CN113839088A - 一种用于锂离子电池的电解液和锂离子电池 - Google Patents
一种用于锂离子电池的电解液和锂离子电池 Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 35
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical group C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 4
- DMWJVLJVMIFAJE-UHFFFAOYSA-N furo[3,4-d]pyridazine-5,7-dione Chemical compound N1=NC=C2C(=O)OC(=O)C2=C1 DMWJVLJVMIFAJE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- KFKMGUPDWTWQFM-UHFFFAOYSA-N furo[3,4-c]pyridine-1,3-dione Chemical compound N1=CC=C2C(=O)OC(=O)C2=C1 KFKMGUPDWTWQFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- -1 heterocyclic carboxylic anhydride Chemical class 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 15
- 239000011255 nonaqueous electrolyte Substances 0.000 description 15
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000008186 active pharmaceutical agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000011883 electrode binding agent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000002955 isolation Methods 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
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
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- 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
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Abstract
本公开涉及一种用于锂离子电池的电解液,该电解液含有有机溶剂、锂盐和添加剂。本公开提供的电解液中含有六元杂环基羧酸酐类添加剂,可以有效抑制电池产气及界面阻抗增加,提升电池高温稳定性能,提升电池的寿命。
Description
技术领域
本公开涉及锂电池领域,具体地,涉及一种用于锂离子电池的电解液和锂离子电池。
背景技术
锂离子电池能量密度大,一直是电池市场不可或缺的电池体系,但由于电池体系在引用过程中总会由界面与电解液之间发生寄生反应而导致产气,界面阻抗增加,从而引起电池发生膨胀,电池寿命降低等问题。尤其近年来对电池能量密度的追求,匹配高电压的正极材料的不断推出,匹配高电压材料的电解液的研究也成为重中之重,现有电解液体系应用极限电压为4.2V,超过4.2V电解液会在正极氧化,造成产气,电解液消耗过快,造成电池安全隐患以及缩短电池使用寿命,因此适合高电压体系的电解液的研究是现在的当务之急。现有技术的方案是使用含氟的电解液溶剂提升电解液的氧化分解电位,含氟溶剂的氧化分解电位虽高,但会造成电解液后期释放出HF,破坏正负极材料颗粒,影响电池寿命。
发明内容
为了进一步提升电解液的氧化分解电位,解决目前高电压下电解液分解的问题,提升锂电池的高电压及高温稳定性,本公开提供了一种用于锂离子电池的电解液和锂离子电池。
为了实现上述目的,本公开第一方面提供一种锂离子电池电解液,所述锂离子电池电解液含有有机溶剂、锂盐和添加剂;所述添加剂含有式(1)所示的第一添加剂;
