CN109830747B - Electrolyte applied to lithium, sodium and potassium batteries - Google Patents
Electrolyte applied to lithium, sodium and potassium batteries Download PDFInfo
- Publication number
- CN109830747B CN109830747B CN201910045144.1A CN201910045144A CN109830747B CN 109830747 B CN109830747 B CN 109830747B CN 201910045144 A CN201910045144 A CN 201910045144A CN 109830747 B CN109830747 B CN 109830747B
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- China
- Prior art keywords
- lithium
- electrolyte
- battery
- sodium
- additive
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- 239000003792 electrolyte Substances 0.000 title claims abstract description 69
- 239000011734 sodium Substances 0.000 title claims abstract description 25
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 20
- 239000011591 potassium Substances 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 48
- 239000000654 additive Substances 0.000 claims abstract description 42
- 230000000996 additive effect Effects 0.000 claims abstract description 37
- -1 organic compound salt Chemical class 0.000 claims abstract description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 150000001450 anions Chemical group 0.000 claims abstract description 9
- 150000001768 cations Chemical group 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 13
- 229920001774 Perfluoroether Polymers 0.000 claims description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000733 Li alloy Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 238000005524 ceramic coating Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 239000001989 lithium alloy Substances 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- PNYNRMYUWZPARE-UHFFFAOYSA-N propan-2-yl carbonofluoridate Chemical compound CC(C)OC(F)=O PNYNRMYUWZPARE-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000002401 inhibitory effect Effects 0.000 abstract description 7
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 31
- 238000001878 scanning electron micrograph Methods 0.000 description 21
- 210000001787 dendrite Anatomy 0.000 description 18
- 239000004698 Polyethylene Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 7
- 229910008029 Li-In Inorganic materials 0.000 description 6
- 229910006670 Li—In Inorganic materials 0.000 description 6
- 229910006309 Li—Mg Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 4
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 4
- 229910021135 KPF6 Inorganic materials 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- 229910021201 NaFSI Inorganic materials 0.000 description 3
- 229910006095 SO2F Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 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 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IVHFHHXLFFHTTA-UHFFFAOYSA-N 1-(2,5-diethoxy-4-methoxyphenyl)propan-2-amine Chemical compound CCOC1=CC(OC)=C(OCC)C=C1CC(C)N IVHFHHXLFFHTTA-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- PWGVOCGNHYMDLS-UHFFFAOYSA-N 3-(2-methoxyethoxy)propan-1-amine Chemical compound COCCOCCCN PWGVOCGNHYMDLS-UHFFFAOYSA-N 0.000 description 1
- 229910017459 CsPF6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020261 KBF4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013874 LiPF2O2 Inorganic materials 0.000 description 1
- 229910020892 NaBOB Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UQFSQHKNYIXJJE-UHFFFAOYSA-N [Na].FC(F)(F)c1nc(C#N)c([nH]1)C#N Chemical compound [Na].FC(F)(F)c1nc(C#N)c([nH]1)C#N UQFSQHKNYIXJJE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000001153 fluoro group Chemical class F* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- XKLXIRVJABJBLQ-UHFFFAOYSA-N lithium;2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound [Li].FC(F)(F)C1=NC(C#N)=C(C#N)N1 XKLXIRVJABJBLQ-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910001546 potassium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001541 potassium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- WKVRKSDUCURJNJ-UHFFFAOYSA-M potassium;difluorophosphinate Chemical compound [K+].[O-]P(F)(F)=O WKVRKSDUCURJNJ-UHFFFAOYSA-M 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- BFDWBSRJQZPEEB-UHFFFAOYSA-L sodium fluorophosphate Chemical compound [Na+].[Na+].[O-]P([O-])(F)=O BFDWBSRJQZPEEB-UHFFFAOYSA-L 0.000 description 1
- 229910001545 sodium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001542 sodium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides an electrolyte additive, an electrolyte and application of the electrolyte, belonging to the technical field of lithium metal batteries, and the specific technical scheme is as follows: the additive is an organic compound salt containing phosphorus and boron, the cation part of the additive is phosphorus-containing cations with four benzene rings, the anion part of the additive is boron-containing anions with four benzene rings, the additive is used in the electrolyte, the effect of inhibiting dendritic crystals is outstanding, the cycle performance and the safety performance of a lithium metal (or sodium or potassium) battery can be improved, and the advantage of high energy density of a lithium metal (or sodium or potassium) negative electrode is ensured to be exerted; the structural general formula of the additive is as follows:
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an electrolyte applied to a lithium, sodium and potassium battery.
