锂离子迁移数和力学强度的聚合物电解质。The present invention also provides a method for preparing a polymer electrolyte, wherein a lithium salt is added before the polymerization of the compound represented by Formula I and the compound represented by Formula II, so that the lithium salt is uniformly dispersed in the cross-linked body formed by the polymerization, thereby obtaining the above-mentioned polymer electrolyte with excellent ionic conductivity, lithium ion migration number and mechanical strength.
本发明还提供一种电池，由于包括上述聚合物电解质，因此该电池兼具优异的倍率性能、循环性能和安全性能。The present invention also provides a battery, which comprises the polymer electrolyte and thus has excellent rate performance, cycle performance and safety performance.
本发明还提供一种电子设备，由于包括上述电池，因此该电子设备在使用过程中也兼具优异的倍率性能、循环性能和安全性能。The present invention also provides an electronic device. Since the electronic device comprises the battery, the electronic device also has excellent rate performance, cycle performance and safety performance during use.
本发明提供一种聚合物电解质，包括聚合物和锂盐，所述聚合物包括式I所示化合物和式II所示化合物共聚后得到的交联体：The present invention provides a polymer electrolyte, comprising a polymer and a lithium salt, wherein the polymer comprises a crosslinked body obtained by copolymerization of a compound represented by Formula I and a compound represented by Formula II:
式I中，m为选自2~20之间的整数；In formula I, m is an integer selected from 2 to 20;
式II中，R选自双三氟甲基磺酰亚胺根、双氟磺酰亚胺根、高氯酸根、四氟硼酸根、二草酸硼酸根、二氟草酸硼酸根或三氟甲基磺酸根，n选自1~10之间的整数。In formula II, R is selected from bis(trifluoromethylsulfonyl)imide, bis(fluorosulfonyl)imide, perchlorate, tetrafluoroborate, dioxalatoborate, difluorooxalatoborate or trifluoromethylsulfonate, and n is selected from an integer between 1 and 10.
如上所述的聚合物电解质，其中，所述式I所示化合物和所述式II所示化合物的共聚摩尔比为（70~95）：（5~30）。The polymer electrolyte as described above, wherein the copolymerization molar ratio of the compound represented by formula I to the compound represented by formula II is (70-95):(5-30).
如上所述的聚合物电解质，其中，所述式I所示化合物和所述式II所示化合物中聚乙二醇结构单元的总和与所述锂盐的摩尔比为（10~25）:1。The polymer electrolyte as described above, wherein the molar ratio of the sum of the polyethylene glycol structural units in the compound represented by Formula I and the compound represented by Formula II to the lithium salt is (10-25):1.
如上所述的聚合物电解质，其中，所述锂盐包括双三氟甲基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、二氟草酸硼酸锂、二草酸硼酸锂、高氯酸锂中的一种或多种。The polymer electrolyte as described above, wherein the lithium salt includes one or more of lithium bis(trifluoromethylsulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalatoborate, lithium dioxalatoborate, and lithium perchlorate.
本发明还提供一种如上所述的聚合物电解质的制备方法，包括以下步骤：The present invention also provides a method for preparing the polymer electrolyte as described above, comprising the following steps:
向式I所示化合物、式II所示化合物和锂盐的混合体系中加入自由基引发剂，引发聚合反应，得到所述聚合物电解质。A free radical initiator is added to a mixed system of the compound represented by formula I, the compound represented by formula II and a lithium salt to initiate a polymerization reaction to obtain the polymer electrolyte.
如上所述的制备方法，其中，所述式II所示化合物通过包括以下步骤的方法制备得到：The preparation method as described above, wherein the compound represented by formula II is prepared by a method comprising the following steps:
1）使1-乙烯基咪唑与式III所示化合物反应，得到式IV所示化合物；1) reacting 1-vinylimidazole with the compound represented by formula III to obtain the compound represented by formula IV;
式III中，X选自Cl、Br或I；In formula III, X is selected from Cl, Br or I;
2）使式IV所示化合物与LiR发生离子交换反应，得到式II所示化合物；2) allowing the compound represented by formula IV to undergo an ion exchange reaction with LiR to obtain a compound represented by formula II;
。 .
如上所述的制备方法，其中，所述聚合反应的温度为60~100℃，时间为4~12h。The preparation method as described above, wherein the polymerization reaction temperature is 60-100° C. and the time is 4-12 hours.
本发明还提供一种电池，包括正极、负极和位于正极与负极之间的电解质层，其中，所述电解质层包括如上所述的聚合物电解质。The present invention also provides a battery, comprising a positive electrode, a negative electrode and an electrolyte layer located between the positive electrode and the negative electrode, wherein the electrolyte layer comprises the polymer electrolyte as described above.
如上所述的电池，其中，所述电解质层的厚度为20~50μm。In the battery as described above, the thickness of the electrolyte layer is 20-50 μm.
本发明还提供一种电子设备，包括如上所述的电池。The present invention also provides an electronic device, comprising the battery as described above.
本发明的实施，至少具有以下有益效果：The implementation of the present invention has at least the following beneficial effects:
1）本发明的聚合物电解质的聚合物包括式I所示化合物和式II所示化合物共聚后得到的交联体，共聚后式I所示化合物的聚乙二醇链段位于交联体的侧链上，具有更好的运动能力，可以更好的传导锂离子，共聚还能够使交联体具有较低的结晶度，从而提升电解质的离子传导率。此外，式II所示化合物还能够向交联体中引入咪唑离子液体单元，咪唑离子液体单元能够通过静电作用吸附锂盐中的阴离子，提高锂离子迁移数，降低浓差极化，提升电池的倍率性能。共聚后的交联体仍保留有适宜含量的聚乙二醇链段，且交联体的三维网状结构还能够使电解质具有较高的力学强度，从而使电解质兼具良好的柔韧性和力学强度，在与正负极界面有良好相容性降低界面阻抗的同时，还能避免正负极接触短路，从而改善电池的循环性能和安全性能。综上，本申请的聚合物电解质具有较高的离子传导率、锂离子迁移数和力学强度，包括该聚合物电解质的电池兼具优异的循环性能、安全性能和倍率性能。1) The polymer of the polymer electrolyte of the present invention includes a crosslinked body obtained by copolymerization of the compound shown in formula I and the compound shown in formula II. After copolymerization, the polyethylene glycol segment of the compound shown in formula I is located on the side chain of the crosslinked body, has better mobility, can better conduct lithium ions, and copolymerization can also make the crosslinked body have a lower crystallinity, thereby improving the ion conductivity of the electrolyte. In addition, the compound shown in formula II can also introduce imidazolium ion liquid units into the crosslinked body. The imidazolium ion liquid unit can adsorb anions in lithium salts through electrostatic action, increase the number of lithium ion migration, reduce concentration polarization, and improve the rate performance of the battery. The crosslinked body after copolymerization still retains an appropriate amount of polyethylene glycol segments, and the three-dimensional network structure of the crosslinked body can also make the electrolyte have a higher mechanical strength, so that the electrolyte has both good flexibility and mechanical strength, and has good compatibility with the positive and negative electrode interfaces to reduce the interface impedance, while also avoiding the positive and negative electrodes from contacting short circuits, thereby improving the battery's cycle performance and safety performance. In summary, the polymer electrolyte of the present application has high ion conductivity, lithium ion transference number and mechanical strength, and the battery including the polymer electrolyte has excellent cycle performance, safety performance and rate performance.
2）本发明提供的聚合物电解质的制备方法，在式I所示化合物和式II所示化合物聚合之前加入锂盐，一方面式I所示化合物和式II所示化合物能够溶解锂盐，另一方面在聚合之前加入能够使锂盐均匀分散于聚合形成的交联体中，从而得到具有优异离子电导率、锂离子迁移数和力学强度的聚合物电解质。2) The preparation method of the polymer electrolyte provided by the present invention comprises adding a lithium salt before the polymerization of the compound represented by Formula I and the compound represented by Formula II. On the one hand, the compound represented by Formula I and the compound represented by Formula II can dissolve the lithium salt. On the other hand, the addition before the polymerization can make the lithium salt uniformly dispersed in the cross-linked body formed by the polymerization, thereby obtaining a polymer electrolyte with excellent ionic conductivity, lithium ion migration number and mechanical strength.
