CN113540561A - Electrolyte additive, secondary battery electrolyte, secondary battery and terminal - Google Patents
Electrolyte additive, secondary battery electrolyte, secondary battery and terminal Download PDFInfo
- Publication number
- CN113540561A CN113540561A CN202010290478.8A CN202010290478A CN113540561A CN 113540561 A CN113540561 A CN 113540561A CN 202010290478 A CN202010290478 A CN 202010290478A CN 113540561 A CN113540561 A CN 113540561A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- secondary battery
- lithium
- negative electrode
- halogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 123
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 85
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 125000003302 alkenyloxy group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 13
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 150
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 145
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 46
- 229910003002 lithium salt Inorganic materials 0.000 claims description 36
- 159000000002 lithium salts Chemical class 0.000 claims description 36
- -1 tin metal compounds Chemical class 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- 239000000654 additive Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 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 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 6
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 6
- 239000001989 lithium alloy Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003106 haloaryl group Chemical group 0.000 claims description 4
- 125000004996 haloaryloxy group Chemical group 0.000 claims description 4
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 229910018928 (FSO2)2N Inorganic materials 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910016850 F2n+1SO2 Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000846 In alloy Inorganic materials 0.000 claims description 3
- 229910000799 K alloy Inorganic materials 0.000 claims description 3
- 229910012213 MAsF6 Inorganic materials 0.000 claims description 3
- 229910012226 MBF4 Inorganic materials 0.000 claims description 3
- 229910018953 MClO4 Inorganic materials 0.000 claims description 3
- 229910016079 MPF6 Inorganic materials 0.000 claims description 3
- 229910000528 Na alloy Inorganic materials 0.000 claims description 3
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 3
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 claims description 3
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 claims description 3
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims description 3
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 claims description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000003660 carbonate based solvent Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- JBTUPCMIRXTEFB-UHFFFAOYSA-N ethenyl trifluoromethyl carbonate Chemical compound FC(F)(F)OC(=O)OC=C JBTUPCMIRXTEFB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 239000007773 negative electrode material Substances 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 57
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 229910013872 LiPF Inorganic materials 0.000 description 27
- 101150058243 Lipf gene Proteins 0.000 description 27
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 26
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 26
- 238000002156 mixing Methods 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- HCBRSIIGBBDDCD-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound FC(F)C(F)(F)COC(F)(F)C(F)F HCBRSIIGBBDDCD-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910012820 LiCoO Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
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- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 4
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- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 125000004122 cyclic group Chemical group 0.000 description 3
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- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical class [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
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- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
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- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 2
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- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
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- 239000011775 sodium fluoride Substances 0.000 description 2
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- 125000006091 1,3-dioxolane group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910006561 Li—F Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910008048 Si-S Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910006336 Si—S Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-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
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCJHRQJSBBKOPE-UHFFFAOYSA-N ethene;trifluoromethyl hydrogen carbonate Chemical compound C=C.OC(=O)OC(F)(F)F PCJHRQJSBBKOPE-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0566—Liquid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The embodiment of the application provides an electrolyte additive, the chemical structural formula of which is shown as a formula (I),
wherein, R is1、R2、R3、R4、R5、R6Respectively selected from any one of alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy, halogenated alkenyloxy, aryl, halogenated aryl, aryloxy and halogenated aryloxy; r7Is haloalkyl, and X is selected from O or S. By adopting the electrolyte additive provided by the embodiment of the application, a stable interface film can be formed on the surface of the negative electrode of the battery, the side reaction of the electrolyte and the negative electrode material is reduced, and the coulombic efficiency and the circulation of the battery are improvedAnd (4) stability. The application also provides a secondary battery electrolyte, a secondary battery and a terminal containing the electrolyte additive.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to an electrolyte additive, a secondary battery electrolyte, a secondary battery and a terminal.
Background
Lithium ion batteries have been widely used in terminal products (smart phones, digital cameras, notebook computers, electric vehicles, etc.) due to their advantages of high energy density, high operating voltage, long service life, low self-discharge rate, environmental friendliness, etc. With the development of economy and science and technology, the energy density of a commercial lithium ion battery using graphite as a negative electrode material is close to the upper limit, and the higher requirement of people on the energy density of the battery cannot be met. The graphite cathode is partially or completely replaced by the cathode materials with higher theoretical capacity, such as silicon-based, tin-based and metal lithium, which is an effective way for improving the energy density of the battery, however, the cathode materials with high theoretical capacity consume a large amount of electrolyte in the battery charging and discharging process due to large volume expansion and high activity, so that the coulomb efficiency of the battery is low, and the overall performance of the battery is poor. To improve this problem, a negative electrode film-forming additive is usually added to the Electrolyte to form an SEI (Solid Electrolyte interface) film on the surface of the negative electrode, thereby preventing the Electrolyte from contacting the negative electrode material and improving the coulombic efficiency. However, the traditional negative electrode film forming additive (such as vinylene carbonate, fluoroethylene carbonate, ethylene sulfate and the like) has no obvious effect on high-volume expanded silicon-based, tin-based, metal lithium and other negative electrode materials, and can only improve the coulombic efficiency to a limited extent.
Disclosure of Invention
In view of this, the embodiments of the present application provide an electrolyte additive, which can form a stable interface film on the surface of a negative electrode of a battery, and effectively improve the coulombic efficiency and the cycle stability of the battery.
In a first aspect, the embodiment of the present application provides an electrolyte additive, the chemical structural formula of which is shown in formula (I),
in the formula (I), R is1、R2、R3、R4、R5、R6Respectively selected from any one of alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy, halogenated alkenyloxy, aryl, halogenated aryl, aryloxy and halogenated aryloxy; the R is7Is haloalkyl, and X is selected from O or S.
In the embodiments, the number of carbon atoms of the alkyl group, the haloalkyl group, the alkoxy group, and the haloalkoxy group is 1 to 20; the carbon atom number of the alkenyl, the halogenated alkenyl, the alkenyloxy and the halogenated alkenyloxy is 2-20; the number of carbon atoms of the aryl, halogenated aryl, aryloxy and halogenated aryloxy is 6-20.
In embodiments herein, the halogen in the haloalkyl, haloalkoxy, haloalkenyl, haloalkenyloxy, haloaryl and haloaryloxy groups comprises fluorine, chlorine, bromine, iodine, said halogen being perhalogenated or partially halogenated.
In the embodiments of the present application, R is7Is a fluorinated alkyl group having 1 to 20 carbon atoms.
A second aspect of embodiments herein provides a secondary battery electrolyte comprising an electrolyte salt, a non-aqueous organic solvent and an additive, the additive comprising an electrolyte additive as described in the first aspect of embodiments herein.
In the embodiment of the application, the electrolyte additive is 0.1-10% by mass of the electrolyte of the secondary battery.
In an embodiment of the present application, the electrolyte salt includes at least one of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a zinc salt, and an aluminum salt.