Background
The theoretical specific capacity of the metallic lithium is as high as 3860 mAh/g, the electrode potential is as low as-3.04V (relative to a standard hydrogen electrode), and the energy density of the lithium battery can be obviously improved when the metallic lithium is used as a negative electrode. However, lithium dendrites are easily generated due to uneven deposition in the lithium metal negative electrode during use, and the lithium dendrites penetrate through a battery separator to cause short circuit and induce battery safety problems, and aggravate side reactions of lithium metal with an electrolyte to generate dead lithium to cause deterioration of cycle performance. There are many methods for solving the problem of the non-uniform deposition of lithium metal, and one of the more effective methods is to add a special additive to the electrolyte to induce the uniform deposition of lithium metal.
A paper (J. Am. chem. Soc., 2013, 135 (11), pp 4450-4456) published in JACS journal by Dingfei et al in 2013 adopts CsPF6 as an electrolyte additive, and can achieve a good effect of inhibiting lithium dendrites. The invention patent application with the application number of 201710482543.5 of Qian Jiangfeng et al in 2017 discloses a lithium metal battery electrolyte based on a sulfate additive, which has a good effect on dendritic crystal inhibition of a metal lithium battery.
Although various lithium metal battery electrolyte additives have been developed at present, and these additives can also inhibit the generation of lithium dendrites to some extent, the inhibition capability of these additives on lithium dendrites is not enough to enable the lithium metal negative electrode to be really applied in commercial batteries on a large scale, the inhibition capability of the additives on lithium dendrites still needs to be further improved, and it is of great significance to develop a novel additive with better effect of inhibiting lithium dendrites for lithium metal battery electrolytes. In addition, even for non-metal negative electrode battery systems, such as lithium ion batteries which are currently in large-scale commercial use, and sodium ion batteries and potassium ion batteries which are still under research, the non-metal negative electrode battery systems do not normally generate metal dendrites on the negative electrode, but still have high dendrite precipitation risk under relatively extreme use conditions such as fast charging, low-temperature charging, long-term cycling and the like. Therefore, the development of a novel additive with better effect of inhibiting lithium dendrite has important significance for improving the performance of lithium ion batteries, sodium ion batteries and potassium ion batteries.
Disclosure of Invention
The invention aims to improve the deposition uniformity of a lithium metal negative electrode in the charging and discharging process and inhibit the generation of lithium dendrites, and can improve the safety performance and the cycle performance of a metal lithium battery and simultaneously exert the advantage of high energy density of the lithium metal battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the electrolyte applied to the lithium, sodium and potassium batteries comprises a solvent, electrolyte salt and an additive, wherein the additive is organic compound salt containing phosphorus and boron, the cation part of the organic compound salt is phosphorus-containing cation with four benzene rings, the anion part of the organic compound salt is boron-containing anion with four benzene rings, and the structural general formula is as follows:
the R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、R19、R20、R21、R22、R23、R24、R25、R26、R27、R28、R29、R30、R31、R32、R33、R34、R35、R36、R37、R38、R39、R40Each independently selected from a hydrogen atom, a halogen atom, C1~C20Alkyl radical, C1~C20Alkoxy radical, C3~C20Alkylsilyl group, C1~C20Halogenated alkyl, sulfonic group, sulfonate group, carboxyl group, carboxylate group, aldehyde group, nitro group, amino group and cyano group.
Further, the electrolyte salt accounts for 4-80% of the total mass of the electrolyte.
Further, the additive accounts for 0.01-10% of the total mass of the electrolyte.
Further, the solvent is ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, dimethyl fluorocarbonate, methylethyl fluorocarbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylethyl carbonate, vinylene carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, methyl difluoroacetate, ethyl difluoroacetate, γ -butyrolactone, γ -valerolactone, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, fluoroether F-EPE, fluoroether D2, fluoroether HFPM, fluoroether MFE, One or more of fluoroether EME, acetonitrile, malononitrile, glutaronitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane, sulfolane and dimethyl sulfoxide are mixed according to any proportion to form a mixture.
Further, the electrolyte salt includes a sodium salt, a potassium salt, or a lithium salt.
