CN115101712A - Positive pole piece, electrolyte, battery pack and power utilization device - Google Patents
Positive pole piece, electrolyte, battery pack and power utilization device Download PDFInfo
- Publication number
- CN115101712A CN115101712A CN202210854137.8A CN202210854137A CN115101712A CN 115101712 A CN115101712 A CN 115101712A CN 202210854137 A CN202210854137 A CN 202210854137A CN 115101712 A CN115101712 A CN 115101712A
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- China
- Prior art keywords
- electrolyte
- active material
- positive electrode
- material layer
- derivative
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 82
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000002161 passivation Methods 0.000 claims abstract description 54
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 35
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229930192474 thiophene Natural products 0.000 claims abstract description 32
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000011149 active material Substances 0.000 claims description 50
- 239000000654 additive Substances 0.000 claims description 47
- 230000000996 additive effect Effects 0.000 claims description 47
- -1 acid anhydride compound Chemical class 0.000 claims description 30
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 13
- 229940014800 succinic anhydride Drugs 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 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
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 6
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 230000009931 harmful effect Effects 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000013543 active substance Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WYJOVVXUZNRJQY-UHFFFAOYSA-N 2-Acetylthiophene Chemical compound CC(=O)C1=CC=CS1 WYJOVVXUZNRJQY-UHFFFAOYSA-N 0.000 description 1
- JCCCMAAJYSNBPR-UHFFFAOYSA-N 2-ethylthiophene Chemical compound CCC1=CC=CS1 JCCCMAAJYSNBPR-UHFFFAOYSA-N 0.000 description 1
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 1
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013302 LiMS Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000979 O alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 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
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The embodiment of the application provides a positive pole piece, electrolyte, battery package and power consumption device. The positive pole piece includes: the electrode plate comprises a pole plate body and a passivation part, wherein the passivation part is formed on the surface of the pole plate body, the passivation part contains a conductive polymer, and a monomer of the conductive polymer comprises at least one selected from the following components: (a) thiophene or a derivative thereof; (b) aniline or a derivative thereof; and (c) phenylacetylene or a derivative thereof. The application provides a positive pole piece in passivation portion parcel can improve anodal electric conductivity at the surface of pole piece body to the charge transfer ability of electrolyte electrode interface is strengthened, the dissolving out of transition metal ion is reduced, and can not produce the harmful effects to the energy density of battery.
Description
Technical Field
The application relates to the technical field of electrochemical energy storage equipment, in particular to a positive pole piece, electrolyte, a battery pack and an electric device.
Background
Lithium ion batteries are widely used due to their advantages of portability, high energy density, small self-discharge, long life, high discharge power, environmental protection, etc. The positive electrode plays an important role in performance of the lithium ion battery, and the currently widely used positive electrode materials of the lithium ion battery, such as lithium cobaltate, lithium manganate, lithium iron phosphate and the like, are often poor in conductivity due to the structure of the positive electrode materials, so that the electrochemical performance of the battery is severely limited, and particularly the charge and discharge performance under high multiplying power is limited. One conventional method for solving this problem is to add a conductive agent to the positive electrode material to improve the conductivity of the positive electrode. In order to establish a conductive network with high efficiency and sufficient contact, the content of the used conductive agent is often high, but the density of the conductive agent is lower than that of the positive electrode active material, and the conductive agent cannot provide capacity per se, so that the energy density of the battery is obviously reduced, and the performance of the battery is influenced.
In summary, the existing lithium ion batteries, especially the positive electrode thereof, still need to be improved.
Disclosure of Invention
To prior art's not enough, the purpose of this application provides a positive pole piece, electrolyte, battery package and power consumption device. The application provides a positive pole piece surface is formed with the passivation portion, and this passivation portion contains conducting polymer for anodal electric conductivity is showing and is promoting and can not cause the reduction of battery energy density. The electrolyte can solve the problems that the conductivity of the anode of the lithium ion battery is poor, the structure is unstable, and the low-temperature cycle performance and the rate performance of the battery are poor.
In order to achieve the above object, the following technical solutions are adopted in the present application:
in a first aspect, the present application provides a positive electrode sheet, comprising:
a pole piece body, and
a passivation portion formed on a surface of the pole piece body, the passivation portion containing a conductive polymer, a monomer of the conductive polymer including at least one selected from the group consisting of:
(a) thiophene or a derivative thereof;
(b) aniline or a derivative thereof; and
(c) phenylacetylene or a derivative thereof.
In some preferred embodiments thereof, the passivation portion further comprises an anhydride-based compound or a derivative thereof.
In some preferred embodiments, the anhydride compound is selected from at least one of succinic anhydride, maleic anhydride and glutaric anhydride.
In some preferred embodiments, the passivation portion comprises a film layer covering at least a portion of the pole piece body, the film layer having a thickness of 5-40 angstroms.
