CN117133980A - 锂离子电池用低温电解液及锂离子电池 - Google Patents
锂离子电池用低温电解液及锂离子电池 Download PDFInfo
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- CN117133980A CN117133980A CN202311178696.2A CN202311178696A CN117133980A CN 117133980 A CN117133980 A CN 117133980A CN 202311178696 A CN202311178696 A CN 202311178696A CN 117133980 A CN117133980 A CN 117133980A
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- Prior art keywords
- lithium
- lithium ion
- ion battery
- low
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 71
- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 229940126062 Compound A Drugs 0.000 claims abstract description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- BAPGOVYLNIGTOU-UHFFFAOYSA-N C=COS(=O)(=O)OS(=O)(=O)O Chemical compound C=COS(=O)(=O)OS(=O)(=O)O BAPGOVYLNIGTOU-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims description 3
- 239000010450 olivine Substances 0.000 claims description 3
- 229910052609 olivine Inorganic materials 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- OWNSEPXOQWKTKG-UHFFFAOYSA-M lithium;methanesulfonate Chemical compound [Li+].CS([O-])(=O)=O OWNSEPXOQWKTKG-UHFFFAOYSA-M 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- WXVUCMFEGJUVTN-UHFFFAOYSA-N phenyl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1 WXVUCMFEGJUVTN-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- MVGWWCXDTHXKTR-UHFFFAOYSA-J tetralithium;phosphonato phosphate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]P([O-])(=O)OP([O-])([O-])=O MVGWWCXDTHXKTR-UHFFFAOYSA-J 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 2
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 2
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims 1
- WJCPMQQLTJQIJK-UHFFFAOYSA-N 1,6-diisocyanohexane Chemical compound [C-]#[N+]CCCCCC[N+]#[C-] WJCPMQQLTJQIJK-UHFFFAOYSA-N 0.000 claims 1