Further, the lithium salt is LiPF6(lithium hexafluorophosphate), LiBF4Lithium tetrafluoroborate (LiClO), LiClO4(lithium perchlorate) LiAsF6(lithium hexafluoroarsenate), LiSbF6(lithium hexafluoroantimonate), LiPF2O2(lithium difluorophosphate), LiDTI (lithium 4, 5-dicyano-2-trifluoromethylimidazole), LiBOB (lithium bis (oxalato) borate), LiDFOB (lithium difluorooxalato borate), LiFSI (lithium bis (fluorosulfonyl) imide), LiN (SO)2RF)2、LiN(SO2F) (SO2RF)、LiNO3One or a combination of more of (lithium nitrate) and LiCl (lithium chloride), wherein R isF＝CnF2n+1And n is an integer of 1 to 10.
Further, the sodium salt is NaPF6(sodium hexafluorophosphate), NaBF4Sodium tetrafluoroborate and NaClO4(sodium perchlorate), NaAsF6Sodium hexafluoroarsenate, NaSbF6Sodium hexafluoroantimonate, NaPF2O2(II)Sodium fluorophosphate), NaDTI (sodium 4, 5-dicyano-2-trifluoromethylimidazole), NaBOB (sodium bisoxalato), NaDFOB (sodium difluorooxalato), NaFSI (sodium bis (fluorosulfonyl) imide), NaN (SO)2RF)2、NaN(SO2F) (SO2RF)、NaNO3One or more of (sodium nitrate) and NaCl (sodium chloride) are combined, wherein R isF＝CnF2n+1And n is an integer of 1 to 10.
Further, the potassium salt is KPF6(Potassium hexafluorophosphate), KBF4(Potassium tetrafluoroborate) and KClO4(Potassium perchlorate), KAsF6(Potassium hexafluoroarsenate), KSbF6(Potassium hexafluoroantimonate), KPF2O2(potassium difluorophosphate), KDTI (potassium 4, 5-dicyano-2-trifluoromethylimidazole), KBOB (potassium bis (oxalato) borate), KDFOB (potassium difluoro (oxalato) borate), KFSI (potassium bis (fluorosulfonyl) imide), KN (SO)2RF)2、KN(SO2F) (SO2RF)、KNO3One or more of potassium nitrate and KCl (potassium chloride), wherein R isF＝CnF2n+1And n is an integer of 1 to 10.
The electrolyte is applied to lithium metal batteries, sodium metal batteries, potassium metal batteries, lithium ion batteries, sodium ion batteries and potassium ion batteries.
Further, the lithium metal battery comprises a positive electrode, a diaphragm, a negative electrode and the electrolyte.
Further, the active material of the positive electrode is at least one of lithium cobaltate, lithium nickelate, spinel lithium manganate, layered lithium manganate, nickel-cobalt binary material, nickel-cobalt-manganese ternary material, nickel-cobalt-aluminum ternary material, lithium iron phosphate, spinel lithium nickel manganate, lithium-rich manganese-based material, transition metal oxide, transition metal sulfide, transition metal phosphate, sulfur and air; the active material of the negative electrode is at least one of lithium metal, lithium alloy, a lithium-carbon composite negative electrode and a lithium-silicon composite negative electrode; the diaphragm is one of PP, PE, PP/PE/PP, cellulose non-woven fabric diaphragm, PET non-woven fabric diaphragm and diaphragm with ceramic coating.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the additive is used in the electrolyte, has a remarkable effect of inhibiting dendritic crystals, can improve the cycle performance and the safety performance of a lithium metal (or sodium or potassium) battery, and simultaneously ensures that the additive exerts the advantage of high energy density of a lithium metal (or sodium or potassium) cathode. The production of the metal lithium (or sodium or potassium) battery by adopting the technology can be compatible with the existing lithium ion battery production line, and the technology has the advantages of simple and convenient operation, strong universality and easy large-scale continuous production; the additive is simultaneously suitable for non-metal cathode batteries such as lithium ion batteries, sodium ion batteries and potassium ion batteries, can effectively inhibit the precipitation of lithium dendrites (or sodium dendrites or potassium dendrites) in the circulation process, reduces the impedance and prolongs the circulation life.
