WO2023045148A1 - Non-aqueous electrolyte and lithium-ion battery thereof - Google Patents

Non-aqueous electrolyte and lithium-ion battery thereof Download PDF

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WO2023045148A1
WO2023045148A1 PCT/CN2021/140301 CN2021140301W WO2023045148A1 WO 2023045148 A1 WO2023045148 A1 WO 2023045148A1 CN 2021140301 W CN2021140301 W CN 2021140301W WO 2023045148 A1 WO2023045148 A1 WO 2023045148A1
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lithium
electrolytic solution
ion battery
electrolyte
carbonate
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PCT/CN2021/140301
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French (fr)
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黄秋洁
白晶
王霹霹
欧霜辉
毛冲
戴晓兵
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珠海市赛纬电子材料股份有限公司
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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
    • 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
    • H01M10/42—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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the application relates to the field of energy storage devices, in particular to a non-aqueous electrolyte and a lithium ion battery thereof.
  • the current high-voltage ternary cathode materials face serious problems such as poor high-temperature storage and cycle gas production.
  • the conventional electrolyte will be oxidized and decomposed on the surface of the positive electrode of the battery at a high voltage of 4.5V. Especially under high temperature conditions, the oxidative decomposition of the electrolyte will be accelerated, and at the same time, the deterioration reaction of the positive electrode material will be promoted.
  • Japanese patent JP1998189042A discloses a vinyl sulfate (DTD) electrolyte.
  • DTD vinyl sulfate
  • the high-temperature storage characteristics of lithium-ion batteries can be improved, but the floating charge performance of vinyl sulfate at a high voltage of 4.5V is not ideal.
  • the purpose of this application is to provide a non-aqueous electrolyte and lithium-ion battery thereof.
  • This non-aqueous electrolyte can inhibit the oxidation and decomposition of the electrolyte, and can improve the high voltage (4.5V) ternary positive electrode material system.
  • the high-temperature storage performance of lithium-ion batteries can also improve the floating charge performance of lithium-ion batteries.
  • the first aspect of the present application provides a non-aqueous electrolyte, including lithium salt, non-aqueous organic solvent and additives, the additives include cyclic nitrogen-containing sulfuric acid ester, the cyclic nitrogen-containing sulfuric acid ester
  • the additives include cyclic nitrogen-containing sulfuric acid ester, the cyclic nitrogen-containing sulfuric acid ester
  • the chemical formula is shown in structural formula I or structural formula II,
  • the cyclic nitrogen-containing sulfuric acid ester additive of the present application reacts at the positive electrode/electrolyte interface when it is charged for the first time, forming an interface film containing S and O, which is relatively stable under high temperature conditions and can It can significantly improve the high-temperature storage performance of lithium-ion batteries.
  • this kind of interfacial film containing S and O is not stable under continuous high voltage (especially at 4.5V), and it is easy to decompose to generate SO 2 and other gases, which will cause the battery to generate gas and deteriorate the battery performance.
  • its trifluoroalkylbenzene ring structure can be polymerized to form a polymer interface film with LiF and adhere to the surface of the interface film containing S and O when it is charged and discharged for the first time. It is extremely stable under high voltage, can inhibit the decomposition of the interfacial film containing S and O under continuous high voltage, and greatly improve the float charge performance of lithium-ion batteries.
  • the -N- structure also participates in the formation of some N x O y -containing interfacial films, which increases the toughness of the former two interfacial films and makes the interfacial films difficult to break.
  • the positive electrode/electrolyte interface can be optimized through the combination of the three structures, and the surface activity of the electrode can be reduced to inhibit the oxidative decomposition of the electrolyte, thereby Improve the floating charge performance and high temperature storage performance of lithium-ion batteries at high voltage (especially at 4.5V).
  • the compound of structural formula I adopts 1,2,5-thiadiazoline-1,1-dioxide and 1-bromo-trifluoro-p-xylene to undergo a substitution reaction under the action of potassium carbonate, and then undergoes recrystallization or column Prepared by chromatographic purification.
  • Its reaction formula is as follows.
  • the synthetic route of the compound of structural formula II is similar to the synthetic route of structural formula I.
  • the mass percentage of the cyclic nitrogen-containing sulfuric acid ester in the non-aqueous electrolyte is 0.1-5%, more preferably 0.5-2%, specifically but not limited to 0.1%, 0.5% , 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
  • the mass percentage of the lithium salt in the non-aqueous electrolyte is 6.5-15.5%.
  • the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), bistrifluoromethanesulfonate Lithium imide (LiN(CF 3 SO 2 ) 2 ), lithium bisoxalate borate (C 4 BLiO 8 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorooxalate borate (C 2 BF 2 LiO 4 ) , at least one of lithium difluorodioxalate phosphate (LiDFBP) and lithium bisfluorosulfonimide (LiFSI).
  • LiPF 6 lithium hexafluorophosphate
  • LiClO 4 lithium per
  • the organic solvent is at least one of chain carbonate, cyclic carbonate and carboxylate. More preferably, described non-aqueous organic solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), At least one of butyl acetate (n-Ba), ⁇ -butyrolactone ( ⁇ -Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb) .