In an embodiment of the present application, the electrolyte salt includes MClO4、MBF4、MPF6、MAsF6、MPF2O2、MCF3SO3、MTDI、MB(C2O4)2(MBOB)、MBF2C2O4(MDFOB)、M[(CF3SO2)2N]、M[(FSO2)2N]And M [ (C)mF2m+1SO2)(CnF2n+1SO2)N]Wherein M is Li, Na or K, and M and n are natural numbers.
In the embodiment of the present application, the molar concentration of the electrolyte salt in the electrolyte solution of the secondary battery is 0.01mol/L to 8.0 mol/L.
In the embodiment of the present application, the non-aqueous organic solvent includes one or more of a carbonate solvent, an ether solvent, and a carboxylate solvent.
In embodiments of the present application, the additive further comprises other additives including one or more of biphenyl, fluorobenzene, vinylene carbonate, vinyl trifluoromethyl carbonate, ethylene carbonate, 1, 3-propanesultone, 1, 4-butanesultone, vinyl sulfate, vinyl sulfite, succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, and 1,3, 6-hexanetrinitrile.
A third aspect of the embodiments provides a secondary battery including a positive electrode, a negative electrode, a separator, and an electrolyte solution including the secondary battery electrolyte solution according to the second aspect of the embodiments.
In an embodiment of the present application, the negative electrode includes one or more of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, a lithium negative electrode, a sodium negative electrode, a potassium negative electrode, a magnesium negative electrode, a zinc negative electrode, and an aluminum negative electrode.
In an embodiment of the present application, the carbon-based negative electrode includes one or more of graphite, hard carbon, soft carbon, and graphene, the silicon-based negative electrode includes one or more of silicon, silicon carbon, silicon oxygen, and a silicon metal compound, the tin-based negative electrode includes one or more of tin, tin carbon, tin oxygen, and a tin metal compound, and the lithium negative electrode includes metallic lithium or a lithium alloy.
In an embodiment of the present application, the lithium alloy includes at least one of a lithium silicon alloy, a lithium sodium alloy, a lithium potassium alloy, a lithium aluminum alloy, a lithium tin alloy, and a lithium indium alloy.
In the embodiments of the present application, the secondary battery includes a lithium secondary battery, a potassium secondary battery, a sodium secondary battery, a magnesium secondary battery, a zinc secondary battery, or an aluminum secondary battery.
The embodiment of the application further provides a terminal, including the casing, and accept in electronic components and batteries in the casing, the battery does electronic components supplies power, the battery includes the third aspect of the embodiment of the application secondary battery.
According to the electrolyte additive provided by the embodiment of the application, on one hand, the additive can be reduced on the surface of a negative electrode in preference to a non-aqueous organic solvent in an electrolyte to form a stable interface film rich in metal halides, carbon-nitrogen bond-containing compounds, silane and other compounds, so that the side reaction of the electrolyte and a negative electrode material is reduced, and the coulombic efficiency and the cycling stability of a battery are improved; on the other hand, the N-Si bond in the additive can react with a small amount of hydrofluoric acid (HF) in the electrolyte containing lithium hexafluorophosphate, so that the lithium hexafluorophosphate is inhibited from being further decomposed, and the stability of the electrolyte is improved.
Drawings
Fig. 1 is a schematic structural diagram of a secondary battery provided in an embodiment of the present application;
fig. 2 is a schematic structural diagram of a terminal according to an embodiment of the present application;
FIG. 3 is a graph showing the cycle profiles of the lithium secondary batteries of examples 1-2 of the present application and comparative example 1;
FIG. 4 is a graph showing the cycle profiles of the lithium secondary batteries of examples 3 to 4 of the present application and comparative example 2;
FIG. 5 is a graph showing the cycle profiles of the lithium secondary batteries of examples 5 to 8 of the present application and comparative examples 3 to 5;
FIG. 6 is a Linear Sweep Voltammetry (LSV) plot of the electrolytes of example 5 and comparative example 3 of the present application;
FIGS. 7, 8 and 9 are XPS (X-ray photoelectron spectroscopy) detection charts corresponding to F1s, N1s and Si2p spectrums of the surface of the graphite pole piece after the lithium secondary battery of example 1 and comparative example 1 of the present application is cycled;
fig. 10, 11 and 12 are XPS detection charts corresponding to F1s, N1s and Si2p spectra on the surface of the lithium sheet after cycling of the lithium secondary batteries of example 5 and comparative example 3 of the present application.
Detailed Description
The embodiments of the present application will be described below with reference to the drawings.
As shown in fig. 1, a core component of a secondary battery (taking a lithium ion battery as an example) includes a positive electrode material 101, a negative electrode material 102, an electrolyte 103, a separator 104, and corresponding communication accessories and circuits. During charging, lithium ions are extracted from the crystal lattice of the positive electrode material 101, pass through the electrolyte 103 and then are deposited to the negative electrode; during discharge, lithium ions are extracted from the negative electrode, pass through the electrolytic solution 103, and are inserted into the crystal lattice of the positive electrode material 101. During the charging and discharging process, the electrolyte and the electrode material react on a solid-liquid phase interface to form an interface film, the performance of the battery is obviously affected by the interface film, and the instability of the interface protective film can cause serious side reaction, so that the coulombic efficiency is reduced and the cycle life of the battery is prolonged. In order to obtain a stable negative electrode interface film, reduce side reactions of electrolyte and a negative electrode, and improve the coulombic efficiency and the cycle life of the battery, the embodiment of the application provides the electrolyte additive.
The chemical structural formula of the electrolyte additive provided by the embodiment of the application is shown as the formula (I),
in the formula (I), R1、R2、R3、R4、R5、R6Can be respectively and independently selected from alkyl and halogenAny one of alkyl, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, aryl, haloaryl, aryloxy and haloaryloxy; r7Is haloalkyl, and X can be selected from O or S.
The electrolyte additive provided by the embodiment of the application has lower LUMO energy and higher reduction potential, can be reduced on the surface of a negative electrode in preference to a non-aqueous organic solvent in an electrolyte to form a stable interface film rich in metal halides, compounds containing carbon-nitrogen bonds, silane and other compounds, reduces side reactions of the electrolyte and a negative electrode material, and improves the coulombic efficiency and the cycle stability of a battery; in addition, the N-Si bond in the additive can also react with a small amount of HF in the lithium hexafluorophosphate-containing electrolyte, so that the lithium hexafluorophosphate is inhibited from being further decomposed, and the stability of the electrolyte is improved.
The metal halide formed in the interfacial film differs depending on the secondary battery system, and specifically, the metal halide may be a lithium halide (e.g., lithium fluoride), a sodium halide (e.g., sodium fluoride), a potassium halide (e.g., potassium fluoride).