Drawings
FIG. 1 is a graph of the cycle life of the batteries of example 1 and comparative example 1;
FIG. 2 is a graph of cell impedance for example 1 and comparative example 1;
FIG. 3 is a scanning electron micrograph of a lithium sheet after 50 cycles of example 1;
FIG. 4 is a scanning electron micrograph of a lithium sheet after 50 cycles of comparative example 1;
FIG. 5 is a graph of the cycle life of the batteries of example 2 and comparative example 2;
FIG. 6 is a graph of cell impedance for example 2 and comparative example 2;
FIG. 7 is a scanning electron micrograph of a lithium sheet of example 2 after 50 cycles;
FIG. 8 is a scanning electron micrograph of a lithium sheet after 50 cycles of comparative example 2;
FIG. 9 is a graph of the cycle life of the batteries of example 3 and comparative example 3;
FIG. 10 is a graph of cell impedance for example 3 and comparative example 3;
FIG. 11 is a scanning electron micrograph of a Li-In alloy negative electrode of example 3 after 50 cycles;
FIG. 12 is a scanning electron micrograph of a Li-In alloy negative electrode of comparative example 3 after 50 cycles;
FIG. 13 is a graph of the cycle life of the batteries of example 4 and comparative example 4;
FIG. 14 is a graph of cell impedance for example 4 and comparative example 4;
FIG. 15 is a scanning electron micrograph of a Li-Mg alloy negative electrode of example 4 after 50 cycles;
FIG. 16 is a scanning electron micrograph of a Li-Mg alloy negative electrode of comparative example 4 after 50 cycles;
FIG. 17 is a graph of the cycle life of the batteries of example 5 and comparative example 5;
FIG. 18 is a graph of cell impedance for example 5 and comparative example 5;
FIG. 19 is a scanning electron micrograph of a lithium metal negative electrode of example 5 after 50 cycles;
fig. 20 is a scanning electron micrograph of a lithium metal negative electrode of comparative example 5 after 50 cycles;
FIG. 21 is a graph of the cycle life of the batteries of example 6 and comparative example 6;
FIG. 22 is a graph of cell impedance for example 6 and comparative example 6;
FIG. 23 is a scanning electron micrograph of a sodium metal negative electrode of example 6 after 50 cycles;
FIG. 24 is a scanning electron micrograph of a sodium metal negative electrode of comparative example 6 after 50 cycles;
FIG. 25 is a graph of the cycle life of the batteries of example 7 and comparative example 7;
FIG. 26 is a graph of cell impedance for example 7 and comparative example 7;
fig. 27 is a photograph of a graphite negative electrode after 50 cycles of example 7;
fig. 28 is a photograph of the graphite negative electrode after 50 cycles of comparative example 7;
FIG. 29 is a graph of the cycle life of the batteries of example 8 and comparative example 8;
fig. 30 is a graph of cell impedance for example 8 and comparative example 8.
Detailed Description
The technical solution of the present invention is further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit of the technical solution of the present invention, and the technical solution of the present invention is covered by the protection scope of the present invention. Materials and instruments used in the present invention are all conventional materials and conventional instruments, and are commercially available, unless otherwise specified.
The experiments of the examples will prefer two additives from the general structural formula of the additives: r in the general formula1~R40All taking hydrogen atoms to obtain the additive: tetraphenylboron tetraphenylphosphonium; r in the general formula1~R20Taking the form of a F atom while simultaneously reacting R21~R40Taking hydrogen atoms to obtain the additive: tetraphenylboron tetrakispentafluorophenylphosphorus.
Example 1: under inert atmosphere, to a solution containing 4% LiPF6Adding tetraphenylboron tetraphenylphosphonium additive accounting for 10% of the total mass of the electrolyte into the EC/EMC (ethylene carbonate/ethyl methyl carbonate) (v ═ 1:1) electrolyte, mixing uniformly, and matching the obtained electrolyte with LiCoO2The positive plate, the PE diaphragm and the metal Li negative electrode are assembled into a lithium metal battery, the impedance of the battery and the cycle performance of the battery are tested at 0.5C/0.5C, and an SEM image of the metal Li after the battery which is cycled for 50 times is disassembled is taken.
Comparative example 1: in an inert atmosphere, with a composition containing 4% LiPF6With LiCoO as the electrolyte of EC/EMC (v 1:1)2The positive plate, the PE diaphragm and the metal Li negative electrode are assembled into a lithium metal battery, the impedance of the battery is tested, the cycle performance of the battery is tested at 0.5C/0.5C, and a scanning electron microscope image of the metal Li is tested after the battery which is cycled for 50 times is disassembled.