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • PC propylene carbonate
  • n-Ba butyl acetate
  • ⁇ -Bt ⁇ -butyrolactone
  • propyl propionate n-Pp
  • EP ethyl propionate
  • Eb
  • the second aspect of the present application provides a lithium-ion battery, including a positive electrode material, a negative electrode material and an electrolyte, the electrolyte is the aforementioned non-aqueous electrolyte, and the positive electrode material is nickel-cobalt-manganese oxide or nickel-cobalt-aluminum Oxide, and the highest charging voltage is 4.5V.
  • the lithium-ion battery of the present application includes a cyclic nitrogen-containing sulfuric acid ester additive with a special structure because of its non-aqueous electrolyte additives.
  • the combination of the three structures can optimize the positive electrode/electrolyte interface and reduce the surface activity of the electrode.
  • the oxidative decomposition of the electrolyte improves the float charge performance and high temperature storage performance of the lithium-ion battery at high voltage (especially at 4.5V).
  • the chemical formula of the nickel-cobalt-manganese oxide is LiNi x Co y Mnz M (1-xyz) O 2
  • the chemical formula of the nickel-cobalt aluminum oxide is LiNi x Co y Al z N ( 1-xyz) O 2
  • M is at least one of Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti
  • N is Mn, Mg, Cu, Zn, Sn, At least one of B, Ga, Cr, Sr, V and Ti, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, x+y+z ⁇ 1.
  • the negative electrode material is at least one selected from artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
  • the electrolyte is prepared in a vacuum glove box with a moisture content of ⁇ 1ppm.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 ternary material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , binder PVDF and conductive agent SuperP are uniformly mixed at a mass ratio of 95:1:4 to make lithium ions with a certain viscosity
  • lithium-ion battery the positive electrode, diaphragm and negative electrode are stacked into square batteries, packed in polymer, filled with the non-aqueous electrolyte of lithium-ion battery prepared above, and processed by chemical formation, volume separation, etc. After the process, a lithium-ion battery with a capacity of 1000mAh is produced.
  • Example 2-7 The electrolyte formulations of Examples 2-7 and Comparative Examples 1-4 are shown in Table 1, and the steps of preparing the electrolyte and preparing the battery are the same as those of Example 1.
  • the lithium-ion batteries produced in Examples 1-7 and Comparative Examples 1-4 were subjected to a float charge performance test and a high-temperature storage test respectively.
  • the specific test conditions are as follows, and the performance test results are shown in Table 2.
  • Lithium-ion battery was discharged at 0.5C to 3.0V at 25°C, then charged at 0.5C to 4.5V, charged at 4.5V to 0.05C at constant voltage, placed in an oven at 45°C, and kept at 4.5V for 50 days to monitor the lithium ion battery.
  • the thickness change value of the ion battery, and the thickness of the initial 50% SOC is used as a benchmark.
  • this kind of interfacial film containing S and O is not stable under continuous high voltage (especially at 4.5V), and it is easy to decompose to generate SO 2 and other gases, which will cause the battery to generate gas and deteriorate the battery performance.
  • its trifluoroalkylbenzene ring structure can be polymerized to form a polymer interface film with LiF and adhere to the surface of the interface film containing S and O when it is charged and discharged for the first time. It is extremely stable under high voltage, can inhibit the decomposition of the interfacial film containing S and O under continuous high voltage, and greatly improve the float charge performance of lithium-ion batteries.
  • the -N- structure also participates in the formation of some N x O y -containing interfacial films, thereby increasing the toughness of the former two interfacial films and making the interfacial films difficult to break, so the floating charge performance and high-temperature storage performance are both better.
  • Comparative Example 2 contains ethylene sulfate (DTD), it can improve the high-temperature storage performance to a certain extent, but the effect is not obvious under the high-voltage system of 4.5V, and it cannot solve the floating charge problem at the same time.
  • DTD ethylene sulfate
  • Comparative Example 3 only contains a single fluorobenzene, although it can improve the floating charge performance to a certain extent, it cannot solve the problem of floating charge and high temperature storage under high voltage system.
  • comparative example 4 contains vinyl sulfate (DTD) and fluorobenzene at the same time, because the oxidation-reduction potential of fluorobenzene and DTD is different, the reaction conditions and the degree of reaction on the electrode surface are all different, although it is added at the same time, it still does not reach much According to this application, as a cyclic nitrogen-containing sulfuric acid ester additive with a special structure, the technical effect achieved by the combination of its -SO 2 - structure and the trifluoroalkylbenzene ring structure, so the floating charge performance and high temperature storage performance are poor .