在式(1)中,X1、X2、X3和X4各自独立地为选自CR或N,且X1、X2、X3和X4中至少一者为N;X1、X2、X3和X4中的R各自独立地选自H、卤素、C1-C4烷基、C1-C4的取代烷基、C4-C7的环烷基、C1-C3的烷氧基。
本公开的发明人出乎意料地发现,式(1)所示的添加剂可在高镍正极界面优先发生氧化反应成膜,所成正极膜层具有良好的导离子性能以及良好的隔绝具有催化氧化反应的正极与电解液在循环和存储过程中的界面劣化反应,因而阻止或降低了界面膜层的不断增加导致的极化增大,以及界面反应带来的气胀问题,由此得到了本发明。
本公开第二方面提供一种锂电池,所述锂电池含有本公开第一方面提供的锂电池电解液。
通过上述技术方案,本公开提供了一种用于锂离子电池的电解液及锂电池,含有本公开提供的电解液的锂离子电池在高电压下具有较好的高温稳定性能和电池循环性能。
本公开的其他特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
以下对本公开的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本公开,并不用于限制本公开。
本公开第一方面提供一种用于锂离子电池的电解液,锂电池电解液含有有机溶剂、锂盐和添加剂;所述添加剂含有式(1)所示的第一添加剂。
其中,X1、X2、X3和X4各自独立地选自CR或N,且X1、X2、X3和X4中至少一者为N;X1、X2、X3和X4中的R各自独立地选自H、卤素、C1-C4烷基、C1-C4的取代烷基、C4-C7的环烷基、C1-C3的烷氧基。
本公开的锂电池电解液中含有六元杂环基羧酸酐类添加剂,可在正极表面成膜,也就是可形成具有优异的导锂离子性能的正极界面膜,可阻挡电解液在高电压条件下在正极表面的劣化反应,抑制电池在循环过程中不断产气,降低电池膨胀,抑制电解液分解,提高电池寿命。
六元杂环优选含有一个N原子或者两个N原子的六元环基团,更优选含有一个N原子的六元环基团,因为此类分子的反应电位更低,更有利于在正极表面发生氧化反应成膜,且成膜组份具有较好的导离子性能。
根据本公开,锂电池电解液中有机溶剂的含量、锂盐的含量和添加剂的含量可以在较大的范围内变化,优选地,有机溶剂的含量可以为50-90重量%、锂盐的含量可以为1-20重量%,添加剂的含量可以为0.1-10重量%;更优选地,有机溶剂的含量可以为60-85重量%、锂盐的含量可以为5-15重量%,添加剂的含量可以为0.5-8重量%。在上述优选的情况下,电池正负极界面可以形成优良的膜层,抑制电解液在正负极界面的活性位点上的副反应,抑制电池产气及界面阻抗增加,提升电池高温性能,从而提升电池寿命。
根据本公开,所述添加剂中,以所述添加剂的总重量为基准,式(1)所示的第一添加剂的含量可以为0.5-4重量%;优选为0.6-3重量%。
根据本公开,式(1)中,优选X1、X2、X3和X4中的R1为H。在该优选情况下,能够具有较小的分子量,有更低的氧化分解电位,更容易在正极表面发生优先氧化反应。
更优选地,式(1)所示的第一添加剂为2,3吡啶二羧酸酐、3,4吡啶二羧酸酐、2,3吡嗪二羧酸酐和4,5哒嗪二羧酸酐。在该优选情况下,能够有较低的氧化分解成膜电位,可优先在正极表面成膜。
2,3吡啶二羧酸酐
3,4吡啶二羧酸酐
2,3吡嗪二羧酸酐
4,5哒嗪二羧酸酐
根据本公开,所述锂盐为本领域技术人员所熟知的,例如可以为LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiC(CF3SO2)3和LiB(C2O4)2中的一种或多种。
根据本公开,所述有机溶剂为本领域技术人员所熟知的,例如可以为碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、亚硫酸乙烯酯、亚硫酸丙烯酯、亚硫酸二乙酯、γ-丁内酯、二甲基亚砜、乙酸乙酯和乙酸甲酯中的一种或多种。
根据本公开,以所述添加剂的总重量为基准,所述添加剂还含有余量的第二添加剂,所述第二添加剂包括碳酸亚乙烯酯、双草酸硼酸锂和双氟磺酰亚胺锂中的一种或几种。
本发明第二方面提供一种锂电池,该锂电池包括壳体和容纳于壳体内的电芯和本公开第一方面提供的锂电池电解液。
根据本公开,电芯可以包括正极、负极和介于正极与负极之间的隔膜。