In some preferred embodiments, the pole piece body includes a body portion, a first side active material layer, and a second side active material layer, the first side active material layer and the second side active material layer are located on two opposite sides of the body portion, the passivation portion includes a first film layer and a second film layer, and at least one of the first film layer or the second film layer includes the conductive polymer;
the first film layer covers at least a portion of the first side active material layer, and the second film layer covers at least a portion of the second side active material layer.
In some preferred embodiments, the side surfaces of the first side active material layer and the second side active material layer opposite to each other in the length direction of the body are end portions, and the passivation portion includes a third film layer covering at least a part of the end portions.
In some preferred embodiments thereof, the third film layer connects two or one of the first and second film layers.
In some preferred embodiments, the ratio of the area of the first film layer covering the first side active material layer to the surface area of the first side active material layer is greater than or equal to 3/10 and less than or equal to 1;
the ratio of the area of the second film layer covering the second side active material layer to the surface area of the second side active material layer is greater than or equal to 3/10 and less than or equal to 1.
In some preferred embodiments, the pole piece body comprises a body part and an active substance layer, the active substance layer is coated on the body part, and the passivation part comprises a film layer, and the film layer covers at least part of the active substance layer.
In some preferred embodiments thereof, the passivation is flexible.
In a second aspect, the present application provides an electrolyte comprising a lithium salt, a solvent, and a first additive; the first additive includes at least one selected from the group consisting of:
(a) thiophene or a derivative thereof;
(b) aniline or a derivative thereof; and
(c) phenylacetylene or a derivative thereof.
In some preferred embodiments, the first additive is contained in an amount of 0.1 to 5 wt% based on the total mass of the electrolyte.
In some preferred embodiments, the electrolyte further comprises a second additive, and the second additive comprises an anhydride compound or a derivative thereof.
In some preferred embodiments, the acid anhydride compound is at least one selected from succinic anhydride, maleic anhydride and glutaric anhydride.
In some preferred embodiments, the second additive is contained in an amount of 0.5 to 3 wt% based on the total mass of the electrolyte.
In some preferred embodiments thereof, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis fluorosulfonylimide, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate.
In some preferred embodiments, the concentration of the lithium salt in the electrolyte is 0.5-1.5 mol/L.
In some preferred embodiments thereof, the solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, sulfolane, dimethyl sulfoxide, acetonitrile, malononitrile, glutaronitrile.
In some preferred embodiments, the electrolyte further comprises a third additive, and the third additive is selected from at least one of fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, vinyl sulfite and tris (trimethylsilane) phosphate.
In a third aspect, the present application provides a method for preparing the positive electrode plate, including:
(1) placing the pole piece body in the electrolyte as described above;
(2) and applying current to the pole piece body and the electrolyte to form a passivation part on the surface of the pole piece body so as to obtain the positive pole piece.
In a fourth aspect, the present application provides a battery comprising a positive electrode sheet as described above or an electrolyte as described above.
In a fifth aspect, the present application provides a battery pack comprising a battery as described above.
In a sixth aspect, the present application provides an electric device comprising the battery or the battery pack as described above.
The technical scheme provided by the embodiment of the application can have the following beneficial effects:
the application provides a positive pole piece in passivation portion parcel can improve anodal electric conductivity at the surface of pole piece body to the charge transfer ability of electrolyte electrode interface is strengthened, the dissolving out of transition metal ion is reduced, and can not produce the harmful effects to the energy density of battery.
The first additive in the electrolyte can form a passivation part with an organic polymer structure in situ on a pole piece body during first-cycle charging and discharging of a battery, and the formed passivation part has high conductivity, can enhance the charge transfer capacity of an electrolyte electrode interface, and restrains the dissolution of metal ions of a positive electrode material.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
fig. 1 is a schematic structural diagram of a positive electrode sheet according to an embodiment of the present application.
Detailed Description
The present application will be described in further detail with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
In the description of the present specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In a first aspect, an embodiment of the present application provides a positive electrode plate, as shown in fig. 1, including a plate body and a passivation portion, where the passivation portion is formed on a surface of the plate body, and the passivation portion includes a conductive polymer, and a monomer of the conductive polymer includes at least one selected from the following: (a) thiophene or a derivative thereof; (b) aniline or a derivative thereof; and (c) phenylacetylene or a derivative thereof.
In this embodiment, thiophene or its derivative, aniline or its derivative, and phenylacetylene or its derivative can undergo a polymerization reaction during the first cycle of charging and discharging of the battery to form a passivation portion in the form of a conductive polymer, i.e., a solid electrolyte interface (CEI) film, in situ on the electrode plate body, where the passivation portion has high flexibility, oxidation resistance, and stability, and can effectively hinder the redox reaction of the electrolyte at the positive electrode, protect the electrolyte from being excessively consumed, and protect the electrode plate body from being damaged. The monomer has conductivity, and a conductive polymer generated after polymerization reaction has high conductivity, and the passivation part is wrapped on the surface of the pole piece body to improve the conductivity of the positive pole, so that the charge transfer capacity of an electrolyte electrode interface is enhanced, and the dissolution of transition metal ions is reduced. The monomer is not used as a raw material for forming the pole piece body, so that the content of the positive active material in the pole piece body is not influenced, and the energy density of the battery is not adversely affected.