  • DTD vinyl sulfate

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Abstract

A non-aqueous electrolyte and a lithium-ion battery thereof. The non-aqueous electrolyte comprises a lithium salt, a non-aqueous organic solvent, and an additive. The additive comprises a cyclic nitrogen-containing sulfate, and the chemical formula of the cyclic nitrogen-containing sulfate is shown in structural formula I or structural formula II. In the cyclic nitrogen-containing sulfate additive having a special structure in the present application, the -SO2-structure thereof can form an interface film containing S and O, which can improve the high-temperature storage performance of a lithium-ion battery. A polymer interface film formed by a trifluoroalkyl benzene ring structure is extremely stable at continuously high voltages, which can inhibit the decomposition of the interface film containing S and O at continuously high voltages, thereby greatly improving the floating charge performance of the lithium-ion battery. By means of the combination of the -SO2-structure, the trifluoroalkyl benzene ring structure, and the-N-structure, the positive electrode/electrolyte interface can be optimized, and the surface activity of an electrode is reduced to thus inhibit the oxidative decomposition of the electrolyte, thereby improving the floating charge performance and the high-temperature storage performance of the lithium-ion battery at a high voltage (especially at 4.5 V).

Description

非水电解液及其锂离子电池Non-aqueous electrolyte and its lithium-ion battery 技术领域technical field
本申请涉及储能器械领域，具体涉及一种非水电解液及其锂离子电池。The application relates to the field of energy storage devices, in particular to a non-aqueous electrolyte and a lithium ion battery thereof.
背景技术Background technique
目前的高电压三元正极材料面临高温存储差、循环产气等严重的问题。一方面可能是新开发的正极材料包覆或掺杂技术不太完善，另一方面即是电解液的匹配问题，常规的电解液在4.5V高电压下是会在电池正极表面氧化分解的，特别在高温条件下，会加速电解液的氧化分解，同时促使正极材料的恶化反应。The current high-voltage ternary cathode materials face serious problems such as poor high-temperature storage and cycle gas production. On the one hand, it may be that the newly developed positive electrode material coating or doping technology is not perfect. On the other hand, it is the matching problem of the electrolyte. The conventional electrolyte will be oxidized and decomposed on the surface of the positive electrode of the battery at a high voltage of 4.5V. Especially under high temperature conditions, the oxidative decomposition of the electrolyte will be accelerated, and at the same time, the deterioration reaction of the positive electrode material will be promoted.
日本专利JP1998189042A公开了一种硫酸乙烯酯(DTD)的电解液，通过引入硫酸乙烯酯，可改善锂离子电池的高温存储特性，但硫酸乙烯酯在高电压4.5V下浮充性能并不理想。Japanese patent JP1998189042A discloses a vinyl sulfate (DTD) electrolyte. By introducing vinyl sulfate, the high-temperature storage characteristics of lithium-ion batteries can be improved, but the floating charge performance of vinyl sulfate at a high voltage of 4.5V is not ideal.
因此，必须开发一种能耐4.5V高电压的电解液，进而实现锂离子电池电性能的优良发挥。Therefore, it is necessary to develop an electrolyte that can withstand a high voltage of 4.5V, and then realize the excellent electrical performance of the lithium-ion battery.
申请内容application content
为了解决上述问题，本申请的目的在于提供一种非水电解液及其锂离子电池，此非水电解液能抑制电解液的氧化分解，可提高高电压(4.5V)三元正极材料体系下锂离子电池的高温存储性能，同时还可改善锂离子电池的浮充性能。In order to solve the above problems, the purpose of this application is to provide a non-aqueous electrolyte and lithium-ion battery thereof. This non-aqueous electrolyte can inhibit the oxidation and decomposition of the electrolyte, and can improve the high voltage (4.5V) ternary positive electrode material system. The high-temperature storage performance of lithium-ion batteries can also improve the floating charge performance of lithium-ion batteries.
为实现上述目的，本申请第一方面提供了一种非水电解液，包括锂盐、非水有机溶剂和添加剂，所述添加剂包括环状含氮硫酸酯，所述环状含氮硫酸酯的化学式如结构式I或结构式II所示，In order to achieve the above object, the first aspect of the present application provides a non-aqueous electrolyte, including lithium salt, non-aqueous organic solvent and additives, the additives include cyclic nitrogen-containing sulfuric acid ester, the cyclic nitrogen-containing sulfuric acid ester The chemical formula is shown in structural formula I or structural formula II,
Figure PCTCN2021140301-appb-000001
Figure PCTCN2021140301-appb-000002
Figure PCTCN2021140301-appb-000001
Figure PCTCN2021140301-appb-000002