Example 2: in an inert atmosphere, 0.01% of tetraphenylboron tetrapentafluorophenylphosphine additive based on the total mass of electrolyte is added into DOL/DME (1, 3-dioxygen pentacyclic/ethylene glycol dimethyl ether) (v is 4:6) electrolyte containing 80% LiFSI and mixed evenly, the obtained electrolyte is matched with a positive plate, a PP diaphragm and a metal Li negative electrode of a carbon-sulfur composite material (wherein a positive active substance is sulfur, and carbon is used as a conductive framework and a sulfur carrier) to assemble a lithium-sulfur battery, the impedance of the battery is tested, the cycle performance of the battery is tested at 0.5C/0.5C, and an SEM image of the metal Li after the battery is disassembled after being cycled for 50 times is taken.
Comparative example 2: in an inert atmosphere, a lithium-sulfur battery is assembled by using a DOL/DME (v is 4:6) electrolyte containing 80% LiFSI, a PP (polypropylene) diaphragm and a metal Li negative electrode which are matched with a carbon-sulfur composite material, the impedance of the battery and the cycle performance of the battery are tested at 0.5C/0.5C, and an SEM (scanning electron microscope) image of metal Li is tested after the battery which is cycled for 50 times is disassembled.
Example 3: under an inert atmosphere, adding 12% LiPF6Adding 1% tetraphenylboron tetraphenylphosphonium additive of the total mass of the electrolyte into the EC/DMC (ethylene carbonate/dimethyl carbonate) (v is 1:1) electrolyte, mixing uniformly, assembling a lithium metal battery by using the obtained electrolyte together with a nickel-cobalt-manganese ternary (NCM) positive plate, a cellulose non-woven fabric diaphragm and a Li-In alloy negative electrode, testing the impedance of the battery and the cycle performance of the battery at 0.5C/0.5C, and taking an SEM image of the Li-In alloy after disassembling the battery after 50 times of cycle.
Comparative example 3: in an inert atmosphere, with a composition containing 12% LiPF6The battery is tested for impedance and cycling performance at 0.5C/0.5C by assembling the EC/DMC (v ═ 1:1) electrolyte with a nickel-cobalt-manganese ternary (NCM) positive plate, a cellulose non-woven fabric diaphragm and a Li-In alloy negative electrode, and an SEM image of the Li-In alloy is tested after disassembling the battery after 50 cycles.
Example 4: adding 2% tetraphenylboron tetrapentafluorophenylphosphine additive based on the total mass of an electrolyte to an EC/THF (ethylene carbonate/tetrahydrofuran) (v ═ 3:7) electrolyte containing 15% LiTFSI in an inert atmosphere, mixing the mixture uniformly, and blending the resulting electrolyte with LiFePO4The positive plate, the PP/PE/PP diaphragm and the Li-Mg alloy negative electrode are assembled into a lithium metal battery, the impedance of the battery is tested, the cycle performance of the battery is tested at 0.5C/0.5C, and an SEM image of the Li-Mg alloy is tested after the battery which is cycled for 50 times is disassembled.
Comparative example 4: LiFePO was combined with an EC/THF (v 3:7) electrolyte containing 15% LiTFSI in an inert atmosphere4The positive plate, the PP/PE/PP diaphragm and the Li-Mg alloy negative electrode are assembled into a lithium metal battery, the impedance of the battery is tested, the cycle performance of the battery is tested at 0.5C/0.5C, and an SEM image of the Li-Mg alloy is tested after the battery which is cycled for 50 times is disassembled.
Example 5: in an inert atmosphere, to a solution containing 10% LiClO4+1%LiNO3 DMSO (dimethyl sulfoxide)) Adding 1.2% tetraphenylboron tetrapentafluorophenylphosphorus additive based on the total mass of the electrolyte into the electrolyte, uniformly mixing, assembling the lithium-air battery by using the obtained electrolyte, an air positive electrode supported by porous carbon, a PE diaphragm and a metal lithium sheet negative electrode, testing the impedance of the battery and the cycle performance of the battery at 0.5C/0.5C, and taking an SEM image of the metal Li after disassembling the battery which is cycled for 50 times.
Comparative example 5: in an inert atmosphere, 10% LiClO4+1%LiNO3 The method comprises the following steps of assembling a DMSO (dimethyl sulfoxide) electrolyte, an air anode supported by porous carbon, a PE (polyethylene) diaphragm and a metal lithium sheet cathode into a lithium air battery, testing the impedance of the battery and the cycle performance of the battery at 0.5C/0.5C, and taking an SEM (scanning electron microscope) image of metal Li after disassembling the battery which is cycled for 50 times.