As used herein, "derivatives of thiophene" refers to compounds obtained by electrophilic substitution reaction at the α -or β -position of the thiophene ring, including α -thiophene derivatives and β -thiophene derivatives, wherein α -thiophene derivatives include, but are not limited to α -methylthiophene, α -acetylthiophene, α -chlorothiophene, α -iodothiophene, α -chloromethylthiophene, α -ethylthiophene, thiophene- α -formaldehyde, thiophene- α -acetic acid, thiophene- α -ethanol, thiophene- α -acetonitrile, thiophene- α -ethylamine, α -nitrothiophene, and the like; beta-thiophene derivatives include, but are not limited to, beta-methylthiophene, beta-chloromethylthiophene, beta-bromothiophene, beta-iodothiophene, thiophene-beta-formaldehyde, thiophene-beta-carboxylic acid, beta-3-thiophenepropionic acid, beta-bromomethylthiophene.
As used herein, the term "derivative of aniline" refers to a compound obtained by substitution of a benzene ring in the parent structure of aniline, wherein the substituents include, but are not limited to, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C5 unsaturated alkyl, substituted or unsubstituted C6-C10 aryl, and substituted or unsubstituted C7-C10 alkylaryl.
As used herein, the term "derivative of phenylacetylene" refers to a compound obtained by substitution of a benzene ring in the parent structure of phenylacetylene, wherein the substituents include, but are not limited to, halogen, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C2-C5 unsaturated alkyl, substituted or unsubstituted C6-C10 aryl, and substituted or unsubstituted C7-C10 alkylaryl.
Further, in some preferred embodiments of the present application, the passivation portion further includes an acid anhydride compound or a derivative thereof.
In the application, in the process of polymerizing thiophene or a derivative thereof, aniline or a derivative thereof, and/or phenylacetylene or a derivative thereof to form a passivation portion, the generated conductive polymer has a long chain structure, and the long chain grows laterally along with the progress of polymerization reaction, and extends laterally to be directly communicated with a negative electrode interface film (SEI) or communicated with the SEI through conductive metal ions in an electrolyte, so that a positive electrode and a negative electrode are conducted to cause micro short circuit. The inventors of the present application have unexpectedly found that when the passivation portion further includes an acid anhydride-based compound or a derivative thereof, the acid anhydride-based compound or the derivative thereof blocks the occurrence of the above phenomenon.
The reason for this is that the acid anhydride compound or its derivative also participates in film formation by ring opening in the process of forming the passivation portion by polymerization of the monomer, and the simultaneous participation thereof blocks the lateral growth of the conductive polymer long chain formed by polymerization of the monomer, thereby effectively preventing conduction between the passivation portion of the positive electrode and the interface film of the negative electrode caused by the extension of the conductive polymer long chain to the negative electrode. And the anhydride compound or the derivative thereof participates in film formation to form organic or inorganic negative ions, so that on one hand, the interface impedance of the positive electrode can be reduced, the low-temperature cycle performance and the rate performance of the battery can be improved, on the other hand, hydrogen (including hydrogen and HF) generated in the polymerization process of the conductive monomer can be removed, the side reaction of thiophene and other monomers during film formation in polymerization can be eliminated, the transition metal oxide type positive electrode material can be prevented from being dissolved and corroded, and the volume expansion of the battery can be inhibited.
Further, in some preferred embodiments of the present application, the acid anhydride compound is selected from at least one of succinic anhydride, maleic anhydride, and glutaric anhydride.
Further, in some preferred embodiments of the present application, the passivation portion includes a film layer covering at least a portion of the pole piece body, the film layer having a thickness of 5-40 angstroms.
Wherein the thickness of the film layer can be detected by XPS, or can be calculated by measuring the loudness intensity change of the lattice oxygen peak of the structure of the anode material.
Further, in some preferred embodiments of the present application, the pole piece body includes a body portion 1, a first side active material layer 2, and a second side active material layer 3, the first side active material layer 2 and the second side active material layer 3 are located on two opposite sides of the body portion 1, the passivation portion includes a first film layer 51 and a second film layer 52, and at least one of the first film layer 51 or the second film layer 52 includes the conductive polymer;
the first film layer 51 covers at least a part of the first side active material layer 2, and the second film layer 52 covers at least a part of the second side active material layer 3.
