CN114976243A - 一种电解液及其电化学装置和电子装置 - Google Patents
一种电解液及其电化学装置和电子装置 Download PDFInfo
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- CN114976243A CN114976243A CN202210594745.XA CN202210594745A CN114976243A CN 114976243 A CN114976243 A CN 114976243A CN 202210594745 A CN202210594745 A CN 202210594745A CN 114976243 A CN114976243 A CN 114976243A
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- Prior art keywords
- electrolyte
- electrochemical device
- dimethyl
- lithium
- active material
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 41
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 carboxylic ester compound Chemical class 0.000 claims abstract description 18
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 29
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 13
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 12
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 11
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 claims description 9
- FMQPBWHSNCRVQJ-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C(F)(F)F)C(F)(F)F FMQPBWHSNCRVQJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- 239000000654 additive Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
Classifications
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Abstract
本发明公开了一种电解液及其电化学装置和电子装置。一种电解液,包含碳酸二甲酯、碳酸亚乙烯酯和羧酸酯类化合物;基于所述电解液的质量,所述碳酸二甲酯的质量含量为A%,所述碳酸亚乙烯酯的质量含量为B%,所述羧酸酯类化合物的质量含量为C%,满足:A的取值范围为5至60,A/(B+C)的取值范围为4至20.88。本发明的电解液可以改善电化学装置的高温、室温循环性能,同时降低电化学装置的内阻。
Description
本申请要求申请号为202110592885.9专利申请的优先权(在先申请的申请日为2021年5月28日,发明名称为一种锂电池用非水电解液及其制备方法和锂离子电池,申请人为远景动力技术(江苏)有限公司)。
技术领域
本发明涉及电解液技术领域,尤其涉及一种电解液及其电化学装置和电子装置。
背景技术
由于锂离子电池具有高电压、高容量的重要优点,且循环寿命长、安全性能好,使其在便携式电子设备、电动汽车、空间技术、国防工业等多方面具有广阔的应用前景。
电解液为锂电池的“血液”,是锂电池四大关键原材料之一,是电池中离子传输的载体,在正负极之间起到传导锂离子的作用,对锂电池的能量密度、比容量、工作温度范围、循环寿命、安全性能等均有重要影响。
为了研发出合适的高性能电解液,往往会在电解液中添加合适的电解液添加剂,常用的电解液添加剂包括含硼添加剂、有机磷类添加剂、碳酸酯类添加剂、羧酸酯类添加剂、含硫添加剂离子液体添加剂等。
当前,随着锂离子电池对快速充电的需求越来越强烈,有必要在使用足量负极成膜添加剂的基础上引入碳酸二甲酯DMC,获得对极片更好地浸润性和锂离子传输性能。
发明内容
针对现有技术的不足,本发明的目的在于提供一种电解液及其电化学装置和电子装置,本发明的电解液可以改善电化学装置的高温、室温循环性能,同时降低电化学装置的内阻。
本发明的目的之一在于提供一种电解液,为达此目的,本发明采用以下技术方案:
一种电解液,包含碳酸二甲酯、碳酸亚乙烯酯和羧酸酯类化合物;
基于所述电解液的质量,所述碳酸二甲酯的质量含量为A%,所述碳酸亚乙烯酯的质量含量为B%,所述羧酸酯类化合物的质量含量为C%,满足:
A的取值范围为0至60,A/(B+C)的取值范围为4至20.88。