In the secondary battery, the nonaqueous organic solvent generally includes a carbonate-based solvent, an ether-based solvent, and a carboxylic acid-based solvent. Due to the R of the electrolyte additive provided by the embodiment of the application7The carbon halogen bond and the Si-N, Si-O or Si-S bond in the electrolyte are unstable and easy to break, so that the electrolyte has higher reduction potential (larger than the reduction potential of the organic solvent), is easier to reduce relative to the organic solvent, and forms a stable interface film rich in metal halides, compounds containing carbon-nitrogen bonds, silane and other compounds to cover the surface of the cathode after being reduced, thereby inhibiting the reduction decomposition of the electrolyte on the surface of the cathode and improving the cycle stability. Wherein, taking a lithium secondary battery whose solvent contains an electrolyte of Ethylene Carbonate (EC) as an example, R in the additive of the embodiment of the present application7In the case of fluoroalkyl groups, the possible mechanisms of action of the electrolyte additive are:
in view of the above mechanism, the electrolyte additive of the embodiment of the present application is added to a lithium secondary battery system in which the electrolyte contains Ethylene Carbonate (EC), and finally, compounds such as lithium fluoride, silane, and polyester having a carbon-nitrogen bond are generated.
In one embodiment of the present application, X is an oxygen atom O, and the chemical structural formula of the electrolyte additive is shown in formula (ii):
in another embodiment of the present application, X is a sulfur atom S, and the electrolyte additive has a chemical formula shown in formula (iii):
in the embodiment of the application, when X is a sulfur atom S, the electrolyte additive can also react in the electrolyte system to generate a sulfide, thereby improving the ionic conductivity.
In the embodiments of the present application, R1、R2、R3、R4、R5、R6In the above-mentioned (C) alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, etc., the number of carbon atoms may be 1 to 20, further, the number of carbon atoms may be 1 to 10, specifically, the number of carbon atoms is, for example, 1,2, 3, 4, 5, 6, 7, 8, 9, 10; the number of carbon atoms of the alkenyl group, the haloalkenyl group, the alkenyloxy group, and the haloalkenyloxy group may be 2 to 20, further, the number of carbon atoms may be 2 to 10, specifically, the number of carbon atoms is, for example, 2,3, 4, 5, 6, 7, 8, 9, 10; the number of carbon atoms of the aryl group, the halogenated aryl group, the aryloxy group, the halogenated aryloxy group may be 6 to 20, further, the number of carbon atoms may be 7 to 10, specifically, the number of carbon atoms is, for example, 7, 8, 9, 10.
Wherein when R is1、R2、R3、R4、R5、R6When the electrolyte additive is a halogenated group, the reduction potential of the electrolyte additive can be further improved, so that the electrolyte additive is more easily reduced.
In the embodiments of the present application, R7The halogen is halogenated alkyl, on one hand, the halogen is a strong electron-withdrawing group, so that the reducibility of the electrolyte additive can be improved, the reduction potential can be improved, on the other hand, a stable interface film rich in metal halides (such as lithium fluoride, sodium fluoride and the like) can be formed, and the interface stability of a negative electrode can be improved. In the embodiments of the present application, R7The number of carbon atoms of the haloalkyl group may be 1 to 20, further, the number of carbon atoms may be 1 to 10, specifically, the number of carbon atoms is, for example, 1,2, 3, 4, 5, 6, 7, 8, 9, 10; in some embodiments of the present application, R7Is a fluoroalkyl group of 1 to 20 carbon atoms, further, R7Is a fluoroalkyl group having 1 to 8 carbon atoms. In particular R7For example, trifluoromethyl, trifluoroethyl, pentafluoroethyl and the like are mentioned. A lower number of carbon atoms favours a better dissolution of the additive in the electrolyte.
In the embodiments of the present application, R1、R2、R3、R4、R5、R6When one or more of the alkyl halide, the alkoxy halide, the alkenyl halide, the alkenyloxy halide, the aryl halide or the aryloxy halide is/are adopted, the flame retardant property of the electrolyte additive is favorably enhanced.
In the embodiments of the present application, the halogen in the haloalkyl group, the haloalkoxy group, the haloalkenyl group, the haloalkenyloxy group, the haloaryl group and the haloaryloxy group includes fluorine, chlorine, bromine and iodine, and the halogenation may be a perhalogenation or a partial halogenation. The alkyl group, haloalkyl group, alkoxy group, haloalkoxy group, alkenyl group, haloalkenyl group, alkenyloxy group, and haloalkenyloxy group may be linear or branched.
In the embodiments of the present application, R1、R2、R3、R4、R5And R6May be the same or different groups. In the embodiments of the present application, R1、R2、R3、R4、R5And R6May also be reacted with R7Are the same or different groups.
In a specific embodiment of the present application, the electrolyte additive may have a molecular structure represented by formulas (a) to (F):
in the embodiments of the present application, the electrolyte additive represented by formula (I) may be prepared by various methods, and in some embodiments of the present application, may be prepared as follows:
pentane is used as a solvent, and a reactant R is added1、R2、R3Substituted chlorosilanes M1, R4、R5、R6And (3) substituted chlorosilane M2 and amide or sulfamide M3, controlling the reaction temperature to be 20-50 ℃, and obtaining the electrolyte additive shown in the formula (I) after the reaction is finished. Wherein, amide or sulfamide is used as an acid-binding agent. The reaction process is shown as the formula (IV):
the embodiment of the application also provides a secondary battery electrolyte, which comprises electrolyte salt, a non-aqueous organic solvent and an additive, wherein the additive comprises the electrolyte additive.
In the embodiment of the application, the mass percentage of the electrolyte additive in the electrolyte of the secondary battery can be 0.1-10%. Further, the electrolyte additive can be 0.5-8%, 1-6%, 2-5% and 0.5-1% by mass in the electrolyte of the secondary battery. In the embodiment of the application, the coulomb efficiency of the battery can be effectively improved by adding the electrolyte additive with lower content. Meanwhile, the addition of the electrolyte additive with lower content can ensure that the viscosity of the electrolyte is not too high, so that the performance of the battery is not influenced.
In the embodiment of the present application, the electrolyte salt may be a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a zinc salt, an aluminum salt, or the like, depending on the secondary battery system. Specifically, the lithium salt, sodium salt, potassium salt may be MClO4、MBF4、MPF6、MAsF6、MPF2O2、MCF3SO3、MTDI、MB(C2O4)2(MBOB)、MBF2C2O4(MDFOB)、M[(CF3SO2)2N]、M[(FSO2)2N]And M [ (C)mF2m+1SO2)(CnF2n+1SO2)N]Wherein M is Li, Na or K, and M and n are natural numbers. Similarly, the magnesium salt, zinc salt, and aluminum salt may be salts of magnesium ion, zinc ion, and aluminum ion with anions of the lithium salt, sodium salt, and potassium salt.
In the embodiment of the present application, the molar concentration of the electrolyte salt in the electrolyte solution of the secondary battery is 0.01mol/L to 8.0 mol/L. Further, it may be 0.05mol/L to 2mol/L, 0.5mol/L to 1.0 mol/L.