In the embodiment, the body portion 1 includes a first surface and a second surface opposite to each other in a thickness direction thereof, the first side active material layer 2 is formed on the first surface thereof, and the second side active material layer 3 is formed on the second surface thereof, and since the first side active material layer 2 and the second side active material layer 3 have a predetermined thickness, the first side active material layer 2 and the second side active material layer 3 respectively include two end portions 4 opposite to each other in a length direction of the body portion 1. Wherein, in the first cycle charge and discharge process of the battery, if the first side active material layer 2 faces the battery negative electrode plate, and is preferentially contacted with thiophene or its derivative, aniline or its derivative, phenylacetylene or its derivative, and the content of thiophene or its derivative, aniline or its derivative, phenylacetylene or its derivative is preset to be only enough to form a conductive polymer in at least partial polymerization of the first side active material layer 2, only the first film layer 51 comprises the conductive polymer; if the first side active material layer 2 and the second side active material layer 3 are simultaneously in contact with thiophene or its derivative, aniline or its derivative, or phenylacetylene or its derivative during the first cycle of charge and discharge of the battery, and the content of the thiophene or its derivative, the aniline or its derivative, or the phenylacetylene or its derivative is sufficient, the conductive polymer is included in both the first film layer 51 and the second film layer 52.
The main body 1 plays a role in current collection and electrical connection, and includes, but is not limited to, a metal foil (e.g., an aluminum foil), and the first side active material layer 2 and the second side active material layer 3 are formed by applying a slurry containing a positive electrode active material, a binder, and the like onto the main body 1, drying the slurry, and performing a rolling process at 0 to 5 MPa. Wherein the positive electrode active material is selected from LiCoO 2 、LiNiO 2 、LiCo x Ni 1-x O 2 (0≤x≤1)、LiCo x Ni 1-x-y Al y O 2 (0≤x≤1,0≤y≤1)、LiMn 2 O 4 、LiFe x Mn y M z O 4 (M is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, x is 0-1, y is 0-1, z is 0-1, and x + y + z is 1), Li 1+x L 1-y-z M y N z O 2 (L, M, N represents at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S, and B-0.1. ltoreq. x.ltoreq.0.2, 0. ltoreq. y.ltoreq.1, 0. ltoreq. z.ltoreq.1, 0. ltoreq. y + z. ltoreq.1), LiFePO 4 、Li 3 V 2 (PO 4 ) 3 、Li 3 V 3 (PO 4 ) 3 、LiVPO 4 F、Li 2 CuO 2 、Li 5 FeO 4 And metal sulfides and oxides such as V 2 S 3 、FeS、FeS 2 、LiMS x (M is at least one of transition metal elements such as Fe, Ni, Cu, Mo and the like, x is more than or equal to 1 and less than or equal to 2.5), TiO 2 、Cr 3 O 8 、V 2 O 5 、MnO 2 And the like; wherein, the binder is a binder commonly used for the positive electrode, and includes but is not limited to one or more of fluorine-containing resin and polyolefin compounds such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE) and Styrene Butadiene Rubber (SBR).
Further, in some preferred embodiments of the present application, the passivation layer includes a third film layer 53, and the third film layer 53 covers at least a portion of the end portion 4. By providing the third film layer 53, the end portion 4 is ensured to be covered, side reactions of the electrolyte and the positive electrode active material layer at the end portion 4 can be reduced, and the positive electrode is further protected.
Further, in some preferred embodiments of the present invention, the third membrane layer 53 connects two or one of the first membrane layer 51 and the second membrane layer 52, so that the continuity of the membrane layer at the end portion and the active material layer is ensured, and side reactions between the electrolyte and the positive active material at the connection portion between the end portion and the active material layer are prevented.
Further, in some preferred embodiments of the present application, the ratio of the area of the first film layer 51 covering the first side active material layer 2 to the surface area of the first side active material layer 2 is greater than or equal to 3/10 and less than or equal to 1;
the ratio of the area of the second film layer 52 covering the second side active material layer 3 to the surface area of the second side active material layer 3 is greater than or equal to 3/10 and less than or equal to 1, so as to ensure that the covered area of the film layer is large enough to protect the positive electrode active material as a whole.
Further, in some preferred embodiments of the present application, the pole piece body includes a body portion and an active substance layer, the active substance layer is coated on the body portion, and the passivation portion includes a film layer, and the film layer covers at least a portion of the active substance layer.
Further, in some preferred embodiments of the present application, the passivation has flexibility, which can effectively improve the folding resistance of the passivation, effectively solve the problem of volume expansion mismatch between the passivation and the positive electrode material, and can increase the overall flexibility and long-term electrochemical cycling stability of the battery.
In a second aspect, embodiments herein provide an electrolyte comprising a lithium salt, a solvent, and a first additive; the first additive includes at least one selected from the group consisting of: (a) thiophene or a derivative thereof; (b) aniline or a derivative thereof; and (c) phenylacetylene or a derivative thereof.