Example 6: in an inert atmosphere, 0.5% tetraphenylboron tetrapentafluorophenylphosphine additive based on the total mass of an electrolyte is added into 40% NaFSI DOL/PC (1, 3-dioxypentacyclo/propylene carbonate) (v is 6:4) electrolyte and uniformly mixed, the obtained electrolyte is used in a sodium metal battery (the positive electrode of the sodium iron phosphate, the negative electrode of the sodium metal battery are a metal sodium sheet, and the diaphragm of the sodium metal battery is a PET non-woven fabric diaphragm), the impedance of the battery and the cycle performance of the battery are tested at 0.5C/0.5C, and an SEM image of test metal Na after the battery is disassembled after 50 times of circulation is taken.
Comparative example 6: in an inert atmosphere, 40% of NaFSI DOL/PC (1, 3-dioxolane/propylene carbonate) (v is 6:4) electrolyte is used in a sodium metal battery (the positive electrode of the sodium iron phosphate, the negative electrode of the sodium metal battery is a metal sodium sheet, and the diaphragm is a PET non-woven fabric diaphragm), the impedance of the battery and the cycle performance of the battery are tested at 0.5C/0.5C, and an SEM image of the metal Na after the battery is disassembled after 50 times of circulation is taken.
Example 7: under inert atmosphere, to a solution containing 13% LiPF6Adding tetraphenylboron tetraphenylphosphonium additive accounting for 1.5 percent of the total mass of the electrolyte into EC/DMC (ethylene carbonate/dimethyl carbonate) (v ═ 1:1) electrolyte, mixing uniformly, and matching the obtained electrolyte with LiCoO2Assembling the positive plate, the PE diaphragm and the graphite negative electrode into a lithium ion battery, testing the impedance of the battery and the cycle performance of the battery under a high rate of 3C/3C, and taking the battery which is cycled for 50 timesAnd taking a picture after disassembly to observe the lithium precipitation state on the surface of the graphite cathode.
Comparative example 7: in an inert atmosphere, with 13% LiPF6EC/DMC (ethylene carbonate/dimethyl carbonate) (v ═ 1:1) electrolyte with LiCoO2The positive plate, the PE diaphragm and the metal graphite negative electrode are assembled into a lithium ion battery, the impedance of the battery and the cycle performance of the battery are tested under a 3C/3C high rate, and the battery which is cycled for 50 times is disassembled and then photographed to observe the lithium precipitation state on the surface of the graphite negative electrode.
Example 8: under an inert atmosphere, the mixture is added with 12 percent KPF6EC/DMC (ethylene carbonate/dimethyl carbonate) (v ═ 1:1) electrolyte was added with tetraphenylboron tetraphenylphosphonium additive in an amount of 0.9% by mass of the total electrolyte and mixed well, and the resulting electrolyte was used in a potassium ion battery (the positive electrode thereof was Prussian blue potassium salt KFeFe (CN))6The negative electrode is graphite, and the diaphragm is a PP/PE diaphragm), and the impedance of the battery and the cycle performance of the battery are tested under 3C/3C high rate.
Comparative example 8: under an inert atmosphere, 12% KPF6EC/DMC (ethylene carbonate/dimethyl carbonate) (v ═ 1:1) electrolyte was used in potassium ion batteries, the impedance of the batteries was tested and the cycling performance of the batteries was tested at 3C/3C high rate.
From the results shown in fig. 1 to 20, it can be seen that the electrolyte using the additive of the present invention can significantly inhibit the growth of lithium dendrites, reduce the battery impedance, prolong the battery cycle life, and improve the battery safety when used in a lithium metal battery.
From the results of fig. 21 to 24, it can be seen that the electrolyte using the additive of the present invention can significantly inhibit the growth of sodium dendrites, reduce the battery impedance, prolong the battery cycle life, and improve the battery safety performance when used in a sodium metal battery.
From the results in fig. 25 to 28, it can be seen that the electrolyte using the additive of the present invention can significantly suppress the phenomenon of lithium precipitation during the battery cycle, reduce the battery impedance, prolong the battery cycle life, and improve the battery safety performance when used in a lithium ion battery.