具体实施方式DETAILED DESCRIPTION
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
PEO分子链具有较高的介电常数，可以溶解众多锂盐，是公认的适于制备全固态电解质的基体。然而，纯的PEO聚合物易于结晶，导致其可以传导锂离子的非晶相结构较少，进而使得固态电解质的离子电导率较低。为了提高其离子电导率，可以提高使用温度以降低PEO聚合物的结晶度，但结晶度降低后电解质的力学强度也随之下降，导致正负极容易接触短路。此外，PEO传导锂离子的原理为通过分子链氧原子中的孤对电子与锂离子配位，进而实现对锂离子进行传输，但是锂盐中的阴离子不会与聚合物作用，因而阴离子在电场下的传输能力强于锂离子，从而使锂离子的迁移数较低，相应地，电池在充放电过程中容易出现浓差极化，锂离子沉积不均等问题，最终使电池的安全性能、倍率性能和循环性能较差。PEO molecular chains have a high dielectric constant and can dissolve many lithium salts. They are recognized as a matrix suitable for preparing all-solid-state electrolytes. However, pure PEO polymers are easy to crystallize, resulting in less amorphous phase structures that can conduct lithium ions, which in turn makes the ionic conductivity of solid electrolytes low. In order to improve its ionic conductivity, the operating temperature can be increased to reduce the crystallinity of PEO polymers, but after the crystallinity decreases, the mechanical strength of the electrolyte also decreases, resulting in easy contact and short circuit between the positive and negative electrodes. In addition, the principle of PEO conducting lithium ions is to coordinate with lithium ions through the lone pair of electrons in the oxygen atoms of the molecular chain, thereby realizing the transmission of lithium ions, but the anions in the lithium salts will not interact with the polymers, so the transmission ability of anions under the electric field is stronger than that of lithium ions, resulting in a lower migration number of lithium ions. Accordingly, the battery is prone to concentration polarization and uneven lithium ion deposition during the charge and discharge process, which ultimately makes the battery's safety performance, rate performance and cycle performance poor.
基于此，本发明提供一种聚合物电解质，包括聚合物和锂盐，其中，聚合物包括式I所示化合物和式II所示化合物共聚后得到的交联体：Based on this, the present invention provides a polymer electrolyte, comprising a polymer and a lithium salt, wherein the polymer comprises a crosslinked body obtained by copolymerization of a compound represented by Formula I and a compound represented by Formula II:
式I中，m为选自2~20之间的整数；In formula I, m is an integer selected from 2 to 20;
式II中，R选自双三氟甲基磺酰亚胺根、双氟磺酰亚胺根、高氯酸根、四氟硼酸根、二草酸硼酸根、二氟草酸硼酸根或三氟甲基磺酸根，n选自1~10之间的整数。In formula II, R is selected from bis(trifluoromethylsulfonyl)imide, bis(fluorosulfonyl)imide, perchlorate, tetrafluoroborate, dioxalatoborate, difluorooxalatoborate or trifluoromethylsulfonate, and n is selected from an integer between 1 and 10.
式I所示化合物是含有聚乙二醇链段的丙烯酸酯类化合物，式II所示化合物是采用乙烯基咪唑对聚乙二醇链段进行化学改性后得到的化合物，其首尾两端含有两个双键，起到交联剂的作用，在与式I所示化合物共聚后能使两者交联形成具有三维网状结构的交联体。The compound shown in formula I is an acrylate compound containing a polyethylene glycol chain segment, and the compound shown in formula II is a compound obtained by chemically modifying the polyethylene glycol chain segment using vinyl imidazole. It contains two double bonds at both ends and acts as a cross-linking agent. After copolymerization with the compound shown in formula I, the two can be cross-linked to form a cross-linked body with a three-dimensional network structure.
一方面，共聚后式I所示化合物的聚乙二醇链段位于交联体的侧链上，具有更好的运动能力，可以更好的传导锂离子，另一方面，共聚还能够使交联体具有较低的结晶度，从而通过以上两方面的作用提升电解质的离子传导率。On the one hand, after copolymerization, the polyethylene glycol segment of the compound shown in Formula I is located on the side chain of the cross-linked body, has better mobility, and can better conduct lithium ions. On the other hand, copolymerization can also make the cross-linked body have a lower crystallinity, thereby improving the ion conductivity of the electrolyte through the above two effects.
通过在交联体中引入咪唑型离子液体单元还能够通过静电作用吸附锂盐中的阴离子，提高锂离子迁移数，降低浓差极化，提升电池的倍率性能。另外，本发明通过在式II所示化合物嵌入咪唑离子液体单元，而非直接采用具有双烯基的咪唑离子液体的交联剂与式I所示化合物共聚，其原因在于，含有双烯基的咪唑离子液体单体在与式I所示化合物共聚时，两者的极性差异过大，容易出现相分离现象，得到的聚合物类似于盐类化合物，玻璃化转变温度和结晶熔融温度会更高，不利于锂离子的传导，而本申请通过在聚乙二醇链段的首尾两端引入咪唑型离子液体，使式II所示化合物与式I所示化合物具有相近的极性，避免了两者共聚时相分离出现，使得到的聚合物可保持较低的玻璃化转变温度和结晶熔融温度，有利于锂离子的传导。By introducing an imidazole-type ionic liquid unit in the cross-linked body, anions in lithium salts can also be adsorbed by electrostatic action, the number of lithium ion migration can be increased, concentration polarization can be reduced, and the rate performance of the battery can be improved. In addition, the present invention embeds an imidazole ionic liquid unit in the compound shown in formula II, rather than directly using a cross-linking agent of an imidazole ionic liquid with a diene group to copolymerize with the compound shown in formula I. The reason is that when the imidazole ionic liquid monomer containing a diene group is copolymerized with the compound shown in formula I, the polarity difference between the two is too large, and phase separation phenomenon is likely to occur. The obtained polymer is similar to a salt compound, and the glass transition temperature and the crystalline melting temperature will be higher, which is not conducive to the conduction of lithium ions. The present application introduces an imidazole-type ionic liquid at both ends of the polyethylene glycol segment, so that the compound shown in formula II has a similar polarity to the compound shown in formula I, avoiding the phase separation when the two copolymerize, so that the obtained polymer can maintain a lower glass transition temperature and crystalline melting temperature, which is conducive to the conduction of lithium ions.
共聚后得到的交联体中仍含有适宜含量分布的聚乙二醇链段，能够使电解质具有良好的柔韧性，与正负极界面具有良好的相容性，有利于降低界面电阻，改善电池的循环性能。The cross-linked body obtained after copolymerization still contains polyethylene glycol segments with appropriate content distribution, which can make the electrolyte have good flexibility and good compatibility with the positive and negative electrode interfaces, which is beneficial to reducing the interface resistance and improving the cycle performance of the battery.
相比于线型的聚合物分子结构，交联体的三维网状结构能够使聚合物电解质具有更高的力学强度，即便应用于具有较高面密度正极的锂金属固态电池中时也不易导致正负极接触短路，使电池兼具优异的能量密度和安全性能。Compared with the linear polymer molecular structure, the three-dimensional network structure of the cross-linked body can make the polymer electrolyte have higher mechanical strength. Even when used in lithium metal solid-state batteries with a high surface density positive electrode, it is not easy to cause short circuit between the positive and negative electrodes, so that the battery has both excellent energy density and safety performance.
综上，本发明通过使聚合物电解质包括式I所示化合物和式II所示化合物共聚后得到的交联体，能够使聚合物电解质具有较高的离子电导率、锂离子迁移数和力学强度，进而使电池能够兼具优异的能量密度、倍率性能、循环性能和安全性能。In summary, the present invention enables the polymer electrolyte to have higher ionic conductivity, lithium ion migration number and mechanical strength by making the polymer electrolyte include a cross-linked body obtained by copolymerization of the compound represented by formula I and the compound represented by formula II, thereby enabling the battery to have excellent energy density, rate performance, cycle performance and safety performance.