In the electrolyte described in this embodiment, the first additive has an oxidation potential lower than that of solvent molecules, and during the first cycle of charging and discharging, a polymerization reaction preferentially occurs at a higher potential on the surface of a positive electrode material with a non-uniform potential, and a passivation portion containing a conductive polymer is formed in situ on the positive electrode material, that is, a CEI film in a conductive organic polymer structure is formed, where the passivation portion has higher flexibility, oxidation resistance and stability, and can effectively hinder the redox reaction of the electrolyte at the positive electrode, protect the electrolyte from being excessively consumed and damage the positive electrode, and also protect the electrolyte solvent from being oxidized and decomposed at a high potential, thereby improving the service life of the battery at a high voltage. The first additive has high conductivity, and a polymer generated after the polymerization reaction has high conductivity, so that the conductivity of the positive electrode can be remarkably improved when the formed passivation part is wrapped on the surface of the positive electrode material, the charge transfer capability of an electrolyte electrode interface is enhanced, the dissolution of transition metal ions is reduced, and the energy density of the battery is not influenced.
Further, in some preferred embodiments of the present application, the first additive is contained in an amount of 0.1 to 5 wt%, for example, 0.1 wt%, 0.2 wt%, 0.5 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, etc., based on the total mass of the electrolyte.
When the content of the first additive is too low, it is not sufficient to react on the surface of the positive active material layer to form a passivation portion, the protective effect on the electrode cannot be exerted and the desired positive electrode conductivity cannot be obtained; when the content of the first additive is too high, the polymerization amount becomes too large, and the surface of the positive electrode active material layer is covered with the first additive, resulting in too large interface resistance and deterioration of cycle performance of the lithium ion battery.
Further, in some preferred embodiments of the present application, the electrolyte further includes a second additive, and the second additive includes an acid anhydride compound or a derivative thereof.
In the electrolyte, the second additive and the first additive cooperate to form a stable passivation part, so that the rate performance and the cycle performance of the lithium ion battery at low temperature can be effectively improved, the prepared battery has high energy density and safety, and the problems of capacity attenuation, failure and safety of the battery caused by micro short circuit of a positive electrode and a negative electrode and electrochemical side reaction can be solved by using the second additive.
Specifically, the anhydride compound or the derivative thereof also participates in film formation through ring opening in the process of forming the passivation part by polymerization of the first additive, and the synchronous participation of the anhydride compound or the derivative thereof can block the transverse growth of the conductive polymer long chain formed by polymerization of the first additive, so that the conduction of the passivation part of the positive electrode and the interface film of the negative electrode caused by the fact that the conductive polymer long chain extends to the negative electrode is effectively prevented. And the anhydride compound or the derivative thereof participates in film formation to form organic or inorganic negative ions, so that on one hand, the interface impedance of the positive electrode can be reduced, the low-temperature cycle performance and the rate performance of the battery can be improved, on the other hand, hydrogen (including hydrogen and HF) generated in the polymerization process of the conductive monomer can be removed, the side reaction of thiophene and other monomers during film formation in polymerization can be eliminated, the transition metal oxide type positive electrode material can be prevented from being dissolved and corroded, and the volume expansion of the battery can be inhibited.
Further, in some preferred embodiments of the present application, the anhydride-based compound is selected from at least one of succinic anhydride, maleic anhydride, and glutaric anhydride.
Further, in some preferred embodiments of the present application, the second additive is contained in an amount of 0.5 to 3 wt%, for example, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, etc., based on the total mass of the electrolyte.
When the content of the second additive is too low, the second additive is not enough to block the communication of the positive and negative electrode interfaces and remove hydrogen ions, and when the content of the second additive is too high, the cycle performance of the lithium ion battery is also deteriorated.
Further, in some preferred embodiments herein, the lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium tetrafluoroborate (LiBF) 4 ) At least one of lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiODFB).
The lithium salt has the advantages of high conductivity, good thermal stability and good electrochemical stability, and can enhance the conductivity and electrochemical stability of the battery electrolyte when being applied to the preparation process of the battery electrolyte.
Further, in some preferred embodiments of the present application, the concentration of the lithium salt in the electrolyte is 0.5-1.5 mol/L, and for example, may be 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, and the like.
Further, in some preferred embodiments herein, the solvent is selected from at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC), sulfolane, dimethyl sulfoxide, acetonitrile, malononitrile, and glutaronitrile.
The nonaqueous organic solvent used as a solvent for the lithium ion battery has the advantages of good oxidation reduction resistance, high dielectric constant and low viscosity.
Further, in some preferred embodiments of the present application, the electrolyte further includes a third additive, and the third additive is selected from at least one of fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, vinyl sulfite, and tris (trimethylsilane) phosphate.
The additive can be used as a positive electrode film forming additive, a negative electrode film forming additive, a high-low temperature additive and the like, can be synergized with the first additive and the second additive to obtain a stable positive and negative electrode interface layer, and can further improve the comprehensive performance of the lithium ion battery adopting the electrolyte
Further, in some preferred embodiments of the present application, the third additive is contained in an amount of 1 to 8 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, etc., based on the total mass of the electrolyte.