根据本公开,所述正极可以包括正极集流体及正极材料,正极材料可以包括正极活性物质、导电剂、正极粘结剂。正极活性物质、导电剂、正极粘结剂可以为本领域常规使用的正极活性物质、导电剂、正极粘结剂。正极活性物质可以为尖晶石或者层状结构的镍锰正极材料以及磷酸铁锂类正极材料,优选为尖晶石LiNi0.5Mn1.5O4。
根据本公开,负极包括负极集流体以及负极材料,负极材料包括负极活性物质、负极粘结剂。负极材料还可以选择性的包括导电剂,该导电剂为常规导电剂,可以与正极材料层中的导电剂相同或不同。负极活性物质、负极粘结剂可以为本领域常规使用的负极活性物质、负极粘结剂。负极活性物质为锂或者石墨负极或者硅碳负极材料,优选为金属锂。
以下通过实施例进一步详细说明本公开。实施例中所用到的原材料均可通过商购途径获得。
实施例1
(1)非水电解液的制备:
在氩气手套箱中将26重量份碳酸乙烯酯(EC)、61重量份碳酸二乙酯(DEC)、12重量份的六氟磷酸锂(LiPF6)、0.5重量份的2,3吡啶二羧酸酐混合均匀,得到本实施例的锂离子电池电解液,记为C1;
(2)锂离子电池的制备:
将正极活性物质(LiNi0.5Mn1.5O4)、乙炔黑、聚偏氟乙烯按配比90:5:5混合均匀后压制于铝箔上,得到正极片;将金属锂片作为负极片;以PE/PP复合隔膜为离子交换膜,采用本实施例的电解液C1,采用本领域常规方法做成扣式电池S1。
实施例2
采用与实施例1相同的步骤制备电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成1重量份的3,4吡啶二羧酸酐,制备得到锂离子电池非水电解液C2以及扣式电池S2。
实施例3
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成3重量份的2,3吡嗪二羧酸酐,得到锂离子电池非水电解液C3以及扣式电池S3。
实施例4
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成5重量份的4,5哒嗪二羧酸酐,得到锂离子电池非水电解液C4以及扣式电池S4。
实施例5
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成0.05重量份的2,3吡啶二羧酸酐,制备得到锂离子电池非水电解液C5以及扣式电池S5。
实施例6
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成0.1重量份的2,3吡啶二羧酸酐,制备得到锂离子电池非水电解液C6以及扣式电池S6。
实施例7
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成8重量份的2,3吡啶二羧酸酐,制备得到锂离子电池电解液C7以及扣式电池S7。
实施例8
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中将0.5重量份的2,3吡啶二羧酸酐替换成10重量份的2,3吡啶二羧酸酐,制备得到锂离子电池电解液C8以及扣式电池S8。
实施例9
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:步骤(1)中加入的12重量份的2,3吡啶二羧酸酐,制备得到锂离子电池电解液C9以及扣式电池S9。
对比例1
采用与实施例1相同的步骤制备电解液和扣式电池,不同之处仅在于:步骤(1)中不采用2,3吡啶二羧酸酐,制备得到锂离子电池非水电解液DC1以及扣式电池DS1。
对比例2
采用与实施例1相同的步骤制备非水电解液和扣式电池,不同之处在于:
步骤(1)中将2,3吡啶二羧酸酐替换为马来酸酐,制备得到锂离子电池电解液DC2以及扣式电池DS2。
对比例3
采用实施例1相同的步骤制备电解液和扣式电池,不同之处在于:步骤(1)中将2,3吡啶二羧酸酐替换为吡啶,制备得到锂离子电池电解液以及DC3扣式电池DS3。
对比例4
采用实施例1相同的步骤制备电解液和扣式电池,不同之处在于:步骤(1)中将2,3吡啶二羧酸酐替换为吡嗪,制备得到锂离子电池电解液以及DC4扣式电池DS4。
对比例5
采用实施例1相同的步骤制备电解液和扣式电池,不同之处在于:步骤(1)中将2,3吡啶二羧酸酐替换为哒嗪,制备得到锂离子电池电解液以及DC5扣式电池DS5。
测试例
(1)氧化分解电位测试
应用三电极测试方法,铂片作为工作电极,锂片做参比电极,以实施例制备的C1-C9和对比例制备的DC1-DC5为电解液组装电池,表征添加剂聚合电位以及电解液氧化分解电位。测试结果如表1所示。