在一种优选的实施方式中，式I所示化合物和式II所示化合物的共聚摩尔比为（70~95）：（5~30）。示例性的，式I所示化合物和式II所示化合物的共聚摩尔比可以是70:30、80:20、90:10、95:5等。In a preferred embodiment, the copolymerization molar ratio of the compound represented by Formula I and the compound represented by Formula II is (70-95): (5-30). Exemplarily, the copolymerization molar ratio of the compound represented by Formula I and the compound represented by Formula II can be 70:30, 80:20, 90:10, 95:5, etc.
需要说明的是，本发明中的共聚摩尔比可以通过式I所示化合物和式II所示的投料比调控。例如，可以通过控制式I所示化合物和式II所示化合物的投料摩尔比为70:30实现式I所示化合物和式II所示化合物的共聚摩尔比为70:30。It should be noted that the copolymerization molar ratio in the present invention can be regulated by the feed ratio of the compound shown in Formula I and the compound shown in Formula II. For example, the copolymerization molar ratio of the compound shown in Formula I and the compound shown in Formula II can be 70:30 by controlling the feed molar ratio of the compound shown in Formula I and the compound shown in Formula II to be 70:30.
当式II所示化合物的含量较低时，得到的交联体强度低，电池有短路的防线，并且不利于离子迁移数的提升，当式II所示化合物的含量较高时，得到的交联体刚性过强，与正负极的接触不好，并且也会使电解质的离子电导率低。When the content of the compound shown in Formula II is low, the strength of the obtained cross-linked body is low, the battery has a short circuit defense line, and it is not conducive to the improvement of the ion migration number. When the content of the compound shown in Formula II is high, the rigidity of the obtained cross-linked body is too strong, the contact with the positive and negative electrodes is poor, and the ionic conductivity of the electrolyte is also low.
如前所述，聚乙二醇链段中的氧原子能够促进锂离子的传导，基于此，本发明对聚合物中的聚乙二醇链段和锂盐的用量比进行了研究，发现当聚合物中的聚乙二醇链段与锂盐的摩尔比为（10~25）:1时，能够使电解质具有更高的离子电导率。示例性的，聚乙二醇链段与锂盐的摩尔比可以是10:1、13:1、15:1、18:1、20:1、23:1、25:1或者以上任意两个摩尔比值所组成的范围。As mentioned above, the oxygen atoms in the polyethylene glycol segment can promote the conduction of lithium ions. Based on this, the present invention studies the usage ratio of the polyethylene glycol segment and the lithium salt in the polymer, and finds that when the molar ratio of the polyethylene glycol segment to the lithium salt in the polymer is (10-25):1, the electrolyte can have a higher ion conductivity. Exemplarily, the molar ratio of the polyethylene glycol segment to the lithium salt can be 10:1, 13:1, 15:1, 18:1, 20:1, 23:1, 25:1 or a range consisting of any two of the above molar ratios.
本发明对锂盐的种类不作具体限定，其可以选自双三氟甲基磺酰亚胺锂、双氟磺酰亚胺锂、六氟磷酸锂、六氟砷酸锂、四氟硼酸锂、二氟草酸硼酸锂、二草酸硼酸锂、高氯酸锂中的一种或多种。The present invention does not specifically limit the type of lithium salt, which can be selected from one or more of lithium bis(trifluoromethylsulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium difluorooxalatoborate, lithium dioxalatoborate, and lithium perchlorate.
本发明还提供一种如上所述的聚合物电解质的制备方法，包括以下步骤：The present invention also provides a method for preparing the polymer electrolyte as described above, comprising the following steps:
向式I所示化合物、式II所示化合物和锂盐的混合体系中加入自由基引发剂，引发聚合反应，得到所述聚合物电解质。A free radical initiator is added to a mixed system of the compound represented by formula I, the compound represented by formula II and a lithium salt to initiate a polymerization reaction to obtain the polymer electrolyte.
本发明的制备方法，在式I所示化合物、式II所示化合物和锂盐的混合体系中加入自由基引发剂，在电解质制备的过程中引发式I所示化合物和式II所示化合物的原位聚合，在形成交联体的同时，使锂盐均匀分布于交联体中，从而得到兼具优异离子导电性、锂离子迁移数和力学强度的聚合物电解质。The preparation method of the present invention comprises adding a free radical initiator to a mixed system of a compound represented by formula I, a compound represented by formula II and a lithium salt, initiating in-situ polymerization of the compound represented by formula I and the compound represented by formula II during the preparation of the electrolyte, and while forming a cross-linked body, making the lithium salt uniformly distributed in the cross-linked body, thereby obtaining a polymer electrolyte having excellent ionic conductivity, lithium ion migration number and mechanical strength.
式I所示化合物可以通过商购获得或者采用本领域公知的技术手段自行制备得到。The compound represented by formula I can be obtained by commercial purchase or prepared by self-preparation using techniques known in the art.
式II所示化合物可以参照本领域常规方法制备得到，例如，可以采用包括以下步骤的方法制备得到式II所示化合物：The compound represented by formula II can be prepared by referring to conventional methods in the art. For example, the compound represented by formula II can be prepared by a method comprising the following steps:
1）使1-乙烯基咪唑与式III所示化合物反应，得到式IV所示化合物；1) reacting 1-vinylimidazole with the compound represented by formula III to obtain the compound represented by formula IV;
式III中，X选自Cl、Br或I；In formula III, X is selected from Cl, Br or I;
2）使式IV所示化合物与LiR发生离子交换反应，得到式II所示化合物；2) allowing the compound represented by formula IV to undergo an ion exchange reaction with LiR to obtain a compound represented by formula II;
。 .
步骤1）中的1-乙烯基咪唑和式III所示化合物均可商购或者通过公知的手段自行合成得到，两者反应可无需加入溶剂，按照至少2：1的摩尔比混合后反应，两者的反应温度为60~100℃，反应时间为4~12h。The 1-vinylimidazole and the compound represented by formula III in step 1) can be purchased commercially or synthesized by known means. The reaction between the two can be carried out without adding a solvent. The two can be mixed in a molar ratio of at least 2:1 and reacted. The reaction temperature of the two is 60-100°C and the reaction time is 4-12h.
步骤2）中的离子交换反应可参照以下具体操作进行：The ion exchange reaction in step 2) can be carried out according to the following specific operations:
将式IV所示化合物溶于去离子水中，得到式IV所示化合物的水溶液，然后将其逐滴加入至LiR的水溶液中，并搅拌使离子交换反应充分进行，待沉淀物完全析出后，倒掉多余的水，洗涤干燥后即可得到式II所示化合物。The compound represented by formula IV is dissolved in deionized water to obtain an aqueous solution of the compound represented by formula IV, which is then added dropwise to the aqueous solution of LiR and stirred to allow the ion exchange reaction to proceed fully. After the precipitate is completely precipitated, excess water is poured off, and the compound represented by formula II is obtained after washing and drying.
其中，LiR中R的定义与式II化合物中R的定义一致。The definition of R in LiR is consistent with the definition of R in the compound of formula II.
本发明对聚合反应中所使用的自由基引发剂不作具体限定，其可以选自本领域常规使用的自由基引发剂，包括但不限于过氧自由基引发剂、偶氮类引发剂或光引发剂。The present invention does not specifically limit the free radical initiator used in the polymerization reaction, which can be selected from free radical initiators conventionally used in the art, including but not limited to peroxy free radical initiators, azo initiators or photoinitiators.
进一步的，自由基引发剂的用量可以是式I所示化合物和式II所示化合物总质量的0.5%~5%。Furthermore, the amount of the free radical initiator used can be 0.5% to 5% of the total mass of the compound represented by Formula I and the compound represented by Formula II.