In the embodiment of the present application, the non-aqueous organic solvent includes one or more of a carbonate solvent, an ether solvent, and a carboxylate solvent. The non-aqueous organic solvent may be mixed in any proportion. The carbonate solvent comprises cyclic carbonate or chain carbonate, and the cyclic carbonate can be one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), gamma-butyrolactone (GBL) and Butylene Carbonate (BC); the chain carbonate may be one or more of dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) and dipropyl carbonate (DPC). The ether solvent includes cyclic ether or chain ether, and the cyclic ether can be 1, 3-Dioxolane (DOL), 1, 4-Dioxan (DX), crown ether, Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH)3-THF), 2-trifluoromethyltetrahydrofuran (2-CF)3-THF); the chain ether may be one or more of Dimethoxymethane (DMM), 1, 2-Dimethoxyethane (DME), and diglyme (TEGDME). The carboxylic ester solvent may be one or more of Methyl Acetate (MA), Ethyl Acetate (EA), propyl acetate (EP), butyl acetate, Propyl Propionate (PP), and butyl propionate.
In the embodiment of the present invention, in addition to the above electrolyte additives, other additives may be added to the electrolyte of the secondary battery according to different performance requirements, and the other additives may be, but are not limited to, one or more of biphenyl, fluorobenzene, vinylene carbonate, ethylene trifluoromethyl carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, vinyl sulfite, succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, and 1,3, 6-hexane trinitrile.
Correspondingly, the embodiment of the application also provides a preparation method of the electrolyte of the secondary battery, which comprises the following steps:
adding the electrolyte additive into a nonaqueous organic solvent in an inert environment or a closed environment (such as an argon-filled glove box), dissolving the fully dried electrolyte salt into the solution, and stirring and mixing uniformly to obtain the electrolyte of the secondary battery.
The operations in the preparation method can be implemented according to the existing conventional electrolyte preparation process, wherein the specific selection of the raw materials such as the electrolyte salt, the non-aqueous organic solvent, the electrolyte additive and the like is as described above and is not repeated herein. When the electrolyte further includes other additives, it may be added together with the electrolyte additive.
The embodiment of the application also provides a secondary battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte adopts the electrolyte of the secondary battery provided by the embodiment of the application. According to the secondary battery provided by the embodiment of the application, the electrolyte additive is added into the electrolyte, so that higher coulombic efficiency and good circulation stability can be obtained. In the embodiment of the present application, the secondary battery may be a lithium secondary battery, a potassium secondary battery, a sodium secondary battery, a magnesium secondary battery, a zinc secondary battery, an aluminum secondary battery, or the like. The secondary battery provided by the embodiment of the application can be used for terminal consumer products, such as mobile phones, tablet computers, mobile power supplies, portable computers, notebook computers, other wearable or movable electronic equipment, automobiles and other products, so as to improve the product performance.
In an embodiment of the present application, the negative electrode may include one or more of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, a lithium negative electrode, a sodium negative electrode, a potassium negative electrode, a magnesium negative electrode, a zinc negative electrode, and an aluminum negative electrode. Wherein the carbon-based negative electrode may include graphite, hard carbon, soft carbon, graphene, and the like; the silicon-based negative electrode can comprise silicon, silicon carbon, silicon oxygen, silicon metal compound and the like; the tin-based negative electrode may include tin, tin carbon, tin oxide, tin metal compounds; the lithium negative electrode may include metallic lithium or a lithium alloy. The lithium alloy may specifically be at least one of a lithium silicon alloy, a lithium sodium alloy, a lithium potassium alloy, a lithium aluminum alloy, a lithium tin alloy, and a lithium indium alloy.
In the embodiments of the present invention, the positive electrode includes a positive electrode active material capable of reversibly intercalating/deintercalating metal ions (lithium ions, sodium ions, potassium ions, magnesium ions, zinc ions, aluminum ions, etc.), and the selection of the positive electrode active material is not particularly limited, and may be a positive electrode active material conventionally used in conventional secondary batteries. Taking a lithium secondary battery as an example, the positive electrode active material may be lithium cobaltate (LiCoO)2) Lithium iron phosphate (LiFePO)4) Lithium nickel cobalt manganese oxide (LiNi)0.6Co0.2Mn0.2) Polyanionic lithium compound LiMx(PO4)y(M is Ni, Co, Mn, Fe, Ti, V, x is more than or equal to 0 and less than or equal to 5, y is more than or equal to 0 and less than or equal to 5), and the like.
In the embodiments of the present application, the separator may be an existing conventional separator, including but not limited to, a single PP (polypropylene), a single PE (polyethylene), a double PP/PE, a double PP/PP, and a triple PP/PE/PP separator.
As shown in fig. 2, the present embodiment further provides a terminal, where the terminal 200 may be a mobile phone, a tablet computer, a notebook computer, a portable device, an intelligent wearable product, an automobile, and the like, and includes a housing 201, and an electronic component and a battery (not shown in the figure) accommodated in the housing 201, where the battery supplies power to the electronic component, where the battery is the secondary battery provided in the present embodiment, and the housing 201 may include a front cover assembled on a front side of the terminal and a rear shell assembled on a rear side, and the battery may be fixed inside the rear shell.
The examples of the present application will be further described with reference to specific examples.
Example 1
A lithium secondary battery electrolyte includes a lithium salt (lithium hexafluorophosphate LiPF)6) The electrolyte comprises a nonaqueous organic solvent formed by mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to the mass ratio of 50:50, and an electrolyte additive with a molecular structural formula shown as a formula (A), wherein lithium salt (LiPF)6) The concentration of the electrolyte additive A is 1.0mol/L, the mass percentage content of the electrolyte additive A is 0.5 percent,
preparation of the electrolyte for the lithium secondary battery in this example:
in an argon-filled glove box, EC and EMC were mixed to form a non-aqueous organic solvent, electrolyte additive a was added to the non-aqueous organic solvent, and then a well-dried lithium salt (LiPF) was added6) The mixture was dissolved in the solvent, and the mixture was stirred and mixed uniformly to obtain an electrolyte solution for a lithium secondary battery of example 1 of the present application.
Preparation of lithium secondary battery
Weighing 2% of polyvinylidene fluoride (PVDF), 2% of conductive agent super P and 96% of lithium cobaltate (LiCoO) in percentage by mass2) Sequentially adding the mixture into N-methylpyrrolidone (NMP), fully stirring and uniformly mixing, coating the slurry on an aluminum foil current collector, drying, cold pressing and cutting to obtain the positive pole piece.
Weighing 1.5 mass percent of sodium carboxymethylcellulose (CMC), 2.5 mass percent of Styrene Butadiene Rubber (SBR), 1 mass percent of acetylene black and 95 mass percent of graphite, sequentially adding the materials into deionized water, fully stirring and uniformly mixing, coating the slurry on a copper foil current collector, drying, cold pressing and slitting to obtain the negative pole piece.
And (2) preparing the prepared positive pole piece, negative pole piece and commercial PE diaphragm into a battery cell, packaging by adopting a polymer, filling the lithium secondary battery electrolyte prepared in the embodiment 1 of the application, and preparing the soft package lithium secondary battery by processes such as formation and the like.