本发明的电解液,通过碳酸二甲酯、碳酸亚乙烯酯和羧酸酯类化合物配合使用,并通过调整三者的用量配比,可以改善电化学装置的高温、室温循环性能,同时降低电化学装置的内阻。
A的取值范围为5至60,例如为5、6、7、8、9、10、15、20、25、30、35、40、45、50、55、60等。
A/(B+C)的取值范围为4至20.88,例如为4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20等。
作为优选方案,A/(B+C)的取值范围为5至8。
作为优选方案,A的取值范围为8至42。
所述羧酸酯类化合物为式(I)所示的化合物:
R1、R3、R4各自独立地选自氢、取代或未取代的C1-12的烃基;R2选自C1-12的取代或未取代的烃基,经取代时,取代基为卤素原子。
其中,作为说明,C1-12的烃基,是指含有碳原子数为1至12的烃基。
所述式(I)所示的化合物为富马酸二甲酯甲基丙烯酸甲酯顺丁烯二酸二甲酯甲基丙烯酸1,1,1,3,3,3-六氟异丙酯甲基丙烯酸乙烯酯中的任意一种或两种以上的混合物。所述混合物典型但非限制的组合为两种、三种、四种或5种的混合物,例如为富马酸二甲酯、甲基丙烯酸甲酯的混合物,富马酸二甲酯、顺丁烯二酸二甲酯的混合物,富马酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物,富马酸二甲酯、甲基丙烯酸乙烯酯的混合物,富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯的混合物,富马酸二甲酯、甲基丙烯酸甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物,富马酸二甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙烯酯的混合物,甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物,甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸乙烯酯的混合物,顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯的混合物,富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯的混合物,富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸乙烯酯的混合物,甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯的混合物,富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯的混合物。
本发明的目的之二在于提供一种电化学装置,包括正极、负极、隔膜和目的之一所述的电解液。
本申请的电化学装置包括发生电化学反应的任何装置,它的具体实例包括所有种类的一次电池、二次电池、燃料电池、太阳能电池或电容。特别地,该电化学装置是锂二次电池,包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
在一些实施例中,本申请的电化学装置是具备具有能够吸留、放出金属离子的正极活性物质的正极以及具有能够吸留、放出金属离子的负极活性材料的负极的电化学装置。
所述正极包含正极活性材料,所述正极活性材料选自磷酸铁锂、锂镍过渡金属复合氧化物、具有尖晶石结构的锂镍锰复合氧化物的任意一种或两种以上的混合物。
所述负极包括负极活性材料和集流体,所述负极活性材料包括石墨。
所述负极还包括碳材料,所述碳材料选自乙炔黑、导电炭黑、碳纤维、碳纳米管和科琴黑中的任意一种或两种以上的混合物。
隔膜中的氯含量为小于或等于20ppm,具体可以为3ppm、4ppm、5ppm、6ppm等,优选的,所述隔膜中的氯含量为7ppm至20ppm,例如为7ppm、8ppm、9ppm、10ppm、11ppm、12ppm、13ppm、14ppm、15ppm、16ppm、17ppm、18ppm、19ppm、20ppm等。如果隔膜中的氯含量太低,会减少氯对电池的影响,但是局限于目前隔膜工艺,较难进一步降低氯含量;如果隔膜中的氯含量超过20ppm,则会淬灭SVC及添加剂的聚合反应,对电池性能有负面影响。
本发明的目的之三在于提供一种电子装置,所述电子装置包括目的之二所述的电化学装置。
所述电子装置包括但不限于如下类型,例如笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池或锂离子电容器等。
与现有技术相比,本发明的有益效果为:
本发明的电解液,通过碳酸二甲酯、碳酸亚乙烯酯和羧酸酯类化合物配合使用,并通过调整三者的用量配比,可以改善电化学装置的高温、室温循环性能,同时降低电化学装置的内阻。
具体实施方式
下面并通过具体实施方式来进一步说明本发明的技术方案。
如无具体说明,本发明的各种原料均可市售购得,或根据本领域的常规方法制备得到。
本发明的电解液,碳酸二甲酯、碳酸亚乙烯酯和羧酸酯类化合物;
基于所述电解液的质量,碳酸二甲酯的质量含量为A%,碳酸亚乙烯酯的质量含量为B%,羧酸酯类化合物的质量含量为C%,满足:
A的取值范围为5至60,A/(B+C)的取值范围为4至20.88。