上述交联反应可以通过加热实现交联固化，也可以在紫外光照射条件下进行交联固化，优选在加热条件下实现交联固化，加热温度可以是50~80℃，时间为1~5h。The cross-linking reaction can be cured by heating or by ultraviolet light irradiation. Preferably, the cross-linking reaction is cured by heating. The heating temperature can be 50-80° C. and the time can be 1-5 hours.
本发明还提供一种电池，包括正极、负极和位于正极与负极之间的电解质层，其中，所述电解质层包括如上所述的聚合物电解质。The present invention also provides a battery, comprising a positive electrode, a negative electrode and an electrolyte layer located between the positive electrode and the negative electrode, wherein the electrolyte layer comprises the polymer electrolyte as described above.
由于本发明的聚合物电解质具有较高的离子导电率、锂离子迁移数和力学强度，因此该电池也兼具优异的倍率性能、循环性能和安全性能。Since the polymer electrolyte of the present invention has high ion conductivity, lithium ion migration number and mechanical strength, the battery also has excellent rate performance, cycle performance and safety performance.
本发明的电解质层可以是仅包括上述聚合物电解质的固态电解质，也可以是上述聚合物电解质和液态电解液混合后得到的半固态电池，相应地，得到的电池既可以是半固态电池也可以是固态电池。The electrolyte layer of the present invention can be a solid electrolyte comprising only the above-mentioned polymer electrolyte, or can be a semi-solid battery obtained by mixing the above-mentioned polymer electrolyte and a liquid electrolyte. Accordingly, the obtained battery can be either a semi-solid battery or a solid battery.
可以理解的是，电解质层的厚度越大，电池的安全性能越好，但较大的厚度也会增加锂离子传输的阻力，导致电池阻抗增加，使电池的倍率性能变差，同时也会使电池的能量密度变差。基于以上考虑，电解质层的厚度优选为20~50μm。示例性的，电解质层的厚度可以是20μm、25μm、30μm、35μm、40μm、45μm、50μm或者以上任意两者数值所组成的范围。It is understandable that the greater the thickness of the electrolyte layer, the better the safety performance of the battery, but a greater thickness will also increase the resistance to lithium ion transmission, resulting in an increase in battery impedance, which will deteriorate the rate performance of the battery and also deteriorate the energy density of the battery. Based on the above considerations, the thickness of the electrolyte layer is preferably 20 to 50 μm. Exemplarily, the thickness of the electrolyte layer can be 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or a range consisting of any two of the above values.
本发明正极和负极都可以参考本领域常规的正负极组成。The positive electrode and the negative electrode of the present invention can refer to the conventional positive and negative electrode compositions in the art.
具体的，正极包括正极集流体和设置于正极集流体至少一个表面的正极活性物质层。Specifically, the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.
本发明对正极集流体的组成不作具体限定，其可以选自本领域常规使用的正极集流体，例如铝箔。The present invention does not specifically limit the composition of the positive electrode current collector, which can be selected from positive electrode current collectors commonly used in the art, such as aluminum foil.
在一种具体的实施方式中，正极活性物质层包括正极活性物质、导电剂、粘结剂、锂盐和增塑剂。In a specific embodiment, the positive electrode active material layer includes a positive electrode active material, a conductive agent, a binder, a lithium salt and a plasticizer.
本发明对正极活性物质、导电剂、粘结剂、锂盐和增塑剂的种类均不作具体限定，均可以选自本领域常规使用的物质。The present invention does not specifically limit the types of the positive electrode active material, the conductive agent, the binder, the lithium salt and the plasticizer, and they can all be selected from materials commonly used in the art.
具体的，正极活性物质可选自钴酸锂（LiCoO2）、镍酸锂（LiNiO2）、磷酸铁锂（LiFePO4）、磷酸钴锂（LiCoPO4）、磷酸锰锂（LiMnPO4）、磷酸镍锂（LiNiPO4）、锰酸锂（LiMnO2）、二元材料LiNixA(1-x)O2（A选自Co、Mn中的一种，0<x<1）、三元材料LiNimBnC(1-m-n)O2（B、C独立地选自Co、Al、Mn中的至少一种，且B和C不相同，0<m<1，0<n<1）中的一种或多种。Specifically, the positive electrode active material can be selected from one or more of lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), lithium iron phosphate (LiFePO 4 ), lithium cobalt phosphate (LiCoPO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium nickel phosphate (LiNiPO 4 ), lithium manganese oxide (LiMnO 2 ), binary material LiNi x A (1-x) O 2 (A is selected from one of Co and Mn, 0<x<1), and ternary material LiNi m B n C (1-mn) O 2 (B and C are independently selected from at least one of Co, Al, and Mn, and B and C are different, 0<m<1, 0<n<1).
导电剂可选自乙炔黑、Super P、Super S、石墨烯、碳纤维、碳纳米管和科琴黑中的一种或多种。The conductive agent may be selected from one or more of acetylene black, Super P, Super S, graphene, carbon fiber, carbon nanotube and Ketjen black.
粘结剂可选自聚偏氟乙烯、偏氟乙烯-六氟丙烯共聚物、聚四氟乙烯、聚丙烯腈、聚碳酸丙烯酯、丁苯橡胶、丁腈橡胶、羧甲基纤维素钠、聚环氧乙烷、环氧乙烷-环氧丙烷共聚物中的一种或多种。The binder can be selected from one or more of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polytetrafluoroethylene, polyacrylonitrile, polypropylene carbonate, styrene-butadiene rubber, nitrile rubber, sodium carboxymethyl cellulose, polyethylene oxide, and ethylene oxide-propylene oxide copolymer.
增塑剂可选自乙二醇二甲醚、乙二醇二乙醚、丙二醇二甲醚、丙二醇二乙醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、二乙二醇二乙醚、三乙二醇二乙醚、四乙二醇二乙醚、二丙二醇二甲醚、三丙二醇二甲醚、四丙二醇二甲醚、二丙二醇二乙醚、三丙二醇二乙醚、四丙二醇二乙醚、1,3-二氧戊环、1,4-二氧六环，碳酸丙烯酯、碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、丁二腈、己二腈中的一种或多种。The plasticizer can be selected from one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol diethyl ether, tetrapropylene glycol diethyl ether, 1,3-dioxolane, 1,4-dioxane, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, succinonitrile and adiponitrile.
锂盐的选择可参考聚合物电解质中锂盐的选择种类，此处不再赘述。The selection of lithium salts can refer to the selection of lithium salts in polymer electrolytes, which will not be described in detail here.
在一种优选的实施方式中，正极活性物质层中正极活性物质、导电剂、粘结剂、锂盐和增塑剂的质量比为（50-90）：（1-10）：（9-20）：（0-10）：（0-10）。In a preferred embodiment, the mass ratio of the positive electrode active material, the conductive agent, the binder, the lithium salt and the plasticizer in the positive electrode active material layer is (50-90): (1-10): (9-20): (0-10): (0-10).
负极包括负极集流体和设置于负极集流体至少一个表面的负极活性物质层。The negative electrode includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
本发明对负极集流体的组成不作具体限定，其可以选自本领域常规使用的负极集流体，如铜箔。The present invention does not specifically limit the composition of the negative electrode current collector, which can be selected from negative electrode current collectors commonly used in the art, such as copper foil.
在一种具体的实施方式中，负极活性物质层包括负极活性物质、导电剂、粘结剂、锂盐和增塑剂。In a specific embodiment, the negative electrode active material layer includes a negative electrode active material, a conductive agent, a binder, a lithium salt and a plasticizer.
本发明对负极活性物质、导电剂、粘结剂、锂盐和增塑剂的种类均不作具体限定，均可以选自本领域常规使用的物质。The present invention does not specifically limit the types of the negative electrode active material, the conductive agent, the binder, the lithium salt and the plasticizer, and they can all be selected from materials commonly used in the art.
具体的，负极活性物质可选自锂金属、锂金属合金、石墨、硅、氧化亚硅、硅碳复合物或硅合金。当负极活性物质选自锂金属及锂金属合金时，负极活性物质层中不包含导电剂、粘结剂、锂盐和增塑剂等组分。Specifically, the negative electrode active material can be selected from lithium metal, lithium metal alloy, graphite, silicon, silicon oxide, silicon carbon composite or silicon alloy. When the negative electrode active material is selected from lithium metal and lithium metal alloy, the negative electrode active material layer does not contain components such as conductive agent, binder, lithium salt and plasticizer.