From the results of fig. 29 to 30, it can be seen that the electrolyte using the additive of the present invention can significantly reduce the battery impedance, prolong the battery cycle life, and improve the battery safety performance when used in a potassium ion battery.
The principle of the additive of the invention for inhibiting the growth of lithium (or sodium or potassium) dendrites is as follows: the delocalized big pi bond on the benzene ring can form stronger electrostatic shielding effect, while the anion and the cation of the additive have 4 benzene ring structures, the delocalization effect is greatly enhanced, and the anion and the cation have 4 benzene ring special structures so that the anion and the cation have larger volume effect. During charging, the positive ions of the additive are enriched on the surface of the lithium metal, and during discharging, the negative ions of the additive are enriched on the surface of the lithium metal (or sodium or potassium), and the additive can form a physical adsorption layer on the surface of the lithium metal (or sodium or potassium) during both charging and discharging. The physical adsorption layer generates stronger electrostatic shielding effect and space effect due to the special structure of 4 benzene rings, so that the electric field distribution on the surface of the metal lithium (or sodium or potassium) is greatly improved, the current distribution on the surface of the metal lithium (or sodium or potassium) is more uniform, the deposition of the metal lithium (or sodium or potassium) is more uniform, and the effect of inhibiting lithium (or sodium or potassium) dendrite is achieved.
Claims (8)
1. The electrolyte applied to the lithium, sodium and potassium batteries comprises a solvent, electrolyte salt and an additive, and is characterized in that: the additive is organic compound salt containing phosphorus and boron, the cation part of the organic compound salt is phosphorus-containing cation with four benzene rings, the anion part of the organic compound salt is boron-containing anion with four benzene rings, and the structural general formula is as follows:
2. The electrolyte of claim 1, wherein: the electrolyte salt accounts for 4-80% of the total mass of the electrolyte.
3. The electrolyte of claim 1, wherein: the additive accounts for 0.01-10% of the total mass of the electrolyte.
4. The electrolyte of claim 1, wherein: the solvent is ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, dimethyl fluorocarbonate, methylethyl fluorocarbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylethyl carbonate, vinylene carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, methyl difluoroacetate, ethyl difluoroacetate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, fluoroether F-EPE, fluoroether D2, fluoroether HFPM, fluoroether MFE, fluoroether EME, One or more of acetonitrile, malononitrile, glutaronitrile, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane, sulfolane and dimethyl sulfoxide is mixed according to any proportion.
5. The electrolyte of claim 1, wherein: the electrolyte salt includes a sodium salt, a potassium salt, or a lithium salt.
6. Use of the electrolyte according to any of claims 1-5 in a lithium metal battery, a sodium metal battery, a potassium metal battery, a lithium ion battery, a sodium ion battery, a potassium ion battery.
7. Use of an electrolyte according to claim 6, characterized in that: the lithium metal battery comprises a positive electrode, a diaphragm, a negative electrode and the electrolyte.
8. Use of an electrolyte according to claim 7, characterized in that: the active material of the positive electrode is at least one of lithium cobaltate, lithium nickelate, spinel lithium manganate, layered lithium manganate, a nickel-cobalt binary material, a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material, lithium iron phosphate, spinel lithium nickel manganate, a lithium-rich manganese-based material, a transition metal oxide, a transition metal sulfide, a transition metal phosphate, sulfur and air; the active material of the negative electrode is at least one of metal lithium, lithium alloy, a lithium-carbon composite negative electrode and a lithium-silicon composite negative electrode; the diaphragm is one of PP, PE, PP/PE/PP, cellulose non-woven fabric diaphragm, PET non-woven fabric diaphragm and diaphragm with ceramic coating.
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| CN112448031B (en) * | 2019-08-30 | 2022-04-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electrolyte and lithium metal battery |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN112864468A (en) * | 2021-01-28 | 2021-05-28 | 苏州酷卡环保科技有限公司 | Formation method of power lithium ion battery |
| CN115133159A (en) * | 2022-09-01 | 2022-09-30 | 河南师范大学 | Functional aqueous zinc ion battery electrolyte and preparation method and application thereof |
| CN115472913A (en) * | 2022-10-26 | 2022-12-13 | 河南省法恩莱特新能源科技有限公司 | Sodium battery electrolyte and sodium ion battery |
| CN117039166B (en) * | 2023-09-08 | 2024-09-27 | 金马能源科技(淮南)有限公司 | Potassium ion battery electrolyte suitable for low-temperature operation |
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