本申请的环状含氮硫酸酯添加剂，其-SO 2-结构在首次充电时于正极/电解液界面发生反应，形成含S、O的界面膜，该界面膜在高温条件下比较稳定，能较为可观的提升锂离子电池的高温存储性能。但这类含S、O的界面膜在持续高电压下(尤其是4.5V时)不太稳定，容易分解产生SO 2等气体，而使电池产气，恶化电池性能。然而其三氟代烷基苯环结构在首次充放电时可聚合形成带有LiF的高聚物界面膜而附着于含S、O的界面膜的表面，该高聚物界面膜在持续高电压下极为稳定，可抑制含S、O的界面膜在持续高电压下的分解，极大提升锂离子电池的浮充性能。同时，-N-结构也参与形成一些含N xO y的界面膜，从而增加了前两者界面膜的韧性，使得界面膜不易破裂。所以本申请的电解液中因加入了具有特殊结构的环状含氮硫酸酯添加剂，通过三种结构的结合可优化正极/电解液界面，降低电极的表面活性从而抑制电解液的氧化分解，从而改善锂离子电池于高电压下(尤其是4.5V时)的浮充性能和高温存储性能。 The cyclic nitrogen-containing sulfuric acid ester additive of the present application, its -SO 2 - structure reacts at the positive electrode/electrolyte interface when it is charged for the first time, forming an interface film containing S and O, which is relatively stable under high temperature conditions and can It can significantly improve the high-temperature storage performance of lithium-ion batteries. However, this kind of interfacial film containing S and O is not stable under continuous high voltage (especially at 4.5V), and it is easy to decompose to generate SO 2 and other gases, which will cause the battery to generate gas and deteriorate the battery performance. However, its trifluoroalkylbenzene ring structure can be polymerized to form a polymer interface film with LiF and adhere to the surface of the interface film containing S and O when it is charged and discharged for the first time. It is extremely stable under high voltage, can inhibit the decomposition of the interfacial film containing S and O under continuous high voltage, and greatly improve the float charge performance of lithium-ion batteries. At the same time, the -N- structure also participates in the formation of some N x O y -containing interfacial films, which increases the toughness of the former two interfacial films and makes the interfacial films difficult to break. Therefore, due to the addition of a cyclic nitrogen-containing sulfuric acid ester additive with a special structure in the electrolyte of the present application, the positive electrode/electrolyte interface can be optimized through the combination of the three structures, and the surface activity of the electrode can be reduced to inhibit the oxidative decomposition of the electrolyte, thereby Improve the floating charge performance and high temperature storage performance of lithium-ion batteries at high voltage (especially at 4.5V).
其中，结构式Ⅰ的化合物采用1,2,5-噻二唑啉-1,1-二氧化物和1-溴-三氟对二甲苯在碳酸钾作用下发生取代反应，再经过重结晶或柱层析纯化制备得到。其反应式如下所述。结构式Ⅱ化合物的合成路线与结构式Ⅰ的合成路线类似。Wherein, the compound of structural formula I adopts 1,2,5-thiadiazoline-1,1-dioxide and 1-bromo-trifluoro-p-xylene to undergo a substitution reaction under the action of potassium carbonate, and then undergoes recrystallization or column Prepared by chromatographic purification. Its reaction formula is as follows. The synthetic route of the compound of structural formula II is similar to the synthetic route of structural formula I.
Figure PCTCN2021140301-appb-000003
Figure PCTCN2021140301-appb-000003
作为一较佳技术方案，所述环状含氮硫酸酯于所述非水电解液中的质量百分比为0.1～5％，更优选为0.5～2％，具体但不限于为0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％。As a preferred technical solution, the mass percentage of the cyclic nitrogen-containing sulfuric acid ester in the non-aqueous electrolyte is 0.1-5%, more preferably 0.5-2%, specifically but not limited to 0.1%, 0.5% , 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%.
作为一较佳技术方案，所述锂盐于所述非水电解液中的质量百分比为6.5～15.5％。所述锂盐选自六氟磷酸锂(LiPF 6)、高氯酸锂(LiClO 4)、四氟硼酸锂(LiBF 4)、三氟甲基磺酸锂(LiCF 3SO 3)、双三氟甲基磺酰亚胺锂 (LiN(CF 3SO 2) 2)、双草酸硼酸锂(C 4BLiO 8)、二氟磷酸锂(LiPO 2F 2)、二氟草酸硼酸锂(C 2BF 2LiO 4)、二氟二草酸磷酸锂(LiDFBP)和双氟磺酰亚胺锂(LiFSI)中的至少一种。 As a preferred technical solution, the mass percentage of the lithium salt in the non-aqueous electrolyte is 6.5-15.5%. The lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), bistrifluoromethanesulfonate Lithium imide (LiN(CF 3 SO 2 ) 2 ), lithium bisoxalate borate (C 4 BLiO 8 ), lithium difluorophosphate (LiPO 2 F 2 ), lithium difluorooxalate borate (C 2 BF 2 LiO 4 ) , at least one of lithium difluorodioxalate phosphate (LiDFBP) and lithium bisfluorosulfonimide (LiFSI).
作为一较佳技术方案，所述有机溶剂为链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。更优选的，所述非水有机溶剂选自碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸丙烯酯(PC)、乙酸丁酯(n-Ba)、γ-丁内酯(γ-Bt)、丙酸丙酯(n-Pp)、丙酸乙酯(EP)和丁酸乙酯(Eb)中的至少一种。As a preferred technical solution, the organic solvent is at least one of chain carbonate, cyclic carbonate and carboxylate. More preferably, described non-aqueous organic solvent is selected from ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), propylene carbonate (PC), At least one of butyl acetate (n-Ba), γ-butyrolactone (γ-Bt), propyl propionate (n-Pp), ethyl propionate (EP) and ethyl butyrate (Eb) .