负极活性物质层中的导电剂、粘结剂、锂盐和增塑剂的种类均可以参考前述正极活性物质层中导电剂、粘结剂、锂盐和增塑剂的选择，此处不再赘述。The types of the conductive agent, binder, lithium salt and plasticizer in the negative electrode active material layer can refer to the selection of the conductive agent, binder, lithium salt and plasticizer in the positive electrode active material layer, and will not be repeated here.
在一种优选的实施方式中，负极活性物质层中负极活性物质、导电剂、粘结剂、锂盐和增塑剂的质量比为（50-90）：（1-10）：（9-20）：（0-10）：（0-10）。In a preferred embodiment, the mass ratio of the negative electrode active material, the conductive agent, the binder, the lithium salt and the plasticizer in the negative electrode active material layer is (50-90): (1-10): (9-20): (0-10): (0-10).
本发明对电池的制备方法不作特殊限定，其可以参考本领域常规方法制备得到。The present invention does not impose any particular limitation on the method for preparing the battery, and the battery can be prepared by referring to conventional methods in the art.
例如，在一种具体的实施方式中，可通过以下步骤制备得到电池：For example, in a specific embodiment, a battery can be prepared by the following steps:
1）将正极活性物质、导电剂、粘结剂、锂盐和增塑剂按照特定质量比分散于溶剂中形成正极活性物质层浆料，然后将正极活性物质层浆料涂覆于正极集流体上，干燥后得到正极；1) dispersing a positive electrode active material, a conductive agent, a binder, a lithium salt and a plasticizer in a solvent according to a specific mass ratio to form a positive electrode active material layer slurry, then coating the positive electrode active material layer slurry on a positive electrode current collector, and drying to obtain a positive electrode;
2）将金属锂复合于负极集流体上，得到负极；2) Compounding metallic lithium on the negative electrode current collector to obtain a negative electrode;
3）按照正极、聚合物电解质、负极的顺序组装后得到电芯，经将电芯封装后即可得到电池。3) The positive electrode, polymer electrolyte, and negative electrode are assembled in order to obtain a cell, and the battery is obtained after the cell is packaged.
本发明还提供一种电子设备，包括如上所述的电池。本发明对电子设备不作特别限定，其可以为包括该电池的任何用电设备，包括但不限于手机、笔记本电脑、电动自行车、电动汽车、电动玩具、储能设备等。The present invention also provides an electronic device, comprising the battery as described above. The present invention does not specifically limit the electronic device, which can be any electrical device comprising the battery, including but not limited to mobile phones, laptop computers, electric bicycles, electric cars, electric toys, energy storage devices, etc.
以下将通过具体的实施例对本发明提供的聚合物电解质及其制备方法和应用进一步进行详细地说明。The polymer electrolyte provided by the present invention and its preparation method and application will be further described in detail below through specific examples.
如无特殊说明，以下实施例中用到的试剂、材料以及仪器均为本领域的常规试剂、常规材料以及常规仪器，均可通过商购获得，所涉及的试剂也可通过本领域常规方法合成获得。Unless otherwise specified, the reagents, materials and instruments used in the following examples are conventional reagents, conventional materials and conventional instruments in the art and can be obtained commercially. The reagents involved can also be synthesized by conventional methods in the art.
以下实施例中，式III-1、式III-2、式III-3、式III-5、式I-1、式I-2、式I-3、式I-4、式I-5、式b所示化合物均购自于西格玛奥德里奇。In the following examples, the compounds represented by formula III-1, formula III-2, formula III-3, formula III-5, formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, and formula b were all purchased from Sigma-Aldrich.
实施例1Example 1
本实施例提供一种聚合物电解质及全固态电池，其制备方法如下：This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is as follows:
1、聚合物电解质的制备1. Preparation of polymer electrolyte
1）将1-乙烯基咪唑和式III-1所示化合物按照摩尔比为2.1:1在圆底烧瓶中混合均匀，加热至60℃反应4h，得到混合液。1) 1-vinylimidazole and the compound represented by formula III-1 were mixed evenly in a round-bottom flask at a molar ratio of 2.1:1, and heated to 60° C. for reaction for 4 h to obtain a mixed solution.
2）将混合液溶于去离子水中，并将得到的溶液逐滴加入至LiTFSI的水溶液中，搅拌4h使离子交换反应充分进行，再将多余的水倒掉，将沉淀物水洗三次，干燥后得到式II-1所示化合物。2) The mixed solution was dissolved in deionized water, and the obtained solution was added dropwise to the aqueous solution of LiTFSI, stirred for 4 hours to allow the ion exchange reaction to proceed fully, and then the excess water was poured off, the precipitate was washed three times with water, and dried to obtain the compound represented by formula II-1.
3）将式I-1所示化合物和式II-1所示化合物按照摩尔比为80:20混合后，得到混合物，按照式I-1所示化合物和式II-1所示化合物中聚乙二醇结构单元的总和与LiTFSI的摩尔比为18:1的比例向混合物中加入LiTFSI，再向其中加入基于式I-1所示化合物和式II-1所示化合物总质量0.5%的AIBN作为引发剂，加热至60℃聚合4h，得到聚合物电解质。3) The compound represented by formula I-1 and the compound represented by formula II-1 are mixed in a molar ratio of 80:20 to obtain a mixture, and LiTFSI is added to the mixture in a molar ratio of 18:1 between the sum of the polyethylene glycol structural units in the compound represented by formula I-1 and the compound represented by formula II-1 and LiTFSI, and then 0.5% of AIBN based on the total mass of the compound represented by formula I-1 and the compound represented by formula II-1 is added as an initiator, and the mixture is heated to 60° C. for polymerization for 4 hours to obtain a polymer electrolyte.
2、全固态电池的制备2. Preparation of all-solid-state batteries
1）将磷酸铁锂、Super P、分子量为60万的聚环氧乙烷、双三氟甲基磺酰亚胺锂和丁二腈按质量比78:2:10:5:5在N,N-二甲基甲酰胺混合均匀，得到正极活性物质层浆料，然后用刮刀将正极活性物质层浆料涂在厚度为15μm的铝集流体上，之后先在60℃下干燥1h，在80℃干燥3h，得到厚度为75μm正极，其中磷酸铁锂的面载量为15mg/cm2。1) Lithium iron phosphate, Super P, polyethylene oxide with a molecular weight of 600,000, lithium bis(trifluoromethylsulfonyl)imide and succinonitrile were mixed evenly in N,N-dimethylformamide at a mass ratio of 78:2:10:5:5 to obtain a positive electrode active material layer slurry, and then the positive electrode active material layer slurry was coated on an aluminum current collector with a thickness of 15 μm with a scraper, and then dried at 60°C for 1 hour and at 80°C for 3 hours to obtain a positive electrode with a thickness of 75 μm, in which the surface loading of lithium iron phosphate was 15 mg/ cm2 .
2）将以上制备得到的正极裁成4.5×6cm2，使用厚度为25μm的锂铜复合带（锂层的厚度为15μm，铜层的厚度为10μm）作为负极并将其裁减为4.7×6.2cm2，将以上制备得到的聚合物电解质裁成4.8×6.3cm2、厚度为40μm的尺寸。在充满氩气的手套箱中(O2含量≤0.5ppm、H2O含量≤0.5 ppm）按照正极、聚合物电解质、锂铜复合带的顺序组装电芯，封装后得到全固态电池。2) The positive electrode prepared above was cut into 4.5×6 cm 2 , a 25 μm thick lithium copper composite tape (lithium layer thickness of 15 μm, copper layer thickness of 10 μm) was used as the negative electrode and cut into 4.7×6.2 cm 2 , and the polymer electrolyte prepared above was cut into 4.8×6.3 cm 2 , 40 μm thick. In a glove box filled with argon (O 2 content ≤ 0.5 ppm, H 2 O content ≤ 0.5 ppm), the battery cell was assembled in the order of positive electrode, polymer electrolyte, and lithium copper composite tape, and the all-solid-state battery was obtained after packaging.