In a third aspect, an embodiment of the present application provides a method for preparing the positive electrode sheet, including:
(1) placing the pole piece body in the electrolyte as described above;
(2) and applying current to the pole piece body and the electrolyte to form a passivation part on the surface of the pole piece body so as to obtain the positive pole piece.
Those skilled in the art will appreciate that the positive electrode sheet can be prepared using a battery comprising the above electrolyte, a negative electrode sheet body, and a separator. Illustratively, the positive electrode plate body, the diaphragm and the negative electrode plate body are made into a flexible package battery, and the injected electrolyte is the lithium ion battery. And carrying out constant current charge and discharge test after standing for 12 h. In the first-week charging and discharging process, the first additive and the second additive in the electrolyte are polymerized in situ on the positive pole piece body to form a film to form a passivation part, and then the positive pole piece is obtained. Wherein the constant current charge and discharge test is carried out at room temperature in 0.05-5V potential interval and 0.1-2C (1C is 1000mA g) -1 ) Under the condition of current density.
In a fourth aspect, embodiments of the present application provide a battery, where the battery includes a positive electrode sheet as described above or an electrolyte as described above. The battery has excellent rate performance, safety performance and higher energy density.
Further, the battery also comprises a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece.
In this embodiment, the negative electrode sheet includes a negative electrode current collector and a negative electrode material layer disposed on the negative electrode current collector; the anode material layer includes an anode active material. Illustratively, the negative electrode current collector may include, but is not limited to, a metal foil or the like (e.g., a copper foil or the like), and the negative electrode active material is selected from at least one of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon-carbon alloy, and silicon-oxygen alloy, which are easily subjected to a lithium ion intercalation and deintercalation reaction, and may be a preferred choice of the negative electrode active material; more preferably, the negative electrode active material includes a silicon-carbon composite containing SiOx, wherein x is 0.9 to 1.8, 0.9 to 1.0, 1.0 to 1.2, 1.2 to 1.4, 1.4 to 1.6, or 1.6 to 1.8.
The membrane may be selected from polyethylene, polypropylene, polyvinylidene fluoride, and multilayer composite membranes of polyethylene, polypropylene, polyvinylidene fluoride.
The outer side of the battery is also provided with a package, such as an aluminum plastic film, a stainless steel cylinder, a square aluminum shell and the like.
In a fifth aspect, embodiments of the present application provide a battery pack, including the battery as described above.
Illustratively, the battery pack may include a case and a battery, the battery is disposed in the case, and the battery is the battery of the above embodiment. The shape of the case is not limited. The box body can be a frame-shaped box body, a disc-shaped box body or a box-shaped box body and the like. Illustratively, the box body comprises a lower shell and an upper shell which is covered with the lower shell. Go up the casing and form the portion of holding after the casing lid closes down, go up the casing and close down the back accessible fastener such as bolt locking fixed. A plurality of battery single cells are arranged in the capacitor receiving part and can be electrically connected in series or in parallel or in series-parallel.
In a sixth aspect, an embodiment of the present application provides an electric device. The electric device provides electric energy through the battery or the battery pack, and can be vehicles, mobile phones, portable equipment, notebook computers, ships, spacecrafts, electric toys, electric tools and the like. The vehicle can be a fuel oil vehicle, a gas vehicle or a new energy vehicle, and the new energy vehicle can be a pure electric vehicle, a hybrid electric vehicle or a range-extended vehicle and the like; spacecraft include aircraft, rockets, space shuttles, and spacecraft, among others; electric toys include stationary or mobile electric toys, such as game machines, electric car toys, electric ship toys, electric airplane toys, and the like; the electric tools include metal cutting electric tools, grinding electric tools, assembly electric tools, and electric tools for railways, such as electric drills, electric grinders, electric wrenches, electric screwdrivers, electric hammers, electric impact drills, concrete vibrators, and electric planers.
The technical effects provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The electrolyte preparation process comprises the following steps: in an argon atmosphere glove box with the moisture content of less than or equal to 1ppm, 30g of EC and 70g of EMC are mixed, then dried lithium salt is added into the mixed solvent, the total amount of lithium hexafluorophosphate solid is 13.9g, after lithium hexafluorophosphate is completely dissolved, the total amount of thiophene is added, the total amount of succinic anhydride is added, the total amount of thiophene is added, 1.15g of succinic anhydride is added, the total amount of vinylene carbonate is added, and the electrolyte is obtained after uniform mixing.
The electrolyte comprises the following components: the solvent composition is EC: EMC 3:7 (mass ratio), the lithium salt concentration was 1mol/L, the thiophene content was 2 wt% of the total mass of the electrolyte, and the succinic anhydride content was 1 wt% of the total mass of the electrolyte.
Example 2
An electrolyte was prepared in substantially the same manner as in example 1, except that vinylene carbonate was not added in this example, and thiophene was replaced with aniline.
Example 3
An electrolyte was prepared in substantially the same manner as in example 1, except that vinylene carbonate was not added in this example, and thiophene was replaced with phenylacetylene.