Example 2
A lithium secondary battery electrolyte includes a lithium salt (LiPF)6) A non-aqueous organic solvent formed by mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) according to a mass ratio of 50:50An agent, and an electrolyte additive having a molecular structural formula as shown in formula (B), wherein the lithium salt (LiPF)6) The concentration of the electrolyte additive B is 1.0mol/L, the mass percentage content of the electrolyte additive B is 0.5 percent,
preparation of the electrolyte for the lithium secondary battery in this example:
in an argon-filled glove box, EC and EMC were mixed to form a non-aqueous organic solvent, electrolyte additive B was added to the non-aqueous organic solvent, and then a fully dried lithium salt (LiPF) was added6) The mixture was dissolved in the solvent, and the mixture was stirred and mixed uniformly to obtain an electrolyte solution for a lithium secondary battery of example 2 of the present application.
A lithium secondary battery was fabricated in the same manner as in example 1.
Example 3
A lithium secondary battery electrolyte includes a lithium salt (LiPF)6) A non-aqueous organic solvent formed by mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) in a mass ratio of 30:60:10, and an electrolyte additive comprising a molecular structural formula shown as a formula (C), wherein the lithium salt (LiPF)6) The concentration of the electrolyte additive C is 1.0mol/L, the mass percentage of the electrolyte additive C is 1 percent,
preparation of the electrolyte for the lithium secondary battery in this example:
in an argon filled glove box, EC, DEC and FEC were mixed to form a non-aqueous organic solvent, electrolyte additive C was added to the non-aqueous organic solvent, and then a fully dried lithium salt (LiPF) was added6) The mixture was dissolved in the solvent, and the mixture was stirred and mixed uniformly to obtain an electrolyte solution for a lithium secondary battery of example 3 of the present application.
Preparation of lithium secondary battery
Weighing2 percent of polyvinylidene fluoride (PVDF), 2 percent of conductive agent super P and 96 percent of lithium cobaltate (LiCoO) in percentage by mass2) Sequentially adding the mixture into N-methylpyrrolidone (NMP), fully stirring and uniformly mixing, coating the slurry on an aluminum foil current collector, drying, cold pressing and cutting to obtain the positive pole piece.
Weighing 1.5% of CMC, 2.5% of SBR, 1% of acetylene black and 95% of silicon carbon in percentage by mass, sequentially adding the materials into deionized water, fully stirring and uniformly mixing, coating the slurry on a copper foil current collector, drying, cold pressing and slitting to obtain the negative pole piece.
And (3) preparing the prepared positive pole piece, negative pole piece and commercial PE diaphragm into a battery cell, packaging by adopting a polymer, filling the lithium secondary battery electrolyte prepared in the embodiment 3 of the application, and preparing the soft package lithium secondary battery by processes such as formation and the like.
Example 4
A lithium secondary battery electrolyte includes a lithium salt (LiPF)6) A non-aqueous organic solvent formed by mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) in a mass ratio of 30:60:10, and an electrolyte additive comprising a molecular structural formula shown in formula (D), wherein the lithium salt (LiPF) is6) The concentration of the electrolyte additive D is 1.0mol/L, the mass percentage of the electrolyte additive D is 1 percent,
preparation of the electrolyte for the lithium secondary battery in this example:
in an argon filled glove box, EC, DEC and FEC were mixed to form a non-aqueous organic solvent, electrolyte additive D was added to the non-aqueous organic solvent, and then a fully dried lithium salt (LiPF) was added6) The mixture was dissolved in the solvent, and the mixture was stirred and mixed uniformly to obtain an electrolyte solution for a lithium secondary battery of example 4 of the present application.
A lithium secondary battery was fabricated in the same manner as in example 3.
Example 5
Lithium secondary battery electrolyte and packageLithium salt (lithium hexafluorophosphate LiPF)6And lithium bis (fluorosulfonyl) imide LiFSI), a non-aqueous organic solvent formed by mixing dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) in a mass ratio of 50:50, and an electrolyte additive comprising a molecular structural formula shown in formula (A), wherein the lithium hexafluorophosphate (LiPF)6) And the concentration of the lithium bis (fluorosulfonyl) imide is 1.0mol/L and 0.2mol/L respectively, the mass percentage of the electrolyte additive A is 1 percent,
preparation of the electrolyte for the lithium secondary battery in this example:
in an argon-filled glove box, DMC and FEC were mixed to form a non-aqueous organic solvent, electrolyte additive a was added to the non-aqueous organic solvent, and then a well-dried lithium salt (LiPF) was added6And LiFSI) was dissolved in the above solvent, and was uniformly mixed by stirring to obtain the lithium secondary battery electrolyte of example 5 of the present application.
Preparation of lithium secondary battery
Weighing 2% of polyvinylidene fluoride (PVDF), 2% of conductive agent super P and 96% of lithium cobaltate (LiCoO) in percentage by mass2) Sequentially adding the mixture into N-methylpyrrolidone (NMP), fully stirring and uniformly mixing, coating the slurry on an aluminum foil current collector, drying, cold pressing and cutting to obtain the positive pole piece.
And (3) preparing the prepared positive pole piece, the metal lithium negative pole piece and the commercial PE diaphragm into a battery cell, packaging by adopting a polymer, filling the lithium secondary battery electrolyte prepared in the embodiment 5 of the application, and preparing the soft package lithium secondary battery after the processes of formation and the like.
Example 6
A lithium secondary battery electrolyte includes a lithium salt (lithium hexafluorophosphate LiPF)6And lithium bis (fluorosulfonyl) imide LiFSI), a non-aqueous organic solvent formed by mixing dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) according to a mass ratio of 50:50, and an electrolyte additive comprising a molecular structural formula shown as a formula (E), wherein the hexafluorophosphoric acid isLithium (LiPF)6) And the concentration of lithium bis (fluorosulfonyl) imide (LiFSI) is 1.0mol/L and 0.2mol/L, the mass percentage of the electrolyte additive E is 1%,
preparation of the electrolyte for the lithium secondary battery in this example:
in an argon-filled glove box, DMC and FEC were mixed to form a non-aqueous organic solvent, electrolyte additive E was added to the non-aqueous organic solvent, and then a well-dried lithium salt (LiPF) was added6And LiFSI) was dissolved in the above solvent, and was uniformly mixed by stirring to obtain the lithium secondary battery electrolyte of example 6 of the present application.
A lithium secondary battery was fabricated in the same manner as in example 5.
Example 7
A lithium secondary battery electrolyte comprises lithium salt (lithium bifluorosulfonylimide LiFSI and lithium difluorooxalatoborate LiDFOB), a non-aqueous organic solvent formed by mixing dimethyl carbonate (DMC), fluoroethylene carbonate (FEC) and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (D2) according to a mass ratio of 50:10:40, and an electrolyte additive with a molecular structural formula shown as a formula (F), wherein the concentrations of the LiFSI and the LiDFOB are respectively 4.0mol/L and 0.5mol/L, and the mass percentage content of the electrolyte additive F is 1%,
preparation of the electrolyte for the lithium secondary battery in this example:
in a glove box filled with argon gas, DMC, FEC and D2 were mixed to form a nonaqueous organic solvent, an electrolyte additive F was added to the nonaqueous organic solvent, and then a sufficiently dried lithium salt (LiFSI and liddob) was dissolved in the solvent and uniformly mixed with stirring to prepare the electrolyte for a lithium secondary battery of example 7 of the present application.