实施例2Example 2
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物和式II-1所示化合物的摩尔比替换为90:10。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the compound represented by Formula I-1 and the compound represented by Formula II-1 is replaced to 90:10.
实施例3Example 3
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物和式II-1所示化合物的摩尔比替换为70:30。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the compound represented by Formula I-1 and the compound represented by Formula II-1 is replaced with 70:30.
实施例4Example 4
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物和式II-1所示化合物的摩尔比替换为60:40。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the compound represented by Formula I-1 and the compound represented by Formula II-1 is replaced to 60:40.
实施例5Example 5
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物替换为式I-2所示化合物。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, in step 3), the compound represented by Formula I-1 is replaced by the compound represented by Formula I-2.
实施例6Example 6
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物替换为式I-3所示化合物。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, in step 3), the compound represented by Formula I-1 is replaced by the compound represented by Formula I-3.
实施例7Example 7
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤1）中的式III-1所示化合物替换为式III-2所示化合物，相应的，步骤2）得到的为式II-2所示化合物，步骤3）中也将式II-1所示化合物替换为式II-2所示化合物。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, the compound represented by formula III-1 in step 1) is replaced by the compound represented by formula III-2, and correspondingly, the compound represented by formula II-2 is obtained in step 2), and the compound represented by formula II-1 is also replaced by the compound represented by formula II-2 in step 3).
实施例8Example 8
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤1）中的式III-1所示化合物替换为式III-3所示化合物，相应的，步骤2）得到的为式II-3所示化合物，步骤3）中也将式II-1所示化合物替换为式II-3所示化合物。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that, in the preparation of the polymer electrolyte, the compound represented by formula III-1 in step 1) is replaced by the compound represented by formula III-3, and correspondingly, the compound represented by formula II-3 is obtained in step 2), and the compound represented by formula II-1 is also replaced by the compound represented by formula II-3 in step 3).
实施例9Example 9
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤3）中，式I-1所示化合物和式II-1所示化合物中聚乙二醇结构单元的总和与LiTFSI的摩尔比替换为10：1。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Example 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the sum of the polyethylene glycol structural units in the compound represented by Formula I-1 and the compound represented by Formula II-1 to LiTFSI is replaced with 10:1.
实施例10Example 10
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤3）中，式I-1所示化合物和式II-1所示化合物中聚乙二醇结构单元的总和与LiTFSI的摩尔比替换为25：1。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that in Example 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the sum of the polyethylene glycol structural units in the compound represented by Formula I-1 and the compound represented by Formula II-1 to LiTFSI is replaced with 25:1.
实施例11Embodiment 11
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤3）中，式I-1所示化合物和式II-1所示化合物中聚乙二醇结构单元的总和与LiTFSI的摩尔比替换为8：1。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Example 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the sum of the polyethylene glycol structural units in the compound represented by Formula I-1 and the compound represented by Formula II-1 to LiTFSI is replaced with 8:1.
实施例12Example 12
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤3）中，式I-1所示化合物和式II-1所示化合物中聚乙二醇结构单元的总和与LiTFSI的摩尔比替换为30：1。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Example 1, except that, in the preparation of the polymer electrolyte, in step 3), the molar ratio of the sum of the polyethylene glycol structural units in the compound represented by Formula I-1 and the compound represented by Formula II-1 to LiTFSI is replaced with 30:1.
实施例13Example 13
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在全固态电池的制备中，将聚合物电解质的厚度替换为20μm。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that in the preparation of the all-solid-state battery, the thickness of the polymer electrolyte is replaced with 20 μm.
实施例14Embodiment 14
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在全固态电池的制备中，将聚合物电解质的厚度替换为50μm。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Embodiment 1, except that in the preparation of the all-solid-state battery, the thickness of the polymer electrolyte is replaced with 50 μm.
实施例15Embodiment 15
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在全固态电池的制备中，将聚合物电解质的厚度替换为15μm。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is substantially the same as that of Embodiment 1, except that in the preparation of the all-solid-state battery, the thickness of the polymer electrolyte is replaced with 15 μm.
实施例16Example 16
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在全固态电池的制备中，将聚合物电解质的厚度替换为60μm。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is substantially the same as that of Embodiment 1, except that, in the preparation of the all-solid-state battery, the thickness of the polymer electrolyte is replaced with 60 μm.
实施例17Embodiment 17
本实施例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤2）和步骤3）中的LiTFSI均替换为高氯酸锂，在步骤2）中，得到式II-4所示化合物，在步骤3）中，将式II-1所示化合物替换为式II-4所示化合物。This embodiment provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that of Example 1, except that, in the preparation of the polymer electrolyte, LiTFSI in step 2) and step 3) is replaced with lithium perchlorate, in step 2), a compound represented by formula II-4 is obtained, and in step 3), the compound represented by formula II-1 is replaced with a compound represented by formula II-4.
对比例1Comparative Example 1
本对比例提供一种聚合物电解质及全固态电池，聚合物电解质的制备步骤如下：This comparative example provides a polymer electrolyte and an all-solid-state battery. The steps for preparing the polymer electrolyte are as follows:
按照聚乙二醇结构单元与LiTFSI的摩尔比为18:1的比例将式I-1所示化合物与LiTFSI混合，再向混合物中加入基于式I-1所示化合物质量0.5%的AIBN作为引发剂，加热至60℃聚合4h，得到聚合物电解质。The compound represented by formula I-1 and LiTFSI were mixed in a molar ratio of polyethylene glycol structural units to LiTFSI of 18:1, and then 0.5% AIBN based on the mass of the compound represented by formula I-1 was added to the mixture as an initiator, and the mixture was heated to 60° C. for polymerization for 4 hours to obtain a polymer electrolyte.
全固态电池的制备方法参照实施例1。The preparation method of the all-solid-state battery refers to Example 1.
对比例2Comparative Example 2
本对比例提供一种聚合物电解质及全固态电池，聚合物电解质的制备步骤如下：This comparative example provides a polymer electrolyte and an all-solid-state battery. The steps for preparing the polymer electrolyte are as follows:
步骤1）和步骤2）与实施例1一致，步骤3）替换为：按照聚乙二醇结构单元与LiTFSI的摩尔比为18:1的比例将式II-1所示化合物与LiTFSI混合，再向混合物中加入基于式II-1所示化合物质量0.5%的AIBN作为引发剂，加热至60℃聚合4h，得到聚合物电解质。Step 1) and step 2) are consistent with Example 1, and step 3) is replaced by: mixing the compound represented by formula II-1 with LiTFSI in a molar ratio of polyethylene glycol structural unit to LiTFSI of 18:1, and then adding 0.5% AIBN as an initiator based on the mass of the compound represented by formula II-1 to the mixture, heating to 60°C for polymerization for 4 hours to obtain a polymer electrolyte.
全固态电池的制备方法参照实施例1。The preparation method of the all-solid-state battery refers to Example 1.
对比例3Comparative Example 3
本对比例提供一种聚合物电解质及全固态电池，聚合物电解质的制备步骤如下：This comparative example provides a polymer electrolyte and an all-solid-state battery. The steps for preparing the polymer electrolyte are as follows:
1）参照实施例1中式II-1的制备方法，将原料式III-1替换为，制备得到式a所示化合物；1) Referring to the preparation method of formula II-1 in Example 1, the raw material formula III-1 is replaced by , to prepare the compound represented by formula a;
2）将式a所示化合物和式b所示化合物按照摩尔比为80:20混合后，得到混合物，按照混合物中聚乙二醇结构单元与LiTFSI的摩尔比为18:1的比例向混合物中加入LiTFSI，再向其中加入基于式a所示化合物和式b所示化合物总质量0.5%的AIBN作为引发剂，加热至60℃聚合4h，得到聚合物电解质。2) The compound represented by formula a and the compound represented by formula b are mixed in a molar ratio of 80:20 to obtain a mixture, LiTFSI is added to the mixture in a ratio of 18:1 between the polyethylene glycol structural unit and LiTFSI in the mixture, and 0.5% of AIBN based on the total mass of the compound represented by formula a and the compound represented by formula b is added as an initiator, and the mixture is heated to 60° C. for polymerization for 4 hours to obtain a polymer electrolyte.