Example 4
An electrolyte was prepared in substantially the same manner as in example 1, except that the content of thiophene was 1% by weight of the total mass of the electrolyte.
Example 5
An electrolyte was prepared in substantially the same manner as in example 1, except that the content of thiophene was 5% by weight of the total mass of the electrolyte.
Comparative example 1
An electrolyte was prepared in substantially the same manner as in example 1, except that thiophene, succinic anhydride and vinylene carbonate were not contained, and the rest was the same as in example 1.
Comparative example 2
An electrolyte was prepared in substantially the same manner as in example 1, except that succinic anhydride was not contained, and the rest was the same as in example 1.
Comparative example 3
An electrolyte was prepared in substantially the same manner as in example 1, except that thiophene and succinic anhydride were not contained.
The electrolytes of examples 1 to 5 and comparative examples 1 to 3 are respectively adopted to prepare lithium ion batteries, and the performance of the batteries is tested, wherein the preparation process and the test method are as follows:
the battery is purchased to obtain a soft package battery without liquid injection, and the electrolyte is injected to obtain the lithium ion battery. The positive electrode material used in the battery was NCM811, the negative electrode material used was an artificially synthesized graphite material, the battery design capacity was 3Ah, and the electrolyte injection amount of the battery was 12.0 g. And carrying out charge-discharge cycle test on the battery on a charge-discharge instrument, wherein the test temperature is 0 ℃, the cycle multiplying power is 1C, and the charging voltage is 3.0V-4.3V. And calculating the capacity retention rate after circulation, wherein the calculation formula is as follows: capacity retention rate after the nth cycle (discharge capacity after the nth cycle/first cycle discharge capacity) × 100%.
Carrying out a rate discharge test on the battery on a charge and discharge instrument, wherein the test temperature is 25 ℃, the charge rate is 0.33C, the discharge rate is 0.33C, 2C, 3C and 5C, the charge voltage is 3.0-4.3V, the discharge retention rate of different rates is calculated,
the calculation formula is as follows: the discharge retention rate (discharge capacity at a certain rate/discharge capacity of 0.33C) × 100%.
The results are shown in the following table:
it can be seen that the combination of the first additive with the second additive can improve the low-temperature cycle performance and rate performance of the battery, as compared to comparative examples 1 to 3.
It can be seen from examples 1 to 3 that thiophene works best in combination with succinic anhydride.
The examples 1, 4 and 5 show that the battery has excellent low-temperature cycle performance and rate performance when the content of thiophene is 0.1-5 wt%, wherein the effect of the content of thiophene is better when the content of thiophene is 2 wt%, which means that the content of thiophene is too low to react on the surface of the cathode material to form a protective film, and the content of thiophene is too high to cause too large polymerization amount and too large interfacial resistance, and conversely, the cycle performance of the lithium ion battery is deteriorated.
According to the lithium ion electrolyte, any one of thiophene or a derivative thereof, aniline or a derivative thereof, and phenylacetylene or a derivative thereof is used as one of lithium ion electrolyte additives, and a polymer generated after polymerization has good conductivity, is attached to the surface of a material, can enhance the charge transfer capacity of an electrode interface, and can also restrict the dissolution of metal ions of a positive electrode material, so that the stability of the structure of the positive electrode material is protected to a certain extent, and side reactions in the electrolyte are reduced. Since thiophene, aniline, phenylacetylene and other conductive organic monomers can react under the conditions of an electric field and heating, chemical and electrochemical polymerization reactions can rapidly occur in the phase of cell formation (first-cycle charge and discharge process), so that the traditional CEI film is improved and contains conductive polymers. Meanwhile, the anhydride compound can also participate in film formation to block the conduction of conductive anode and cathode interfacial films, so that the occurrence of micro short circuit is effectively prevented, organic or inorganic negative ions formed by polymerization of the anhydride compound can reduce the interfacial impedance, synergistically improve the low-temperature cycle performance and the rate capability of the battery, and remove H generated in the electrolyte + The transition metal oxide type anode material is prevented from being dissolved and corroded, and the problems of battery capacity attenuation, invalidation and safety are avoided.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by those skilled in the art that the scope of the disclosure herein is not limited to the particular combination of features described above, but also encompasses other arrangements formed by any combination of the above features or their equivalents without departing from the spirit of the disclosure. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (23)
1. A positive electrode sheet, comprising:
a pole piece body, and
a passivation portion formed on a surface of the pole piece body, the passivation portion containing a conductive polymer, a monomer of the conductive polymer including at least one selected from the group consisting of:
(a) thiophene or a derivative thereof;
(b) aniline or a derivative thereof; and
(c) phenylacetylene or a derivative thereof.
2. The positive electrode sheet according to claim 1, wherein the passivation portion further comprises an acid anhydride compound or a derivative thereof.
3. The positive electrode sheet according to claim 2, wherein the acid anhydride compound is at least one selected from succinic anhydride, maleic anhydride and glutaric anhydride.