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 claims 1
- ACNASVKDYHUAHH-UHFFFAOYSA-N ethene silane Chemical compound [SiH4].C=C.C=C.C=C.C=C ACNASVKDYHUAHH-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 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 description 4
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 239000006256 anode slurry Substances 0.000 description 2
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
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- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
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- OSSBKXMASZTOSG-UHFFFAOYSA-N 2-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCCO1 OSSBKXMASZTOSG-UHFFFAOYSA-N 0.000 description 1
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
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- 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
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
本发明公开了一种锂离子电池用低温电解液和锂离子电池,该电解液包括锂盐、有机溶剂和添加剂,所述添加剂包括结构式Ⅰ和/或结构式Ⅱ所示的化合物A:其中,R1、R2、R3、R4各自独立地选自卤素或C1‑C6烷基。本发明在电解液中引入了特殊结构的添加剂,从而能够使得该电解液能兼顾锂离子电池的高温性能和低温性能,且可适应更低的温度。
Description
技术领域
本发明属于锂离子电池技术领域,尤其涉及一种锂离子电池用低温电解液及锂离子电池。
背景技术
锂离子电池具有电压高、比能量大、充放电寿命长、安全环保等特点,成为便携式电源和动力电池的首选。随着科技的不断进步,例如航空器、船舶、车辆、移动通信设备等各类移动设备不仅常在高温环境下运作,还会常在严寒的环境下运作,这就需要高低温性能优异的锂离子电池,所以开发能兼顾高低温性能的锂离子电池是国内外一个比较热点的课题。目前,锂离子电池在低温下的容量保持率是非常低的,容量衰减有很大一部分的原因是由于锂离子在电解液中移动缓慢造成的。低温下,电解液电导率的骤降、电极界面膜阻抗的增大、电荷传递电阻的增大都会造成锂离子电池放电容量下降,这些因素都受电解液成分的影响,因此,电解液对锂离子电池低温性能起着重要的作用。
通常来说,常温下性能良好的电池只能兼顾低温性能好或者高温性能良好,很难做到高低温性能兼顾,其中最主要的原因就是锂离子电池电解液的液态温度窗口窄,不能兼顾高低温下的热稳定性和电化学稳定性。为了解决锂离子电池在高低温条件下的应用问题,进一步拓展锂离子电池应用的温度范围,目前已采用多种方法进行改善,例如中国专利202010900795.7公开了采用具有环状焦碳酸酯结构和噻吩官能团的化合物作为电解液添加剂,以实现锂离子电池不仅具有高温性能,而且在-10℃下还具有良好的低温性能,然而,该化合物的环外含有酸酐结构,其容易形成过厚的界面聚合层,有碍进一步提高锂离子电池的低温性能,换言之,该化合物作为电解液添加剂时并不能实现锂离子电池在更低温条件(如-20℃)下还具有良好的低温性能。