全固态电池的制备方法参照实施例1。The preparation method of the all-solid-state battery refers to Example 1.
对比例4Comparative Example 4
本对比例提供一种聚合物电解质及全固态电池，聚合物电解质的制备步骤如下：This comparative example provides a polymer electrolyte and an all-solid-state battery. The steps for preparing the polymer electrolyte are as follows:
将式I-1所示化合物与式b所示化合物按照摩尔比为80:20混合后，得到混合物，按照混合物中聚乙二醇结构单元与LiTFSI的摩尔比为18:1的比例向混合物中加入LiTFSI，再向其中加入基于式I-1所示化合物和式b所示化合物总质量0.5%的AIBN作为引发剂，加热至60℃聚合4h，得到聚合物电解质。The compound represented by formula I-1 and the compound represented by formula b are mixed in a molar ratio of 80:20 to obtain a mixture, and LiTFSI is added to the mixture in a ratio of 18:1 between the polyethylene glycol structural unit and LiTFSI in the mixture, and then 0.5% of AIBN based on the total mass of the compound represented by formula I-1 and the compound represented by formula b is added as an initiator, and the mixture is heated to 60° C. for polymerization for 4 hours to obtain a polymer electrolyte.
对比例5Comparative Example 5
本对比例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物替换为式I-4所示化合物。This comparative example provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that in Example 1, except that, in the preparation of the polymer electrolyte, in step 3), the compound represented by formula I-1 is replaced by the compound represented by formula I-4.
对比例6Comparative Example 6
本对比例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，步骤3）中，将式I-1所示化合物替换为式I-5所示化合物。This comparative example provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that in Example 1, except that, in the preparation of the polymer electrolyte, in step 3), the compound represented by formula I-1 is replaced by the compound represented by formula I-5.
对比例7Comparative Example 7
本对比例提供一种聚合物电解质及全固态电池，其制备方法与实施例1基本一致，不同之处在于，在聚合物电解质的制备中，将步骤1）中的式III-1所示化合物替换为式III-5所示化合物，相应的，步骤2）得到的为式II-5所示化合物，步骤3）中也将式II-1所示化合物替换为式II-5所示化合物。This comparative example provides a polymer electrolyte and an all-solid-state battery, and the preparation method thereof is basically the same as that in Example 1, except that, in the preparation of the polymer electrolyte, the compound represented by formula III-1 in step 1) is replaced by the compound represented by formula III-5, and correspondingly, the compound represented by formula II-5 is obtained in step 2), and the compound represented by formula II-1 is also replaced by the compound represented by formula II-5 in step 3).
测试例Test Case
一、对以上实施例和对比例制备得到的聚合物电解质进行以下性能的测试1. The polymer electrolytes prepared in the above examples and comparative examples were tested for the following properties:
1、锂离子迁移数1. Lithium ion migration number
测试方法：使用直径为16mm的锂片作为电极，将聚合物电解质裁成直径为19mm的圆片，组装为Li||Li对称电池，并对Li||Li对称电池进行锂离子迁移数和离子电导率的测试。使用电化学工作站对电池施加10mV的极化电压，极化时间为2h，测试极化前后对称电池的电流及阻抗，根据以下公式计算得到锂离子迁移数。Test method: Use a lithium sheet with a diameter of 16 mm as an electrode, cut the polymer electrolyte into a disc with a diameter of 19 mm, assemble it into a Li||Li symmetric battery, and test the lithium ion migration number and ion conductivity of the Li||Li symmetric battery. Use an electrochemical workstation to apply a polarization voltage of 10 mV to the battery, and the polarization time is 2 hours. Test the current and impedance of the symmetric battery before and after polarization, and calculate the lithium ion migration number according to the following formula.
其中，t+为锂离子迁移数，I0和Iss分别为极化开始前的电流和极化稳定后的电流，R0和Rss分别为极化开始前的阻抗和极化稳定后的阻抗，∆V为极化电压。Where t + is the lithium ion transfer number, I0 and Iss are the current before polarization starts and the current after polarization stabilizes, R0 and Rss are the impedance before polarization starts and the impedance after polarization stabilizes, and ∆V is the polarization voltage.
2、离子电导率2. Ionic conductivity
测试方法：使用冲片机分别裁切直径16mm、厚度200μm的不锈钢片，和直径19mm的聚合物电解质膜；将得到的不锈钢片、聚合物电解质膜按顺序叠好，使聚合物电解质膜处于不锈钢片之间，组装得到不锈钢对称电池。将不锈钢对称电池放入60℃的烘箱中10分钟后测试不锈钢对称电池的阻抗。Test method: Use a punching machine to cut stainless steel sheets with a diameter of 16 mm and a thickness of 200 μm, and a polymer electrolyte membrane with a diameter of 19 mm; stack the stainless steel sheets and polymer electrolyte membrane in order, so that the polymer electrolyte membrane is between the stainless steel sheets, and assemble a stainless steel symmetrical battery. Put the stainless steel symmetrical battery in a 60°C oven for 10 minutes and then test the impedance of the stainless steel symmetrical battery.
根据以下公式计算聚合物电解质的离子电导率：The ionic conductivity of the polymer electrolyte was calculated according to the following formula:
其中，σ为电解质的离子电导率，L为聚合物电解质膜的厚度，S为不锈钢片的面积，R为不锈钢对称电池的阻抗。Where σ is the ionic conductivity of the electrolyte, L is the thickness of the polymer electrolyte membrane, S is the area of the stainless steel sheet, and R is the impedance of the stainless steel symmetric cell.
以上测试结果如表1所示。The above test results are shown in Table 1.
二、对以上实施例和对比例制备得到的全固态电池进行以下性能的测试2. The following performance tests were performed on the all-solid-state batteries prepared in the above embodiments and comparative examples:
1、循环性能1. Cycle performance
测试方法：在60℃下，将电池以0.05C的倍率恒流充电至3.8V，静置5min，再以0.05C的倍率恒流放电至2.5V，将以上过程循环3次。然后以0.2C的倍率充电至3.8V，并于3.8V恒压充电至0.01C截止，再静置5min，最后以0.2C的倍率放电至2.5V，最后静置5min，如此循环至电池的比容量为初始容量的80%时截止，记录此时的循环圈数。Test method: At 60℃, charge the battery to 3.8V at a constant current of 0.05C, let it stand for 5 minutes, and then discharge it to 2.5V at a constant current of 0.05C, and repeat the above process 3 times. Then charge it to 3.8V at a rate of 0.2C, and charge it to 0.01C at 3.8V, let it stand for 5 minutes, and finally discharge it to 2.5V at a rate of 0.2C, and let it stand for 5 minutes. The cycle is terminated when the specific capacity of the battery is 80% of the initial capacity, and the number of cycles at this time is recorded.
2、倍率性能2. Rate performance
测试方法：在60℃下，将电池以0.05C的倍率恒流充电至3.8V，静置5min，再以0.05C的倍率恒流放电至2.5V，将以上过程循环3次。然后以0.1C的倍率充电至3.8V，静置5min后以0.1C的倍率放电至2.5V，静置5min之后以0.5C的倍率充电至3.8V，记录0.5C和0.1C的充电容量，通过0.5C的充电容量/0.1C的充电容量计算得到0.5C/0.1C倍率充电容量保持率。Test method: At 60°C, charge the battery to 3.8V at a constant current of 0.05C, let it stand for 5 minutes, and then discharge it to 2.5V at a constant current of 0.05C. Repeat the above process 3 times. Then charge it to 3.8V at a rate of 0.1C, let it stand for 5 minutes, then discharge it to 2.5V at a rate of 0.1C, let it stand for 5 minutes, then charge it to 3.8V at a rate of 0.5C, record the charging capacity of 0.5C and 0.1C, and calculate the 0.5C/0.1C rate charging capacity retention rate by 0.5C charging capacity/0.1C charging capacity.