A lithium secondary battery was fabricated in the same manner as in example 5.
Example 8
A lithium secondary battery electrolyte comprises lithium salt (lithium bifluorosulfonylimide LiFSI and lithium difluorooxalatoborate LiDFOB), a non-aqueous organic solvent formed by mixing ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (D2) according to a mass ratio of 50:10:40, and an electrolyte additive with a molecular structural formula shown in a formula (A), wherein the concentrations of the LiFSI and the LiDFOB are respectively 6.0mol/L and 0.5mol/L, the mass percentage content of the electrolyte additive A is 1%,
preparation of the electrolyte for the lithium secondary battery in this example:
in a glove box filled with argon gas, DME, FEC and D2 were mixed to form a nonaqueous organic solvent, and electrolyte additive a was added to the nonaqueous organic solvent, and then, sufficiently dried lithium salts (LiFSI and liddob) were dissolved in the solvent, and uniformly mixed with stirring, thereby obtaining an electrolyte for a lithium secondary battery of example 8 of the present application.
A lithium secondary battery was fabricated in the same manner as in example 5.
Comparative example 1
A lithium secondary battery electrolyte includes a lithium salt (lithium hexafluorophosphate LiPF)6) A non-aqueous organic solvent formed by mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) in a mass ratio of 50:50, wherein the lithium salt (LiPF)6) The concentration of (2) is 1.0 mol/L.
Comparative example preparation of the above electrolyte for lithium secondary battery:
in an argon filled glove box, EC and EMC were mixed to form a non-aqueous organic solvent, and a well dried lithium salt (LiPF) was added6) The mixture was dissolved in the above solvent and uniformly mixed by stirring to obtain the electrolyte for lithium secondary battery of comparative example 1 of the present application.
Preparation of lithium secondary battery
Weighing 2 percent of polyvinylidene fluoride by massEthylene (PVDF), 2% conductive agent super P and 96% lithium cobaltate (LiCoO)2) Sequentially adding the mixture into N-methylpyrrolidone (NMP), fully stirring and uniformly mixing, coating the slurry on an aluminum foil current collector, drying, cold pressing and cutting to obtain the positive pole piece.
Weighing 1.5% of CMC, 2.5% of SBR, 1% of acetylene black and 95% of graphite in percentage by mass, sequentially adding the materials into deionized water, fully stirring and uniformly mixing, coating the slurry on a copper foil current collector, drying, cold pressing and slitting to obtain the negative pole piece.
And (2) preparing the prepared positive pole piece, negative pole piece and commercial PE diaphragm into a battery cell, packaging by adopting a polymer, filling the lithium secondary battery electrolyte prepared in the comparative example 1, and preparing the soft package lithium secondary battery by the processes of formation and the like.
Comparative example 2
A lithium secondary battery electrolyte includes a lithium salt (LiPF)6) A non-aqueous organic solvent formed by mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) in a mass ratio of 30:60:10, wherein the lithium salt (LiPF)6) The concentration of (2) is 1.0 mol/L.
Comparative example preparation of the above electrolyte for lithium secondary battery:
in an argon filled glove box, EC, DEC and FEC were mixed to form a non-aqueous organic solvent, and the fully dried lithium salt (LiPF) was added6) And dissolved in the above solvent, and stirred and mixed uniformly to prepare the electrolyte for a lithium secondary battery of comparative example 2 of the present application.
Preparation of lithium secondary battery
Weighing 2% of polyvinylidene fluoride (PVDF), 2% of conductive agent super P and 96% of lithium cobaltate (LiCoO) in percentage by mass2) Sequentially adding the mixture into N-methylpyrrolidone (NMP), fully stirring and uniformly mixing, coating the slurry on an aluminum foil current collector, drying, cold pressing and cutting to obtain the positive pole piece.
Weighing 1.5% of CMC, 2.5% of SBR, 1% of acetylene black and 95% of silicon carbon in percentage by mass, sequentially adding the materials into deionized water, fully stirring and uniformly mixing, coating the slurry on a copper foil current collector, drying, cold pressing and slitting to obtain the negative pole piece.
And (3) preparing the prepared positive pole piece, negative pole piece and commercial PE diaphragm into a battery cell, packaging by adopting a polymer, filling the lithium secondary battery electrolyte prepared in the comparative example 2, and preparing the soft package lithium secondary battery by the processes of formation and the like.
Comparative example 3
A lithium secondary battery electrolyte includes a lithium salt (lithium hexafluorophosphate LiPF)6And lithium bis (fluorosulfonyl) imide LiFSI), a non-aqueous organic solvent formed by mixing dimethyl carbonate (DMC) and fluoroethylene carbonate (FEC) in a mass ratio of 50:50, wherein the lithium hexafluorophosphate (LiPF)6) And the concentration of lithium bis (fluorosulfonyl) imide (LiFSI) was 1.0mol/L and 0.2mol/L, respectively.
Comparative example preparation of the above electrolyte for lithium secondary battery:
in an argon-filled glove box, DMC and FEC were mixed to form a non-aqueous organic solvent, and a well-dried lithium salt (LiPF) was added6And LiFSI) was dissolved in the above solvent, and stirred and mixed uniformly to prepare the electrolyte for a lithium secondary battery of comparative example 3 of the present application.
Preparation of lithium secondary battery
Weighing 2% of polyvinylidene fluoride (PVDF), 2% of conductive agent super P and 96% of lithium cobaltate (LiCoO) in percentage by mass2) Sequentially adding the mixture into N-methylpyrrolidone (NMP), fully stirring and uniformly mixing, coating the slurry on an aluminum foil current collector, drying, cold pressing and cutting to obtain the positive pole piece.
And (3) preparing the prepared positive pole piece, the metal lithium negative pole piece and the commercial PE diaphragm into a battery cell, packaging by adopting a polymer, filling the lithium secondary battery electrolyte prepared in the comparative example 3, and preparing the soft package lithium secondary battery by the processes of formation and the like.
Comparative example 4
A lithium secondary battery electrolyte comprises lithium salt (lithium bifluorosulfonylimide LiFSI and lithium difluorooxalatoborate LiDFOB) and a non-aqueous organic solvent formed by mixing dimethyl carbonate (DMC), fluoroethylene carbonate (FEC) and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (D2) according to a mass ratio of 50:10:40, wherein the concentrations of the LiFSI and the LiDFOB are respectively 4.0mol/L and 0.5 mol/L.
Comparative example preparation of the above electrolyte for lithium secondary battery:
in a glove box filled with argon gas, DMC, FEC and D2 were mixed to form a non-aqueous organic solvent, and then sufficiently dried lithium salts (LiFSI and liddob) were dissolved in the above solvent and uniformly mixed with stirring to prepare an electrolyte for a lithium secondary battery of comparative example 4 of the present application.
The lithium secondary battery was fabricated in the same manner as in comparative example 3.
Comparative example 5
A lithium secondary battery electrolyte comprises lithium salt (lithium bifluorosulfonylimide LiFSI and lithium difluorooxalato borate LiDFOB) and a non-aqueous organic solvent formed by mixing ethylene glycol dimethyl ether (DME), fluoroethylene carbonate (FEC) and 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (D2) according to a mass ratio of 50:10:40, wherein the concentrations of the LiFSI and the LiDFOB are 6.0mol/L and 0.5mol/L respectively.