因此,为了改善锂离子电池在更低的温度下仍具有较好的性能,亟需开发一种锂离子电池用低温电解液及锂离子电池。
发明内容
本发明的目的是提供一种锂离子电池用低温电解液,在电解液中引入了特殊结构的添加剂,从而能够使得该电解液能兼顾锂离子电池的高温性能和低温性能,且可适应更低的温度。
为了实现以上目的,本发明提供了一种锂离子电池用低温电解液,包括锂盐、有机溶剂和添加剂,添加剂包括结构式Ⅰ和/或结构式Ⅱ所示的化合物A:
其中,R1、R2、R3、R4各自独立地选自卤素或C1-C6烷基。
可以理解的是,R1选自卤素或C1-C6烷基,R2选自卤素或C1-C6烷基,R3选自卤素或C1-C6烷基,R4选自卤素或C1-C6烷基。R1、R2、R3、R4可以相同,也可以不同。作为示例地,R1、R2、R3、R4均为CH3-;还比如,R1、R4均为F,R2、R3均为CH3-,但不以此为限。
在一优选的实施例中,C1~C6烷基表示碳原子数为1~6的烷基,烷基可为链状烷基,也可以为环烷基,位于环烷基的环上的氢可被烷基取代,作为示例地,烷基可为但不限于甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基和环己基等。
在一优选的实施例中,卤素包括但不限于氟(F)、氯(Cl)、溴(Br)、碘(I)。
在一优选的实施例中,本发明的化合物A选自化合物Ⅰ~化合物Ⅴ中的至少一种:
在一优选的实施例中,本发明添加剂的质量占电解液总质量的0.1%~6.0%,进一步地,添加剂的质量占电解液总质量的0.1~4%。作为示例地,本发明的添加剂的质量占电解液总质量的0.1%、0.2%、0.5%、0.8%、1%、1.5%、2%、2.2%、2.5%、3%、3.2%、3.5%、3.8%、4%、4.2%、4.5%、4.8%、5%、5.2%、5.5%、5.8%、6%,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
在一优选的实施例中,本发明的锂盐包括六氟磷酸锂(LiPF6)、高氯酸锂(LiClO4)、四氟硼酸锂(LiBF4)、双氟磺酰亚胺锂(LiFSI)、双三氟甲基磺酰亚胺锂(LiTFSI)、甲基磺酸锂(LiCH3SO3)、三氟甲基磺酸锂(LiCF3SO3)、氟磺酸锂(LiSO2F)、二草酸硼酸锂(C4BLiO8)、二氟草酸硼酸锂(C2BF2LiO4)、二氟磷酸锂(LiPO2F2)、二氟双草酸磷酸锂(LiDFBP)、二磷酸锂(LiPO2F2)、双三氟甲基磺酰亚胺锂(LiTFSI)和低级脂肪族羧酸锂中的至少一种。进一步地,低级脂肪族羧酸锂包括但不限于氯硼烷锂、四苯基硼酸锂、锂酰亚胺盐等。
在一优选的实施例中,按质量百分数计,所述锂盐的质量占所述电解液总质量的5~30%。进一步地,锂盐的质量占所述电解液总质量的6~20%,优选地,锂盐的质量占所述电解液总质量的8~18%。作为示例地,锂盐的质量占所述电解液总质量的8%、9%、10%、11%、12%、13%、14%、15%、16%、17%、18%,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
在一优选的实施例中,所述有机溶剂为碳酸酯、羧酸酯和醚类化合物中的至少一种。
进一步地,碳酸酯包括但不限于环状碳酸酯、链状碳酸酯,其中,环状碳酸酯可为但不限于碳酸乙烯酯(EC)、碳酸亚丙酯、碳酸亚丁酯(BC)、碳酸亚戊酯、碳酸亚乙烯基酯(VC)或它们的衍生物;链状碳酸酯包括但不限于碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)。
进一步地,羧酸酯包括但不限于环状羧酸酯、链状羧酸酯,环状羧酸酯具体可以包括但不限于γ-丁内酯、γ-戊内酯、δ-戊内酯中的至少一种;链状羧酸酯包括但不限于乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(EP)、乙酸丁酯、丙酸丙酯(PP)、丙酸丁酯。