以上数值的测试结果均在表1中列出。The test results of the above values are listed in Table 1.
表1Table 1
从表1中可分析得出以下结论：The following conclusions can be drawn from Table 1:
1）从实施例1~8以及对比例5~7的对比可看出，咪唑离子液体单元的占比对聚合物电解质的锂离子迁移数有明显影响，咪唑离子液体单元的占比越大，锂离子迁移数越高；聚乙二醇链段的含量对聚合物电解质的离子电导率有明显影响，聚乙二醇链段的含量与n和m的数值有关，聚乙二醇链段的含量越小时，影响锂离子的传输，导致离子电导率低，聚乙二醇链段的含量越高时，容易增加聚合物电解质的结晶度，也会导致离子电导率降低，其中，实施例4相比于其余实施例，式II所示化合物的占比较大，咪唑含量相对较多，因此具有较高的锂离子迁移数，但相比之下聚乙二醇链段的含量较少，导致离子电导率较低，进而循环性能和倍率性能都相对较差。1) From the comparison of Examples 1 to 8 and Comparative Examples 5 to 7, it can be seen that the proportion of imidazole ionic liquid units has a significant effect on the lithium ion migration number of the polymer electrolyte. The greater the proportion of imidazole ionic liquid units, the higher the lithium ion migration number; the content of polyethylene glycol segments has a significant effect on the ionic conductivity of the polymer electrolyte. The content of polyethylene glycol segments is related to the values of n and m. The smaller the content of polyethylene glycol segments, the more it affects the transmission of lithium ions, resulting in low ionic conductivity. When the content of polyethylene glycol segments is higher, it is easy to increase the crystallinity of the polymer electrolyte, which also leads to a decrease in ionic conductivity. Among them, compared with the other embodiments, Example 4 has a larger proportion of the compound represented by Formula II and a relatively high imidazole content, so it has a higher lithium ion migration number, but in comparison, the content of polyethylene glycol segments is relatively low, resulting in lower ionic conductivity, and thus the cycle performance and rate performance are relatively poor.
2）从实施例1、9~12的对比可看出，式I-1所示化合物、式II所示化合物中聚乙二醇链段与LiTFSI的摩尔比在（10~25）:1范围内时，聚合物电解质兼具优异的锂离子迁移数和离子电导率、同时电池兼具优异的循环性能和倍率性能，然而两者的摩尔比在上述范围外，分别为8:1和30:1时，锂盐的含量过多或者过少，锂盐的含量过多时，锂盐无法解离，导致可以解离传输的锂离子数目少，锂盐的含量过少时，也会导致传输的锂离子数目少，进而导致聚合物电解质的锂离子迁移数和离子电导率均较低，电池的循环性能和倍率性能也相对较差。2) From the comparison of Examples 1 and 9 to 12, it can be seen that when the molar ratio of the polyethylene glycol segment to LiTFSI in the compound represented by Formula I-1 and the compound represented by Formula II is in the range of (10 to 25): 1, the polymer electrolyte has both excellent lithium ion migration number and ion conductivity, and the battery has both excellent cycle performance and rate performance. However, when the molar ratio of the two is outside the above range, namely 8: 1 and 30: 1, respectively, the content of the lithium salt is too much or too little. When the content of the lithium salt is too much, the lithium salt cannot be dissociated, resulting in a small number of lithium ions that can be dissociated and transmitted. When the content of the lithium salt is too little, it will also lead to a small number of lithium ions transmitted, which will lead to a low lithium ion migration number and ion conductivity of the polymer electrolyte, and the cycle performance and rate performance of the battery are also relatively poor.
3）从实施例1、13~16的对比可看出，聚合物电解质的厚度对电池的循环性能和倍率性能有一定影响，聚合物电解质的厚度在20~50μm内能够使电池兼具较为优异的锂离子循环性能和倍率性能，当聚合物电解质的厚度较低（15μm）时，锂离子的传输路径较短，具有更为优异的倍率性能，但电池较易短路，导致循环性能较差，当聚合物电解质的厚度较高（60μm）时，电池不易短路，循环性能较好，但锂离子的传输路径较长，导致电池的倍率性能变差。3) From the comparison of Examples 1 and 13 to 16, it can be seen that the thickness of the polymer electrolyte has a certain influence on the cycle performance and rate performance of the battery. When the thickness of the polymer electrolyte is within 20 to 50 μm, the battery can have both relatively excellent lithium ion cycle performance and rate performance. When the thickness of the polymer electrolyte is low (15 μm), the lithium ion transmission path is shorter, and it has more excellent rate performance, but the battery is more prone to short circuit, resulting in poor cycle performance. When the thickness of the polymer electrolyte is high (60 μm), the battery is not prone to short circuit and has better cycle performance, but the lithium ion transmission path is longer, resulting in poor rate performance of the battery.
4）从实施例1和17的对比可看出，不同种类的锂盐和R阴离子均能使聚合物电解质兼具优异的锂离子迁移数和离子电导率，电池兼具优异的循环性能和倍率性能。4) From the comparison between Examples 1 and 17, it can be seen that different types of lithium salts and R anions can make the polymer electrolyte have both excellent lithium ion transference number and ion conductivity, and the battery has both excellent cycle performance and rate performance.
5）从实施例1和对比例1和2的对比可看出，当仅采用式I-1所示化合物作为单体得到的聚合物与锂盐混合得到的聚合物电解质时，得到的聚合物无交联，力学强度较差，导致电池容易短路，电池的各方面性能均较差，尤其是循环性能更差，当仅采用式II-1所示化合物作为单体得到的聚合物与锂盐混合得到的聚合物电解质时，得到的聚合物交联程度过大，导致聚合物电解质刚性过强，与正负极界面的相容性差，接触不好，进而导致离子导电率、循环性能和倍率性能均较差。5) From the comparison between Example 1 and Comparative Examples 1 and 2, it can be seen that when only the polymer obtained by using the compound shown in Formula I-1 as a monomer is mixed with a lithium salt to obtain a polymer electrolyte, the obtained polymer has no cross-linking and has poor mechanical strength, which causes the battery to be easily short-circuited. The battery has poor performance in all aspects, especially the cycle performance. When only the polymer obtained by using the compound shown in Formula II-1 as a monomer is mixed with a lithium salt to obtain a polymer electrolyte, the obtained polymer has too much cross-linking, resulting in the polymer electrolyte being too rigid, having poor compatibility with the positive and negative electrode interfaces, and having poor contact, which in turn leads to poor ionic conductivity, cycle performance and rate performance.
6）从实施例1和对比例3的对比可看出，式a所示化合物与式b所示化合物交联聚合时，容易使出现微相分离现象，进而使聚合物电解质的锂离子迁移数、离子电导率较低，电池的循环性能和倍率性能也较差。6) From the comparison between Example 1 and Comparative Example 3, it can be seen that when the compound represented by Formula a and the compound represented by Formula b are cross-linked and polymerized, microphase separation is likely to occur, thereby reducing the lithium ion migration number and ion conductivity of the polymer electrolyte, and the cycle performance and rate performance of the battery are also poor.
7）从实施例1、对比例3和对比例4的对比中可看出，当对比例4的两个聚合单体中均不含有咪唑离子液体基团时，虽然聚乙二醇链段的存在能够使电解质具有较高的离子电导率，但锂离子迁移数较差，相应地，电池的循环性能和倍率性能也较差。7) From the comparison between Example 1, Comparative Example 3 and Comparative Example 4, it can be seen that when the two polymerized monomers of Comparative Example 4 do not contain imidazolium ionic liquid groups, although the presence of the polyethylene glycol segment can make the electrolyte have a higher ionic conductivity, the lithium ion migration number is poor, and accordingly, the cycle performance and rate performance of the battery are also poor.
以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions described in the above embodiments may still be modified, or some or all of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.
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