(2)电池充放电性能测试
将各实验扣式电池S1-S9、DS1-DS5在常温下以0.1mA的电流恒流充电至4.95V,然后以0.1mA恒流放电至2.8V,记录电池的放电容量和充电容量,计算充放电效率(%)=充电容量/放电容量×100%。测试结果如表2所示。
(3)电池循环测试
将上述电池在常温下以1C倍率(约0.5mA)恒流恒压充至4.95V,充电截止电流为0.05mA,然后以0.5mA恒流放电至2.8V,即为1次循环。记录首次充电容量和放电容量,并计算放电效率(%);如此反复充放电循环100次后,记录第100次循环的放电容量,计算循环后容量保持率(%)=循环100次的放电容量/首次放电容量×100%;截止电压为4.95V。测试结果如表3所示。
表1
表2
电池编号 | 放电容量/mAh·g<sup>-1</sup> | 充电容量/mAh·g<sup>-1</sup> | 放电效率/% |
S1 | 133 | 148 | 89.8 |
S2 | 125 | 150 | 83.2 |
S3 | 123 | 147 | 83.6 |
S4 | 128 | 143 | 89.5 |
S5 | 125 | 166 | 75.3 |
S6 | 101 | 135 | 74.8 |
S7 | 105 | 167 | 62.8 |
S8 | 98 | 176 | 55.7 |
S9 | 120 | 175 | 70.9 |
DS1 | 105 | 148 | 68.5 |
DS2 | 103 | 182 | 56.5 |
DS3 | 98 | 175 | 56.0 |
DS4 | 104 | 178 | 58.4 |
DS5 | 92 | 189 | 48.7 |
表3
从表1-表3的数据可以看出,本公开通过在锂离子电解液中加入吡啶基二羧酸酐添加剂,有效抑制电解液分解,提升锂电池的高温稳定性,从而提高电池寿命。
以上详细描述了本公开的优选实施方式,但是,本公开并不限于上述实施方式中的具体细节,在本公开的技术构思范围内,可以对本公开的技术方案进行多种简单变型,这些简单变型均属于本公开的保护范围。
另外需要说明的是,在上述具体实施方式中所描述的各个具体技术特征,在不矛盾的情况下,可以通过任何合适的方式进行组合,为了避免不必要的重复,本公开对各种可能的组合方式不再另行说明。
此外,本公开的各种不同的实施方式之间也可以进行任意组合,只要其不违背本公开的思想,其同样应当视为本公开所公开的内容。
Claims (10)
2.根据权利要求1所述的电解液,其中,X1、X2、X3和X4中的R为H;优选地,X1、X2、X3和X4中的任意一者或二者为N。
3.根据权利要求1所述的电解液,其中,以所述电解液的总重量为基准,所述有机溶剂的含量为50-90重量%、所述锂盐的含量为1-20重量%,所述添加剂的含量为0.1-10重量%。
4.根据权利要求3所述的电解液,其中,优选地,以所述电解液的总重量为基准,所述有机溶剂的含量为60-85重量%、所述锂盐的含量为5-15重量%,所述添加剂的含量为0.5-8重量%。
5.根据权利要求1-4中任意一项所述的电解液,其中,所述添加剂中,以所述添加剂的总重量为基准,所述第一添加剂的含量为30-100重量%;优选为50-100重量%。
6.根据权利要求1所述的电解液,其中,所述第一添加剂为2,3吡啶二羧酸酐、3,4吡啶二羧酸酐、2,3吡嗪二羧酸酐和4,5哒嗪二羧酸酐。
7.根据权利要求1所述的电解液,其中,所述有机溶剂为选自碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、亚硫酸乙烯酯、亚硫酸丙烯酯、亚硫酸二乙酯、γ-丁内酯、二甲基亚砜、乙酸乙酯和乙酸甲酯中的一种或多种。
8.根据权利要求1所述的电解液,其中,所述锂盐为LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2、LiN(C2F5SO2)2、LiC(CF3SO2)3和LiB(C2O4)2中的一种或多种。
9.根据权利要求5所述的电解液,其中,所述添加剂中,以所述添加剂的总重量为基准,所述添加剂还含有余量的第二添加剂,所述第二添加剂包括碳酸亚乙烯酯、双草酸硼酸锂和双氟磺酰亚胺锂中的一种或几种。
10.一种锂离子电池,其特征在于,该锂电池含有权利要求1-9中任意一项所述的电解液。
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