本发明中,电化学装置为锂离子电池,锂离子电池为一次锂电池或二次锂电池,包括:正极、负极、位于正极和负极之间的隔膜以及电解液。
本发明的二次锂电池的制备方法如下:
(1)LFP(LiFePO4)正极的制备:
将正极活性材料(LiFePO4)、作为粘结剂的聚偏氟乙烯以及作为导电剂的Super P按照重量比97:2:1进行混合后,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌至体系呈均一透明状,获得正极浆料;将正极浆料均匀涂覆于铝箔上;将铝箔在室温晾干后转移至烘箱干燥,然后经过冷压、分切得到正极(极片);
(2)石墨负极的制备:
将人造石墨作为负极活性材料、Super P作为导电剂、羧甲基纤维素钠(CMC-Na)作为增稠剂、丁苯橡胶(SBR)作为粘结剂,按质量比96:1:1:2进行混合,加入去离子水,在真空搅拌机作用下获得负极浆料;将负极浆料均匀涂覆在负极集流体铜箔上;将铜箔在室温晾干后转移至烘箱干燥,然后经过冷压、分切得到负极(极片);
(3)电解液的制备:
在含水量<10ppm的氩气气氛手套箱中,将电池级碳酸乙烯酯(EC)与碳酸甲乙酯(EMC)按照配比进行混合,形成有机溶剂。按照后述表格所述电解液组成定量加入其他成分,混合均匀,得到电解液。表中各成分含量为基于电解液的总重量计算得到的重量百分数;下文所述作为电解液成分的“DMC”为碳酸二甲酯,“DTD”为硫酸乙烯酯,“VC”为碳酸亚乙烯酯。
(4)隔离膜的制备:
以聚丙烯膜作为隔离膜;
(5)二次电池的制备:
以厚度12μm的聚丙烯薄膜(PP)作为隔离膜,将上述制得的正极、隔离膜、负极依次进行叠片,使隔离膜处于正、负极中间起到隔离的作用。然后外包铝塑膜,转移至真空烘箱中120℃干燥,注入上述制得的电解液3.0g/Ah之后封口,进行电解液化成,最终制备得容量为1Ah的软包电池(即锂离子电池)。
本发明制得的锂离子电池,负极克容量为350mAh/g,注液系数为3g/Ah,电芯容量为1Ah,负极质量为3g,电解液质量为3g。
电解液在本发明涉及的铁锂电芯中的化成条件如下所述。
所述电解液在铁锂电芯的化成步骤具体为:将电解液进行注液后,保持0.1MPa的热压环境,以静置状态在45℃下以0.02C充电17min,静置5min后再以0.02C充到0.3Ah,之后割去气袋并真空封装,常温静置48h,从而使电解液完成化成。
其中,本发明的示例中,式(I)所示的化合物采用以下五种,化合物1为甲基丙烯酸甲酯,化合物2为富马酸二甲酯,化合物3为顺丁烯二酸二甲酯,化合物4为甲基丙烯酸1,1,1,3,3,3-六氟异丙酯,化合物5为甲基丙烯酸乙烯酯。
本发明的二次电池可以通过如下方法进行测试:
(1)二次电池循环测试
在指定温度(室温25℃或高温45℃)的烘箱内,以1C的电流在指定电位区间内进行循环充放电,记录每一圈的放电容量,当电池容量到达首圈容量80%时结束测试。
(2)二次电池直流电阻(DCR)测试
在指定温度下,将电池以1C电流放电至50%SOC(荷电状态,反映电池的剩余容量)时,将电流调高至4C,并保持30s,检测更新的稳定电压与原平台电压的差,其数值与3C电流值的比值即为电池的直流电阻。电池首次满充后进行的DCR测试结果为电池的初始DCR。
(3)二次电池高温存储容量保持率测试
将二次电池充满电后放置在60℃的恒温箱中,30天后取出,待冷却到室温后以0.33C倍率放电至截止电压,对照其容量相对于初始放电容量的百分比。
其中,充放电的截止电压具体如下:LFP-石墨是2.5V至3.65V。
(4)隔膜中从烧结成型体溶出的有机物溶出量通过如下方法测试:
将10g烧结成型体和40mL和光纯药工业株式会社制造的PCB试验用己烷加入到180mL容积的SUS制容器中并进行密闭。将该SUS制容器整体浸入70℃的水浴中,在以50分钟-1的速度进行振动的同时提取2小时,然后浸入20℃的水中进行骤冷。将上清液利用安装有0.2微米过滤器(PTFE制)的玻璃注射器进行过滤,从而制成试样。对于碳原子数12和14的标准物质,将和光纯药工业株式会社制造的特级正十二烷与正十四烷溶解于和光纯药工业株式会社制造的PCB试验用己烷中而用作标准物质,对于碳原子数16至碳原子数34的标准物质,将Sigma Aldrich公司制造的ASTM D5442C16-C44Qualitative RetentionTime Mix溶解于和光纯药工业株式会社制造的PCB试验用己烷中而用作标准物质。
对于上述试样,使用株式会社岛津制作所制造的气相色谱仪GC-2014AF进行测定。对于柱而言,使用信和化工株式会社的填充了Silicone OV-1(3%)/CW80-100mesh/AW-DMCS处理的、玻璃制3mmφ×1.5m的柱。条件设定为:温度为注射温度350℃、检测温度350℃,在初始温度100℃下保持2分钟后,以10℃/分钟进行升温,在330℃下保持20分钟。根据由试样得到的相同保持时间的检测峰的峰面积相对于上述标准试剂的检测峰的峰面积(C12~20为各6重量ppm、C22~C34为各8.3重量ppm)的相对比,计算出碳原子数为12以上且34以下的烃成分量,并分类为以下3级。
○:溶出量小于150ppm
△:溶出量大于等于150ppm且小于300ppm
×:溶出量大于等于300ppm