进一步地,醚类化合物包括环状醚或链状醚,环状醚具体可以包括但不限于1,3-二氧戊烷(DOL)、1,4-二氧惡烷(DX)、冠醚、四氢呋喃(THF)、2-甲基四氢呋喃(2-CH3-THF)、2-三氟甲基四氢呋喃(2-CF3-THF)中的至少一种;链状醚具体可以包含但不限于二甲氧基甲烷、二乙氧基甲烷、乙氧基甲氧基甲烷、乙二醇二正丙基醚、乙二醇二正丁基醚、二乙二醇二甲基醚。
在一优选的实施例中,本发明的电解液还包括助剂,助剂选自碳酸亚乙烯酯、亚乙烯基碳酸乙烯酯、氟代碳酸乙烯酯、亚硫酸乙烯酯、1,3丙磺酸内酯、1,3-丙烯磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、丁二酸酐、马来酸酐、2-甲基马来酸酐、甲基碳酸-2-丙炔基酯、四乙烯硅烷、三烯丙基异氰脲酸酯、六亚甲基二异腈酸酯、邻菲罗啉、对苯二异氰酸酯、2,4-甲苯二异氰酸酯、N-苯基双(三氟甲烷磺酰)亚胺、双硫酸乙烯酯、甲磺酸苯酯、双硫酸乙烯酯、双螺硫酸丙烯酯、对苯二酚二氟磺酸酯、三烯丙基磷酸酯、三炔丙基磷酸酯、2,4-丁烷磺内酯、甲基丙烯酸异氰基乙酯、甲烷二磺酸亚甲酯、三(三甲硅烷)硼酸酯、三(三甲硅烷)磷酸酯、三(乙烯基二甲硅烷)磷酸酯中的至少一种。作为示例地,助剂为氟代碳酸乙烯酯(FEC)或1,3丙磺酸内酯,还比如助剂为碳酸亚乙烯酯和氟代碳酸乙烯酯的混合物。
在一优选的实施例中,本发明助剂的质量占电解液总质量的0.1%-5%,进一步地,助剂的质量占电解液总质量的0.2%-2%。作为示例地,助剂的质量占所述电解液总质量的0.1%、0.2%、0.5%、0.8%、1%、1.5%、2%、2.2%、2.5%、3%、3.2%、3.5%、3.8%、4%、4.2%、4.5%、4.8%、5%,但并不仅限于所列举的数值,该数值范围内其他未列举的数值同样适用。
相应地,本发明还提供一种锂离子电池,该锂离子电池采用了上述的电解液,锂离子电池不仅具有良好的高温存储及高温循环性能,还能进一步改善锂离子电池的低温性能,使得该锂离子电池在-20℃下还具有良好的低温性能。
在一优选的实施例中,锂离子电池包括正极、负极和隔膜,正极活性材料可包括以下材料中的至少一种:橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物。但本申请并不限定于这些材料,还可以使用其他可被用作电池正极活性材料的传统材料。这些正极活性材料可以仅单独使用一种,也可以将两种以上组合使用。其中,锂过渡金属氧化物的示例可包括但不限于锂钴氧化物(如LiCoO2)、锂镍氧化物(如LiNiO2)、锂锰氧化物(如LiMnO2、LiMn2O4)、锂镍钴氧化物、锂锰钴氧化物、锂镍锰氧化物、锂镍钴锰氧化物(结构如LiNixCoyMn(1-x-y)MzO2,其中0.6≤x<0.9,x+y<1,0≤z<0.08,M为Al、Mg、Zr和Ti中的至少一种)。橄榄石结构的含锂磷酸盐的示例可包括但不限于磷酸铁锂(如LiFePO4(也可以简称为LFP))、磷酸铁锂与碳的复合材料、磷酸锰锂(如LiMnPO4)、磷酸锰锂与碳的复合材料、磷酸锰铁锂、磷酸锰铁锂与碳的复合材料中的至少一种。
在一优选的实施例中,正极由镍钴锰氧化物材料制成,镍钴锰氧化物材料为LiNixCoyMn(1-x-y)MzO2,其中0.6≤x<0.9,x+y<1,0≤z<0.08,M为Al、Mg、Zr和Ti中的至少一种。作为示例地,x=0.8,y=0.1,M为Zr,z=0.03。
在一优选的实施例中,负极活性材料包括碳基负极、硅基负极、锡基负极、锂负极中的至少一种。其中碳基负极可包括石墨、硬碳、软碳、石墨烯、中间相碳微球等;硅基负极可包括硅材料、硅的氧化物、硅碳复合材料以及硅合金材料等;锡基负极可包括锡、锡碳、锡氧、锡金属化合物;锂负极可包括金属锂或锂合金。锂合金具体可以是锂硅合金、锂钠合金、锂钾合金、锂铝合金、锂锡合金和锂铟合金中的至少一种。
与现有技术相比,本发明的锂离子电池用低温电解液,包括锂盐、有机溶剂和添加剂,添加剂特殊结构的化合物A,可能是其含有对称的O=S=O结构,耐氧化性较强,能在电极界面处被吸附,形成耐氧化吸附层,该吸附层具有良好的热稳定性和物理包覆特性,能显著抑制电解液/电极界面副反应,改善电极/电解液在高温下的界面稳定性,电池的高温存储性能得到了改善。同时,S-O键容易与Li形成含硫锂化物界面,该界面具有较好的韧性,能提高SEI在锂离子脱嵌过程中的结构稳定性,进而提高电池的循环特性。且该锂化物界面具有较好的低温稳定性,能够保持锂离子在低温下的传输通道不闭孔、不缩合,电池的低温性能得到了显著提高。综上,本发明采用结构式Ⅰ和/或结构式Ⅱ所示的化合物A能改善电极电解液界面稳定性、SEI低温传输锂离子特性,电池的高温存储、循环和低温特性得到了提高。