4. The positive electrode sheet according to claim 1, wherein the passivation portion comprises a film layer covering at least a portion of the electrode sheet body, the film layer having a thickness of 5 to 40 angstroms.
5. The positive electrode sheet of claim 4, wherein the sheet body comprises a body portion, a first side active material layer, and a second side active material layer, the first side active material layer and the second side active material layer are located on opposite sides of the body portion, the passivation portion comprises a first film layer and a second film layer, and at least one of the first film layer or the second film layer comprises the conductive polymer;
the first film layer covers at least a portion of the first side active material layer, and the second film layer covers at least a portion of the second side active material layer.
6. The positive electrode sheet according to claim 5, wherein the side surfaces of the first side active material layer and the second side active material layer which face each other in the longitudinal direction of the body are end portions, and the passivation portion includes a third film layer which covers at least part of the end portions.
7. The positive electrode sheet of claim 6, wherein the third film layer connects two or more of the first and second film layers.
8. The positive electrode sheet according to claim 5, wherein the ratio of the area of the first film layer covering the first side active material layer to the surface area of the first side active material layer is greater than or equal to 3/10 and less than or equal to 1;
the ratio of the area of the second film layer covering the second side active material layer to the surface area of the second side active material layer is greater than or equal to 3/10 and less than or equal to 1.
9. The positive electrode sheet according to claim 1, wherein the sheet body includes a body portion substrate and an active material layer applied to the body portion, and the passivation portion includes a film layer covering at least a part of the active material layer.
10. The positive electrode tab as claimed in claim 1, wherein the passivation has flexibility.
11. An electrolyte comprising a lithium salt, a solvent, and a first additive; the first additive includes at least one selected from the group consisting of:
(a) thiophene or a derivative thereof;
(b) aniline or a derivative thereof; and
(c) phenylacetylene or a derivative thereof.
12. The electrolyte of claim 11, wherein the first additive is present in an amount of 0.1 to 5 wt.%, based on the total mass of the electrolyte.
13. The electrolyte of claim 11, further comprising a second additive comprising an anhydride-based compound or a derivative thereof.
14. The electrolyte of claim 13, wherein the anhydride-based compound is selected from at least one of succinic anhydride, maleic anhydride, and glutaric anhydride.
15. The electrolyte of claim 13, wherein the second additive is present in an amount of 0.5 to 3 wt.%, based on the total mass of the electrolyte.
16. The electrolyte of claim 11, wherein the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonyl) imide, lithium tetrafluoroborate, lithium bis (oxalato) borate, and lithium difluoro (oxalato) borate.
17. The electrolyte of claim 11 or 16, wherein the concentration of the lithium salt in the electrolyte is 0.5-1.5 mol/L.
18. The electrolyte of claim 11, wherein the solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, sulfolane, dimethyl sulfoxide, acetonitrile, malononitrile, and glutaronitrile.
19. The electrolyte of claim 11, further comprising a third additive selected from at least one of fluoroethylene carbonate, vinylene carbonate, vinyl sulfate, vinyl sulfite, tris (trimethylsilane) phosphate.
20. A method for preparing the positive electrode sheet according to any one of claims 1 to 10, comprising:
(1) placing the body of the pole piece in the electrolyte of any one of claims 11-19;
(2) and applying current to the pole piece body and the electrolyte to form a passivation part on the surface of the pole piece body so as to obtain the positive pole piece.
21. A battery comprising the positive electrode sheet according to any one of claims 1 to 10 or the electrolyte according to any one of claims 11 to 19.
22. A battery pack comprising the battery of claim 21.
23. An electric device comprising the battery of claim 21 or the battery pack of claim 22.
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CN105449279A (en) * | 2015-12-30 | 2016-03-30 | 东莞新能源科技有限公司 | Non-aqueous electrolyte solution and lithium-ion battery using same |
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CN111785925A (en) * | 2020-08-11 | 2020-10-16 | 天津市捷威动力工业有限公司 | Pole piece, application and low-temperature-rise safety lithium ion battery containing pole piece |
CN113659206A (en) * | 2021-08-13 | 2021-11-16 | 深圳新宙邦科技股份有限公司 | High-compaction lithium ion battery |
WO2022042373A1 (en) * | 2020-08-31 | 2022-03-03 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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CN106063002A (en) * | 2014-03-05 | 2016-10-26 | A123***有限责任公司 | Multivalent metal salts for lithium ion cells having oxygen containing electrode active materials |
CN105449279A (en) * | 2015-12-30 | 2016-03-30 | 东莞新能源科技有限公司 | Non-aqueous electrolyte solution and lithium-ion battery using same |
CN111785925A (en) * | 2020-08-11 | 2020-10-16 | 天津市捷威动力工业有限公司 | Pole piece, application and low-temperature-rise safety lithium ion battery containing pole piece |
WO2022042373A1 (en) * | 2020-08-31 | 2022-03-03 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
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