Comparative example preparation of the above electrolyte for lithium secondary battery:
in a glove box filled with argon gas, DME, FEC and D2 were mixed to form a non-aqueous organic solvent, and then, sufficiently dried lithium salts (LiFSI and liddob) were dissolved in the above solvent and uniformly mixed with stirring to prepare an electrolyte for a lithium secondary battery of comparative example 5 of the present application.
The lithium secondary battery was fabricated in the same manner as in comparative example 3.
In order to strongly support the beneficial effects brought by the technical schemes in the examples 1 to 8 and the comparative examples 1 to 5 of the application, the following tests are provided:
and (3) testing the performance of the copper/lithium battery: and assembling the copper sheet positive electrode, the metal lithium negative electrode and the diaphragm into a button cell, and dropwise adding 100uL of the electrolyte solution described in the above examples 1-8 and comparative examples 1-5. The test was conducted according to the following test procedures, and the test results are shown in Table 1.
The copper/lithium battery test flow is set as follows: the first charge-discharge current density is 0.5mA/cm2The first deposition amount is 4.0mAh/cm2The current density of the cyclic discharge is 0.5mA/cm2The cyclic charging current density is 1.5mA/cm2The circulating deposition amount is 1.0mAh/cm2The cycle number was 50 weeks, and the first discharge capacity (Q) of the battery was measured by comparisonT) Cyclic charge capacity (Q)C) And last charge capacity (Q)S) The coulombic efficiency of the charge-discharge cycle of the copper/lithium battery is calculated.
The Coulombic Efficiency (CE) of the cell was calculated as follows:
testing the performance of the lithium secondary battery: the lithium secondary batteries assembled in examples 1 to 8 and comparative examples 1 to 5 were subjected to a charge-discharge cycle test at a charge-discharge rate of 0.2/0.5C, the voltage range of the batteries was 3.0V to 4.45V, and the capacity retention ratio after 100 weeks was recorded, with the test results shown in table 1, fig. 3, fig. 4, and fig. 5.
TABLE 1 coulombic efficiency and cycle performance test results for batteries of examples 1-8 and comparative examples 1-5
| Examples/comparative examples | Coulombic efficiency/% of copper/lithium cell | Capacity retention ratio/% of lithium secondary battery |
| Example 1 | 95.2 | 95.7 |
| Example 2 | 93.5 | 94.8 |
| Example 3 | 97.8 | 92.9 |
| Example 4 | 96.7 | 92.6 |
| Example 5 | 98.8 | 90.9 |
| Example 6 | 98.2 | 88.4 |
| Example 7 | 99.4 | 85.7 |
| Example 8 | 99.6 | 82.1 |
| Comparative example 1 | 80.2 | 91.8 |
| Comparative example 2 | 85.7 | 85.6 |
| Comparative example 3 | 93.5 | 68.8 |
| Comparative example 4 | 97.8 | 79.7 |
| Comparative example 5 | 98.4 | 69.5 |
As can be seen from the test results in table 1 and fig. 3, compared with comparative example 1, in example 1 and example 2 of the present application, since the electrolyte additive a and the electrolyte additive B are added to the electrolyte respectively, the 50-week average coulombic efficiency of the copper/lithium battery in example 1 and example 2 of the present application is higher than the 50-week average coulombic efficiency of the copper/lithium battery in comparative example 1, and the capacity retention rate after 100 weeks of the lithium cobaltate/graphite lithium secondary battery in example 1 and example 2 of the present application is higher than the capacity retention rate after 100 weeks of the lithium cobaltate/graphite lithium secondary battery in comparative example 1.
As can be seen from the test results in table 1 and fig. 4, compared with comparative example 2, in example 3 and example 4 of the present application, since the electrolyte additive C and the electrolyte additive D are respectively added to the electrolyte, the average coulombic efficiency at 50 weeks of the copper/lithium battery in example 3-4 of the present application is higher than the average coulombic efficiency at 50 weeks of the copper/lithium battery in comparative example 2, and the capacity retention rate after 100 weeks of the lithium cobaltate/silicon carbon battery in example 3-4 of the present application is higher than the capacity retention rate after 100 weeks of the lithium cobaltate/silicon carbon battery in comparative example 2.
As can be seen from the test results in table 1 and fig. 5, compared with comparative example 3, in example 5 and example 6 of the present application, since the electrolyte additive a and the electrolyte additive E are respectively added to the electrolyte, the 50-week average coulombic efficiency of the copper/lithium battery in example 5 and example 6 of the present application is higher than that of the copper/lithium battery in comparative example 3, and the capacity retention rate after 100 weeks of the lithium cobaltate/lithium battery in example 5 and example 6 of the present application is higher than that after 100 weeks of the lithium cobaltate/lithium battery in comparative example 3. Compared with the comparative example 4, in the example 7 of the present application, the electrolyte additive F is added to the electrolyte, so that the average coulombic efficiency at 50 weeks of the copper/lithium battery in the example 7 of the present application is higher than the average coulombic efficiency at 50 weeks of the copper/lithium battery in the comparative example 4, and the capacity retention rate after 100 weeks of the lithium cobaltate/lithium battery in the example 7 of the present application is higher than the capacity retention rate after 100 weeks of the lithium cobaltate/lithium battery in the comparative example 4. Compared with the comparative example 5, the electrolyte additive a is added into the electrolyte in the example 8, so that the average coulombic efficiency at 50 weeks of the copper/lithium battery in the example 8 is higher than that at 50 weeks of the copper/lithium battery in the comparative example 5, and the capacity retention rate after 100 weeks of the lithium cobaltate/lithium battery in the example 8 is higher than that after 100 weeks of the lithium cobaltate/lithium battery in the comparative example 5.
The above test results show that the electrolyte containing the electrolyte additive in the embodiments of the present application can significantly improve the coulombic efficiency and the cycle performance of the battery, because the electrolyte additive in the embodiments of the present application can be reduced on the surface of a negative electrode (a graphite negative electrode, a silicon-carbon negative electrode, a lithium negative electrode) in preference to an organic solvent in the electrolyte to form a stable interface film rich in lithium fluoride, a compound containing a carbon-nitrogen bond, silane and other compounds, not only can reduce the side reaction of the electrolyte and the negative electrode, and improve the coulombic efficiency and the cycle performance of the battery, but also an N-Si bond in the electrolyte additive can react with a small amount of HF in the electrolyte containing lithium hexafluorophosphate, so that the lithium hexafluorophosphate is inhibited from being further decomposed, and the stability of the electrolyte is improved.
Fig. 6 is a linear sweep voltammogram of the electrolytes of example 5 and comparative example 3, from which it can be seen that the LSV curve of comparative example 3 without additives has a reduction potential of about 0.9V, while the LSV curve of example 5 with additives is about 1.6V, which is significantly higher than that of comparative example 3, indicating that the additives are preferentially reduced to form a stable SEI film covering the surface of the negative electrode, and the reductive decomposition of the electrolyte on the surface of the negative electrode is inhibited, thereby improving the cycling stability of the battery.