本申请的第二方面提供了一种锂离子电池，包括正极材料、负极材料和电解液，所述电解液为前述的非水电解液，所述正极材料为镍钴锰氧化物或镍钴铝氧化物，且最高充电电压为4.5V。The second aspect of the present application provides a lithium-ion battery, including a positive electrode material, a negative electrode material and an electrolyte, the electrolyte is the aforementioned non-aqueous electrolyte, and the positive electrode material is nickel-cobalt-manganese oxide or nickel-cobalt-aluminum Oxide, and the highest charging voltage is 4.5V.
本申请的锂离子电池因其非水电解液的添加剂包括具有特殊结构的环状含氮硫酸酯添加剂，通过其中的三种结构的结合可优化正极/电解液界面，降低电极的表面活性从而抑制电解液的氧化分解，从而改善锂离子电池于高电压下(尤其是4.5V时)的浮充性能和高温存储性能。The lithium-ion battery of the present application includes a cyclic nitrogen-containing sulfuric acid ester additive with a special structure because of its non-aqueous electrolyte additives. The combination of the three structures can optimize the positive electrode/electrolyte interface and reduce the surface activity of the electrode. The oxidative decomposition of the electrolyte improves the float charge performance and high temperature storage performance of the lithium-ion battery at high voltage (especially at 4.5V).
作为一较佳技术方案，所述镍钴锰氧化物的化学式为LiNi xCo yMn zM (1-x-y-z)O 2，所述镍钴铝氧化物的化学式为LiNi xCo yAl zN (1-x-y-z)O 2，其中，M为Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，N为Mn、Mg、Cu、Zn、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，0<x<1，0<y<1，0<z<1，x+y+z≤1。所述负极材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种。 As a preferred technical solution, the chemical formula of the nickel-cobalt-manganese oxide is LiNi x Co y Mnz M (1-xyz) O 2 , and the chemical formula of the nickel-cobalt aluminum oxide is LiNi x Co y Al z N ( 1-xyz) O 2 , wherein M is at least one of Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and N is Mn, Mg, Cu, Zn, Sn, At least one of B, Ga, Cr, Sr, V and Ti, 0<x<1, 0<y<1, 0<z<1, x+y+z≤1. The negative electrode material is at least one selected from artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
具体实施方式Detailed ways
下面通过具体实施例来进一步说明本申请的目的、技术方案及有益效果，但不构成对本申请的任何限制。实施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。The purpose, technical solutions and beneficial effects of the present application will be further described below through specific examples, but this does not constitute any limitation to the present application. Those who do not indicate specific conditions in the examples can be carried out according to conventional conditions or conditions suggested by the manufacturer. The reagents or instruments used, whose manufacturers are not indicated, are all commercially available conventional products.
实施例1Example 1
(1)非水电解液的制备：在氩气氛围下，水分含量＜1ppm的真空手套箱中配制电解液，在干燥的氩气气氛手套箱中，将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)、碳酸二乙酯(DEC)按照重量比为EC:EMC:DEC＝30:50:20进行混合，接着加入添加剂，溶解并充分搅拌后加入锂盐，混合均匀后获得电解液。(1) Preparation of non-aqueous electrolyte: under argon atmosphere, the electrolyte is prepared in a vacuum glove box with a moisture content of <1ppm. In a dry argon atmosphere glove box, ethylene carbonate (EC), methyl ethyl carbonate Ester (EMC) and diethyl carbonate (DEC) are mixed according to the weight ratio of EC:EMC:DEC=30:50:20, then the additive is added, dissolved and fully stirred, then lithium salt is added, and the electrolyte is obtained after mixing evenly.
(2)正极的制备：将镍钴铝酸锂三元材料LiNi 0.5Co 0.2Mn 0.3O 2、粘接剂PVDF和导电剂SuperP按质量比95:1:4混合均匀制成一定粘度的锂离子电池正极浆料，将混制的浆料涂布在铝箔的两面后，烘干、辊压后得到正极片。 (2) Preparation of positive electrode: LiNi 0.5 Co 0.2 Mn 0.3 O 2 ternary material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , binder PVDF and conductive agent SuperP are uniformly mixed at a mass ratio of 95:1:4 to make lithium ions with a certain viscosity The positive electrode slurry of the battery, after coating the mixed slurry on both sides of the aluminum foil, drying and rolling to obtain the positive electrode sheet.
(3)负极的制备：将人造石墨与导电剂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。(3) Preparation of negative electrode: artificial graphite and conductive agent SuperP, thickener CMC, and adhesive SBR (styrene-butadiene rubber emulsion) are made into a slurry in a mass ratio of 95:1.5:1.0:2.5, and mixed evenly. The mixed slurry is coated on both sides of the copper foil, dried and rolled to obtain a negative electrode sheet.
(4)锂离子电池的制备：将正极、隔膜以及负极以叠片的方式制成方形电芯，采用聚合物包装，灌装上述制备的锂离子电池非水电解液，经化成、分容等工序后制成容量为1000mAh的锂离子电池。(4) Preparation of lithium-ion battery: the positive electrode, diaphragm and negative electrode are stacked into square batteries, packed in polymer, filled with the non-aqueous electrolyte of lithium-ion battery prepared above, and processed by chemical formation, volume separation, etc. After the process, a lithium-ion battery with a capacity of 1000mAh is produced.