本发明的实施例1至8,对比例1的电解液组成如表1-1所示,采用上述制备方法制备锂离子电池,对其性能进行测试,测试结果如表1-2所示。
表1-1
表1-2
由表1-2的数据可以看出,当负极成膜添加剂的量固定时,随着碳酸二甲酯的添加,电池的高温循环、室温循环性能都有提升,尤其是室温循环,提升显著。同时,DMC的加入有效降低了初始DCR,并且一定程度上提高了高温容量保持率。基于此我们可以发现,在DMC的质量含量与负极成膜添加剂(VC+化合物1)的质量含量比例A/(B+C)在4.18-20.88时效果更佳。
为了进一步探索该比例含量与性能的影响,我们控制DMC添加量不变,更改负极成膜添加剂(VC+化合物1)的含量,发现该比例在4.05-8.35时效果更佳,兼顾了高温与常温循环性能,同时有效降低了DCR,提升了容量保持率。
实施例9至实施例12
实施例9至实施例12的电解液组成与实施例3的区别在于式(I)所示的化合物种类不同,实施例3采用化合物1,实施例9采用化合物2,实施例10采用化合物3,实施例11采用化合物4,实施例12采用化合物5,其他的与实施例3的均相同。
对比例3
本对比例与实施例3的区别之处在于,不加式(I)所示的化合物,减少的式(I)所示的化合物的量增加至VC中。
采用上述制备方法制备锂离子电池,对其性能进行测试,测试结果如表2所示。
表2
由表2数据可以看出,相对于对比例3不加式(I)所示的化合物,实施例3、实施例9至实施例12,式(I)所示的化合物采用不同种类,均能使电池的高温、室温循环性能、高温存储性能更好,电阻更低。
实施例13至实施例14与实施例2的区别之处在于,其所使用的隔膜从烧结成型体溶出的有机物溶出量不同,实施例2中的溶出量为75ppm,实施例14的为203ppm,实施例15的为800ppm,其他的与实施例2的均相同。
采用上述制备方法制备锂离子电池,对其性能进行测试,测试结果如表3所示。
表3
添加DMC后,电解液对隔膜的浸润能力大幅增强,因此隔膜本身的有机溶出物也会增多,影响电池性能。因此有必要选择低有机溶出量的隔膜。由表3数据可以看出,隔膜从烧结成型体溶出的有机物溶出量越少,综合电池性能越好。
本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程,但本发明并不局限于上述详细工艺设备和工艺流程,即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
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,本发明对各种可能的组合方式不再另行说明。
此外,本发明的各种不同的实施方式之间也可以进行任意组合,只要其不违背本发明的思想,其同样应当视为本发明所公开的内容。
Claims (10)
1.一种电解液,其特征在于,包含碳酸二甲酯、碳酸亚乙烯酯和羧酸酯类化合物;
基于所述电解液的质量,所述碳酸二甲酯的质量含量为A%,所述碳酸亚乙烯酯的质量含量为B%,所述羧酸酯类化合物的质量含量为C%,满足:
A/(B+C)的取值范围为4至20.88。
2.根据权利要求1所述的电解液,其特征在于,A/(B+C)的取值范围为5至8。
3.根据权利要求1所述的电解液,其特征在于,A的取值范围为8至42。
5.根据权利要求4所述的电解液,其特征在于,所述式(I)所示的化合物为富马酸二甲酯、甲基丙烯酸甲酯、顺丁烯二酸二甲酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸乙烯酯中的任意一种或两种以上的混合物。
6.一种电化学装置,其特征在于,包含正极、负极、隔膜和权利要求1至5的任一项所述的电解液。
7.根据权利要求6所述的电化学装置,其特征在于,所述正极包含正极活性材料;所述正极活性材料选自磷酸铁锂、锂镍过渡金属复合氧化物、具有尖晶石结构的锂镍锰复合氧化物的任意一种或两种以上的混合物。
8.根据权利要求6或7所述的电化学装置,其特征在于,所述负极包括负极活性材料和集流体,所述负极活性材料包括石墨。
9.根据权利要求6所述的电化学装置,其特征在于,所述隔膜中的从烧结成型体溶出的有机物溶出量为小于150ppm。
10.一种电子装置,其特征在于,包含权利要求6至9的任一项所述的电化学装置。
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Effective date of registration: 20240326 Address after: Kanagawa Prefecture, Japan Applicant after: AESC Japan Country or region after: Japan Address before: 214400 No.66, Shentai Road, Shengang street, Jiangyin City, Wuxi City, Jiangsu Province Applicant before: Vision power technology (Jiangsu) Co.,Ltd. Country or region before: China Applicant before: Vision Ruitai Power Technology (Shanghai) Co.,Ltd. |