具体实施方式
为了进一步说明本发明的目的、技术方案及有益效果,下面将结合具体实施例对本发明作进一步说明。需要说明的是,实施例和对比例中未注明具体条件者,可按照常规条件或制造商建议的条件进行,所用试剂或仪器未注明生产厂商者,均为可通过市售而获得的常规产品。
实施例1
电解液的制备:
在充满氮气的手套箱(O2<1ppm,H2O<1ppm)中,将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸甲乙酯(EMC)按照质量比2:2:6混合均匀后所得到的混合溶剂作为有机溶剂,再加入添加剂和助剂,得到混合溶液。将混合溶液密封打包放置急冻间(-4℃)冷冻2h之后取出,在充满氮气的手套箱(O2<1ppm,H2O<1ppm)中,向混合溶液中缓慢加入六氟磷酸锂,混合均匀后即制成锂离子电池电解液。
正极片的制备:
将三元材料LiNi0.8Co0.1Mn0.1Zr0.03O2、导电剂SuperP、粘接剂PVDF和碳纳米管(CNT)按质量比96.5:1.5:1:1混合均匀制成一定粘度的锂离子电池正极浆料,涂布在集流体用铝箔上,其涂布量为324g/m2,在85℃下烘干后进行冷压;然后进行切边、裁片、分条,分条后在真空条件下85℃烘干4h,焊接极耳,制成满足要求的锂离子电池正极片。
负极片的制备:
将人造石墨、硅按质量比90:10混合后,与导电剂SuperP、增稠剂CMC、粘接剂SBR(丁苯橡胶乳液)按质量比95:1.5:1.0:2.5的比例制成浆料,混合均匀,用混制的浆料涂布在铜箔的两面后,烘干、辊压后得到负极片,制成满足要求的锂离子电池负极片
锂离子电池的制备:
将根据上述工艺制备的正极片、负极片和隔膜经叠片工艺制作成厚度为4.7mm,宽度为55mm,长度为60mm的锂离子电池,在75℃下真空烘烤10h,注入上述电解液。静置24h后,用0.lC(180mA)的恒流充电至4.45V,然后以4.45V恒压充电至电流下降到0.05C(90mA);然后以0.2C(180mA)放电至3.0V,重复2次充放电,最后再以0.2C(180mA)将电池充电至3.8V,完成锂离子电池的制作。
实施例1~13的锂离子电池电解液的组成成分如表1所示,其中,实施例2~13的锂离子电池电解液、正极片、负极片、锂离子电池的制备工艺均与实施例1相同。
表1实施例的锂离子电池电解液的组成成分
将实施例1~13制得的锂离子电池参照下述条件进行高温储存、高温循环性能、常温循环性能、低温性能测试,其结果如表2所示。
高温存储性能测试:
在常温(25℃)条件下,对锂离子电池进行一次0.5C/0.5C充电和放电(电池放电容量记录为C0),上限电压为4.4V,然后在0.5C恒流恒压条件下将电池充电至4.4V,测量电池厚度(厚度记为D0);将电池放置于60℃烘箱中搁置30d,取出并测量电池厚度(厚度记为D1);将电池放置于25℃环境中,进行0.5C放电(放电容量记录为C1);继续在常温(25℃)条件下对锂离子电池进行一次0.5C/0.5C充电和放电(电池放电容量记录为C2),上限电压为4.4V,计算容量保持率、容量恢复率和厚度膨胀率。
容量保持率=(C1/C0)*100%
容量恢复率=(C2/C0)*100%
厚度膨胀率=(D1/D0)*100%
常温循环性能测试:
在常温(25℃)条件下,对锂离子电池进行一次1.0C/1.0C充电和放电(电池放电容量为C0),上限电压为4.4V,然后在常温条件下进行1.0C/1.0C充电和放电500周(电池放电容量为C1),计算容量保持率。
容量保持率=(C1/C0)*100%
高温循环测试:
在过高温(45℃)条件下,对锂离子电池进行一次1.0C/1.0C充电和放电(电池放电容量为C0),上限电压为4.4V,然后在常温条件下进行1.0C/1.0C充电和放电400周(电池放电容量为C1),计算容量保持率。