实施例2～7和对比例1～4的电解液配方如表1所示，配制电解液及制备电池的步骤同实施例1。The electrolyte formulations of Examples 2-7 and Comparative Examples 1-4 are shown in Table 1, and the steps of preparing the electrolyte and preparing the battery are the same as those of Example 1.
表1各实施例的电解液组分The electrolyte composition of each embodiment of table 1
组别group 非水有机溶剂/质量(g)Non-aqueous organic solvent/mass (g) 锂盐/质量(g)Lithium salt/mass (g) 添加剂(g)Additive (g)
实施例1Example 1 EC/EMC/DEC＝3:5:2(86.5g)EC/EMC/DEC＝3:5:2(86.5g) LiPF 6(12.5g) LiPF6 (12.5g) 结构式I(1.0g)Structural formula I (1.0g)
实施例2Example 2 EC/EMC/DEC＝3:5:2(86.5g)EC/EMC/DEC＝3:5:2(86.5g) LiPF 6(12.5g) LiPF6 (12.5g) 结构式II(1.0g)Structural Formula II (1.0g)
实施例3Example 3 EC/EMC/DEC＝3:5:2(87.0g)EC/EMC/DEC＝3:5:2(87.0g) LiPF 6(12.5g) LiPF6 (12.5g) 结构式II(0.5g)Structural formula II (0.5g)
实施例4Example 4 EC/EMC/DEC＝3:5:2(85.5g)EC/EMC/DEC＝3:5:2(85.5g) LiPF 6(12.5g) LiPF6 (12.5g) 结构式II(2.0g)Structural Formula II (2.0g)
实施例5Example 5 EC/EMC/DEC＝3:5:2(86.5g)EC/EMC/DEC＝3:5:2(86.5g) LiPF 6(12.5g) LiPF6 (12.5g) 结构式I(0.5g)+结构式II(0.5g)Structural Formula I (0.5g) + Structural Formula II (0.5g)
实施例6Example 6 EC/EMC/DEC＝2:5:2(87.8g)EC/EMC/DEC＝2:5:2(87.8g) LiPF 6(12g) LiPF6 (12g) 结构式I(0.2g)Structural formula I (0.2g)
实施例7Example 7 PC/DEC/EMC＝3:5:2(88g)PC/DEC/EMC＝3:5:2(88g) LiPF 6+LiBF 4(3.2g+3.8g) LiPF 6 +LiBF 4 (3.2g+3.8g) 结构式I(5g)Structural formula I (5g)
对比例1Comparative example 1 EC/EMC/DEC＝3:5:2(87.5g)EC/EMC/DEC＝3:5:2(87.5g) LiPF 6(12.5g) LiPF6 (12.5g) //
对比例2Comparative example 2 EC/EMC/DEC＝3:5:2(86.5g)EC/EMC/DEC＝3:5:2(86.5g) LiPF 6(12.5g) LiPF6 (12.5g) DTD(1.0g)DTD (1.0g)
对比例3Comparative example 3 EC/EMC/DEC＝3:5:2(86.5g)EC/EMC/DEC＝3:5:2(86.5g) LiPF 6(12.5g) LiPF6 (12.5g) 氟苯(1.0g)Fluorobenzene (1.0g)
对比例4Comparative example 4 EC/EMC/DEC＝3:5:2(86.5g)EC/EMC/DEC＝3:5:2(86.5g) LiPF 6(12.5g) LiPF6 (12.5g) DTD(0.5g)+氟苯(0.5g)DTD(0.5g)+fluorobenzene(0.5g)
对实施例1～7和对比例1～4制成的锂离子电池分别进行浮充性能测试和高温存储测试，其具体测试条件如下，性能测试结果如表2所示。The lithium-ion batteries produced in Examples 1-7 and Comparative Examples 1-4 were subjected to a float charge performance test and a high-temperature storage test respectively. The specific test conditions are as follows, and the performance test results are shown in Table 2.
(1)锂离子电池浮充性能测试(1) Lithium-ion battery float charge performance test
锂离子电池在25℃下以0.5C放电至3.0V，再以0.5C充电至4.5V，4.5V下恒压充电至0.05C，放置到45℃烘箱当中，4.5V恒压50d后，监控锂离子电池的厚度变化值，且以初始50％SOC的厚度作为基准。Lithium-ion battery was discharged at 0.5C to 3.0V at 25°C, then charged at 0.5C to 4.5V, charged at 4.5V to 0.05C at constant voltage, placed in an oven at 45°C, and kept at 4.5V for 50 days to monitor the lithium ion battery. The thickness change value of the ion battery, and the thickness of the initial 50% SOC is used as a benchmark.