Fig. 7, 8 and 9 are XPS detection charts showing the correspondence of F1s, N1s and Si2p spectra on the surface of the graphite electrode sheet after cycling of the lithium cobaltate/graphite lithium secondary batteries of example 1 and comparative example 1 of the present application. Fig. 10, 11 and 12 are XPS detection charts corresponding to F1s, N1s and Si2p spectra on the surface of the lithium sheet after cycling of the lithium cobaltate/lithium batteries of example 5 and comparative example 3 of the present application. As can be seen from the spectrum, the enhancement of Li-F, C-N and Si-C indicates the formation of a stable interfacial film rich in LiF, C-N, and silane compounds on the surface of the negative electrode.
Comparing the data of examples 7 to 8 with the data of comparative examples 4 to 5, it can be found that the electrolyte additive provided by the embodiment of the present application can effectively improve the coulombic efficiency and the cycle performance of the battery in the carbonate electrolyte, and has an obvious effect in the ether solvent electrolyte.
Claims (17)
1. An electrolyte additive is characterized in that the chemical structural formula of the electrolyte additive is shown as a formula (I),
in the formula (I), R is1、R2、R3、R4、R5、R6Respectively selected from any one of alkyl, halogenated alkyl, alkoxy, halogenated alkoxy, alkenyl, halogenated alkenyl, alkenyloxy, halogenated alkenyloxy, aryl, halogenated aryl, aryloxy and halogenated aryloxy; the R is7Is haloalkyl, and X is selected from O or S.
2. The electrolyte additive of claim 1 wherein the alkyl, haloalkyl, alkoxy, haloalkoxy have from 1 to 20 carbon atoms; the carbon atom number of the alkenyl, the halogenated alkenyl, the alkenyloxy and the halogenated alkenyloxy is 2-20; the number of carbon atoms of the aryl, halogenated aryl, aryloxy and halogenated aryloxy is 6-20.
3. The electrolyte additive of claim 1 or 2 wherein the halogen of the haloalkyl, haloalkoxy, haloalkenyl, haloalkenyloxy, haloaryl and haloaryloxy groups comprises fluorine, chlorine, bromine, iodine, said halogen being perhalogenated or partially halogenated.
4. The electrolyte additive of any one of claims 1-3 wherein R is7Is a fluorinated alkyl group having 1 to 20 carbon atoms.
5. A secondary battery electrolyte comprising an electrolyte salt, a non-aqueous organic solvent and an additive comprising the electrolyte additive of any one of claims 1-4.
6. The secondary battery electrolyte of claim 5 wherein the electrolyte additive is present in the secondary battery electrolyte in an amount of 0.1% to 10% by weight.
7. The secondary-battery electrolyte of claim 5 or 6 wherein the electrolyte salt comprises at least one of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a zinc salt, and an aluminum salt.
8. The secondary battery electrolyte of any of claims 5-7 wherein the electrolyte salt comprises MClO4、MBF4、MPF6、MAsF6、MPF2O2、MCF3SO3、MTDI、MB(C2O4)2、MBF2C2O4、M[(CF3SO2)2N]、M[(FSO2)2N]And M [ (C)mF2m+1SO2)(CnF2n+1SO2)N]Wherein M is Li, Na or K, and M and n are natural numbers.
9. The secondary-battery electrolyte of claim 5 wherein the molar concentration of the electrolyte salt in the secondary-battery electrolyte is from 0.01mol/L to 8.0 mol/L.
10. The secondary battery electrolyte as claimed in claim 5, wherein the non-aqueous organic solvent includes one or more of a carbonate-based solvent, an ether-based solvent, and a carboxylic acid-based solvent.
11. The secondary battery electrolyte of claim 5 wherein the additives further comprise other additives including one or more of biphenyl, fluorobenzene, vinylene carbonate, vinyl trifluoromethyl carbonate, vinyl ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, vinyl sulfite, succinonitrile, adiponitrile, 1, 2-bis (2-cyanoethoxy) ethane, and 1,3, 6-hexanetrinitrile.
12. A secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolyte comprising the secondary battery electrolyte according to any one of claims 5 to 11.
13. The secondary battery of claim 12, wherein the negative electrode comprises one or more of a carbon-based negative electrode, a silicon-based negative electrode, a tin-based negative electrode, a lithium negative electrode, a sodium negative electrode, a potassium negative electrode, a magnesium negative electrode, a zinc negative electrode, and an aluminum negative electrode.
14. The secondary battery of claim 13, wherein the carbon-based negative electrode comprises one or more of graphite, hard carbon, soft carbon, graphene; the silicon-based negative electrode comprises one or more of silicon, silicon carbon, silicon oxygen and silicon metal compounds; the tin-based negative electrode comprises one or more of tin, tin carbon, tin oxygen and tin metal compounds; the lithium negative electrode includes metallic lithium or a lithium alloy.
15. The secondary battery of claim 14, wherein the lithium alloy comprises at least one of a lithium silicon alloy, a lithium sodium alloy, a lithium potassium alloy, a lithium aluminum alloy, a lithium tin alloy, and a lithium indium alloy.
16. The secondary battery according to claim 13, wherein the secondary battery comprises a lithium secondary battery, a potassium secondary battery, a sodium secondary battery, a magnesium secondary battery, a zinc secondary battery, or an aluminum secondary battery.
17. A terminal comprising a housing, and an electronic component and a battery housed in the housing, the battery supplying power to the electronic component, the battery comprising the secondary battery according to any one of claims 12 to 16.
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| CN202010290478.8A CN113540561A (en) | 2020-04-14 | 2020-04-14 | Electrolyte additive, secondary battery electrolyte, secondary battery and terminal |
| PCT/CN2021/087200 WO2021208955A1 (en) | 2020-04-14 | 2021-04-14 | Electrolyte additive, secondary battery electrolyte, secondary battery and terminal |
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| CN114069050A (en) * | 2022-01-17 | 2022-02-18 | 河北工业大学 | High-stability potassium ion battery amide electrolyte and application thereof |
| CN114069043A (en) * | 2021-10-26 | 2022-02-18 | 惠州锂威新能源科技有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
| CN116264323A (en) * | 2021-12-15 | 2023-06-16 | 张家港市国泰华荣化工新材料有限公司 | Sodium ion battery electrolyte and sodium ion battery |
| WO2024029973A1 (en) * | 2022-08-04 | 2024-02-08 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte and lithium secondary battery comprising same |
| KR20240019744A (en) * | 2022-08-04 | 2024-02-14 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte and lithium secondary battery comprising the same |
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| CN114069043A (en) * | 2021-10-26 | 2022-02-18 | 惠州锂威新能源科技有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
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| KR20240019744A (en) * | 2022-08-04 | 2024-02-14 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte and lithium secondary battery comprising the same |
| KR102703534B1 (en) | 2022-08-04 | 2024-09-06 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte and lithium secondary battery comprising the same |
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