容量保持率=(C1/C0)*100%
低温性能测试:
在常温(25℃)条件下,对锂离子电池进行一次0.5C/0.5充放电(电池截止电压为3.0V,放电容量为C0),上限电压为4.4V(截止电流0.05C)。然后将电池在常温(25℃)以0.5C充满电至4.4V(截止电流0.05C)后,将电池转移至-20℃条件下搁置4小时,0.5C放电至3.0V,放电容量为C1,计算容量保持率。
容量保持率=(C1/C0)*100%
表2锂离子电池性能测试结果
由表2可知,实施例1~13由于使用了本发明的含有特殊结构的化合物A作为添加剂,锂离子电池不仅具有较好的高温性能,而且兼具较好的低温性能,可能是由于化合物A含有对称的O=S=O结构,耐氧化性较强,能在电极界面处被吸附,形成耐氧化吸附层,该吸附层具有良好的热稳定性和物理包覆特性,能显著抑制电解液/电极界面副反应,改善电极/电解液在高温下的界面稳定性,电池的高温存储性能得到了改善。同时,S-O键容易与Li形成含硫锂化物界面,该界面具有较好的韧性,能提高SEI在锂离子脱嵌过程中的结构稳定性,进而提高电池的循环特性。且该锂化物界面具有较好的低温稳定性,能够保持锂离子在低温下的传输通道不闭孔、不缩合,电池的低温性能得到了显著提高。
最后应当说明的是,以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,但是也并不仅限于实施例中所列,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
Claims (10)
1.一种锂离子电池用低温电解液,包括锂盐、有机溶剂和添加剂,其特征在于,所述添加剂包括结构式Ⅰ和/或结构式Ⅱ所示的化合物A:
其中,R1、R2、R3、R4各自独立地选自卤素或C1-C6烷基。
2.如权利要求1所述的锂离子电池用低温电解液,其特征在于,所述烷基选自甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基和环己基中的至少一种。
3.如权利要求1所述的锂离子电池用低温电解液,其特征在于,所述化合物A选自化合物Ⅰ~化合物Ⅴ中的至少一种:
4.如权利要求1所述的锂离子电池用低温电解液,其特征在于,所述添加剂的质量占电解液总质量的0.1%~6.0%。
5.如权利要求1所述的锂离子电池用低温电解液,其特征在于,所述锂盐选自六氟磷酸锂、高氯酸锂、四氟硼酸锂、双氟磺酰亚胺锂、双三氟甲基磺酰亚胺锂、甲基磺酸锂、三氟甲基磺酸锂、氟磺酸锂、二草酸硼酸锂、二氟草酸硼酸锂、二氟磷酸锂、二氟双草酸磷酸锂、二磷酸锂、双三氟甲基磺酰亚胺锂和低级脂肪族羧酸锂中的至少一种。
6.如权利要求1所述的锂离子电池用低温电解液,其特征在于,所述有机溶剂为碳酸酯、羧酸酯和醚类化合物中的至少一种。
7.如权利要求1所述的锂离子电池用低温电解液,其特征在于,还包括助剂,所述助剂选自碳酸亚乙烯酯、亚乙烯基碳酸乙烯酯、氟代碳酸乙烯酯、亚硫酸乙烯酯、1,3丙磺酸内酯、1,3-丙烯磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、丁二酸酐、马来酸酐、2-甲基马来酸酐、甲基碳酸-2-丙炔基酯、四乙烯硅烷、三烯丙基异氰脲酸酯、六亚甲基二异腈酸酯、邻菲罗啉、对苯二异氰酸酯、2,4-甲苯二异氰酸酯、N-苯基双(三氟甲烷磺酰)亚胺、双硫酸乙烯酯、甲磺酸苯酯、双硫酸乙烯酯、双螺硫酸丙烯酯、对苯二酚二氟磺酸酯、三烯丙基磷酸酯、三炔丙基磷酸酯、2,4-丁烷磺内酯、甲基丙烯酸异氰基乙酯、甲烷二磺酸亚甲酯、三(三甲硅烷)硼酸酯、三(三甲硅烷)磷酸酯、三(乙烯基二甲硅烷)磷酸酯中的至少一种。
8.一种锂离子电池,包括正极、负极和隔膜,其特征在于,还包括如权利要求1~7任意一项所述的锂离子电池用低温电解液。
9.如权利要求8所述的锂离子电池,其特征在于,所述正极的活性材料选自橄榄石结构的含锂磷酸盐、锂过渡金属氧化物及其各自的改性化合物中的至少一种。
10.如权利要求8所述的锂离子电池,其特征在于,所述负极的活性材料选自碳基负极、硅基负极、锡基负极、锂负极中的至少一种。
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