(2)锂离子电池高温存储测试(2) Lithium-ion battery high temperature storage test
在常温(25℃)条件下，对锂离子电池进行一次0.3C/0.3C充电和放电(电池放电容量记录为C0)，上限电压为4.5V；将电池放置于60℃烘箱中搁置15d，取出电池，将电池放置于25℃环境中，进行0.3C放电，放电容量记录为C1；然后对锂离子电池进行一次0.3C/0.3C充电和放电(电池放电容量记录为C2)，利用下面公式计算锂离子电池的容量保持率、容量恢复率和厚度膨胀率。At room temperature (25°C), charge and discharge the lithium-ion battery once at 0.3C/0.3C (the discharge capacity of the battery is recorded as C0), and the upper limit voltage is 4.5V; place the battery in an oven at 60°C for 15 days, and take it out For the battery, place the battery in an environment of 25°C, discharge at 0.3C, and record the discharge capacity as C1; then charge and discharge the lithium-ion battery once at 0.3C/0.3C (record the discharge capacity of the battery as C2), and use the following formula to calculate Capacity retention rate, capacity recovery rate and thickness expansion rate of lithium-ion batteries.
容量保持率＝C1/C0*100％Capacity retention = C1/C0*100%
容量恢复率＝C2/C0*100％Capacity recovery rate = C2/C0*100%
表2锂离子电池性能测试结果Table 2 Li-ion battery performance test results
Figure PCTCN2021140301-appb-000004
Figure PCTCN2021140301-appb-000004
由表2的结果可知，实施例1～7的浮充性能和高温储存性能皆好于对比例1～4，这是由于本申请含有特殊结构的环状含氮硫酸酯添加剂，其-SO 2-结构在首次充电时于正极/电解液界面发生反应，形成含S、O的界面膜，该界面膜在高温条件下比较稳定，能较为可观的提升锂离子电池的高温存储性能。但这类含S、O的界面膜在持续高电压下(尤其是4.5V时)不太稳定，容易分解产生SO 2等气体，而使电池产气，恶化电池性能。然而其三氟代烷基苯环结构在首次充放电时可聚合形成带有LiF的高聚物界面膜而附着于含S、O的界面膜的表面，该高聚物界面膜在持续高电压下极为稳定，可抑制含S、O的界面膜在持续高电压下的分解，极大提升锂离子电池的浮充性能。同时，-N-结构也参与形成一些含N xO y的界面膜，从而增加了前两者界面膜的韧性，使得界面膜不易破裂，故浮充性能和高温存储性能皆较佳。 As can be seen from the results in Table 2, the float performance and high-temperature storage performance of Examples 1 to 7 are better than those of Comparative Examples 1 to 4. This is because the present application contains a cyclic nitrogen-containing sulfuric acid ester additive with a special structure, and its -SO 2 -The structure reacts at the positive electrode/electrolyte interface during the first charge to form an interfacial film containing S and O. This interfacial film is relatively stable under high temperature conditions and can considerably improve the high-temperature storage performance of lithium-ion batteries. However, this kind of interfacial film containing S and O is not stable under continuous high voltage (especially at 4.5V), and it is easy to decompose to generate SO 2 and other gases, which will cause the battery to generate gas and deteriorate the battery performance. However, its trifluoroalkylbenzene ring structure can be polymerized to form a polymer interface film with LiF and adhere to the surface of the interface film containing S and O when it is charged and discharged for the first time. It is extremely stable under high voltage, can inhibit the decomposition of the interfacial film containing S and O under continuous high voltage, and greatly improve the float charge performance of lithium-ion batteries. At the same time, the -N- structure also participates in the formation of some N x O y -containing interfacial films, thereby increasing the toughness of the former two interfacial films and making the interfacial films difficult to break, so the floating charge performance and high-temperature storage performance are both better.
对比例2的添加剂中虽然含有硫酸乙烯酯(DTD)，能于一定程度上改善高温存储性能，但是在4.5V的高压体系下，其效果并不明显，同时也无法解决浮充问题。Although the additive in Comparative Example 2 contains ethylene sulfate (DTD), it can improve the high-temperature storage performance to a certain extent, but the effect is not obvious under the high-voltage system of 4.5V, and it cannot solve the floating charge problem at the same time.
对比例3的添加剂中仅含有单一的氟苯，虽能于一定程度上改善浮充性能，但是无法解决高电压体系下的浮充和高温存储问题。The additive in Comparative Example 3 only contains a single fluorobenzene, although it can improve the floating charge performance to a certain extent, it cannot solve the problem of floating charge and high temperature storage under high voltage system.
对比例4中虽然同时含有硫酸乙烯酯(DTD)和氟苯，但由于氟苯和DTD的氧化还原电位不同，在电极表面的反应条件、反应程度均不同，虽然同时添加，其仍然达不大到本申请作为一种具有特殊结构的环状含氮硫酸酯添加剂，其-SO 2-结构和三氟代烷基苯环结构结合所实现的技术效果，故浮充性能和高温存储性能较差。 Though comparative example 4 contains vinyl sulfate (DTD) and fluorobenzene at the same time, because the oxidation-reduction potential of fluorobenzene and DTD is different, the reaction conditions and the degree of reaction on the electrode surface are all different, although it is added at the same time, it still does not reach much According to this application, as a cyclic nitrogen-containing sulfuric acid ester additive with a special structure, the technical effect achieved by the combination of its -SO 2 - structure and the trifluoroalkylbenzene ring structure, so the floating charge performance and high temperature storage performance are poor .
最后应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that Modifications or equivalent replacements are made to the technical solutions of the present application without departing from the essence and scope of the technical solutions of the present application.

Claims (10)

  1. 一种非水电解液，包括锂盐、非水有机溶剂和添加剂，其特征在于，所述添加剂包括环状含氮硫酸酯，所述环状含氮硫酸酯的化学式如结构式I或结构式II所示，A kind of non-aqueous electrolytic solution, comprises lithium salt, non-aqueous organic solvent and additive, is characterized in that, described additive comprises cyclic nitrogen-containing sulfuric acid ester, and the chemical formula of described cyclic nitrogen-containing sulfuric acid ester is as shown in structural formula I or structural formula II Show,
    Figure PCTCN2021140301-appb-100001
    Figure PCTCN2021140301-appb-100001
  2. 如权利要求1所述的非水电解液，其特征在于，所述环状含氮硫酸酯于所述非水电解液中的质量百分比为0.1～5％。The non-aqueous electrolytic solution according to claim 1, wherein the mass percentage of the cyclic nitrogen-containing sulfuric acid ester in the non-aqueous electrolytic solution is 0.1-5%.
  3. 如权利要求2所述的非水电解液，其特征在于，所述环状含氮硫酸酯于所述非水电解液中的质量百分比为0.5～2％。The non-aqueous electrolytic solution according to claim 2, characterized in that, the mass percentage of the cyclic nitrogen-containing sulfuric acid ester in the non-aqueous electrolytic solution is 0.5-2%.
  4. 如权利要求1所述的非水电解液，其特征在于，所述锂盐于所述非水电解液中的质量百分比为6.5～15.5％。The non-aqueous electrolytic solution according to claim 1, wherein the mass percentage of the lithium salt in the non-aqueous electrolytic solution is 6.5-15.5%.
  5. 如权利要求1所述的非水电解液，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、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂、双草酸硼酸锂、二氟磷酸锂、二氟草酸硼酸锂、二氟二草酸磷酸锂和双氟磺酰亚胺锂中的至少一种。The nonaqueous electrolytic solution according to claim 1, wherein the lithium salt is selected from lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, bistrifluoromethylsulfonyl At least one of lithium amine, lithium bisoxalate borate, lithium difluorophosphate, lithium difluorooxalate borate, lithium difluorodioxalate phosphate and lithium bisfluorosulfonyl imide.
  6. 如权利要求1所述的非水电解液，其特征在于，所述有机溶剂为链状碳酸酯、环状碳酸酯和羧酸酯中的至少一种。The non-aqueous electrolytic solution according to claim 1, wherein the organic solvent is at least one of chain carbonate, cyclic carbonate and carboxylate.
  7. 如权利要求6所述的非水电解液，其特征在于，所述非水有机溶剂选自碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸丙烯酯、乙酸丁酯、γ-丁内酯、丙酸丙酯、丙酸乙酯和丁酸乙酯中的至少一种。nonaqueous electrolytic solution as claimed in claim 6, is characterized in that, described nonaqueous organic solvent is selected from ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate , at least one of γ-butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
  8. 一种锂离子电池，包括正极材料、负极材料和电解液，其特征在于，所述电解液为权利要求1～7任一项所述的非水电解液，所述正极材料为镍钴锰氧化物或镍钴铝氧化物，且最高充电电压为4.5V。A lithium ion battery, comprising a positive electrode material, a negative electrode material and an electrolyte, characterized in that the electrolyte is the non-aqueous electrolyte according to any one of claims 1 to 7, and the positive electrode material is nickel-cobalt-manganese oxide material or nickel cobalt aluminum oxide, and the maximum charging voltage is 4.5V.
  9. 如权利要求8所述的锂离子电池，其特征在于，所述镍钴锰氧化物的化学式为LiNi xCo yMn zM (1-x-y-z)O 2，所述镍钴铝氧化物的化学式为LiNi xCo yAl zN (1-x-y-z)O 2，其中，M为Mg、Cu、Zn、Al、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，N为Mn、Mg、Cu、Zn、Sn、B、Ga、Cr、Sr、V和Ti中的至少一种，0<x<1，0<y<1，0<z<1，x+y+z≤1。 The lithium ion battery as claimed in claim 8, wherein the chemical formula of the nickel-cobalt-manganese oxide is LiNixCoyMnzM (1-xyz) O2 , and the chemical formula of the nickel-cobalt-aluminum oxide is LiNi x Co y Al z N (1-xyz) O 2 , wherein, M is at least one of Mg, Cu, Zn, Al, Sn, B, Ga, Cr, Sr, V and Ti, and N is Mn, At least one of Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, V and Ti, 0<x<1, 0<y<1, 0<z<1, x+y+z≤1 .
  10. 如权利要求8所述的锂离子电池，其特征在于，所述负极材料选自人造石墨、天然石墨、钛酸锂、硅碳复合材料和氧化亚硅中的至少一种。The lithium ion battery according to claim 8, wherein the negative electrode material is selected from at least one of artificial graphite, natural graphite, lithium titanate, silicon-carbon composite material and silicon oxide.
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