WO2018196426A1 - 一种非水电解液及二次电池 - Google Patents

一种非水电解液及二次电池 Download PDF

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WO2018196426A1
WO2018196426A1 PCT/CN2017/119155 CN2017119155W WO2018196426A1 WO 2018196426 A1 WO2018196426 A1 WO 2018196426A1 CN 2017119155 W CN2017119155 W CN 2017119155W WO 2018196426 A1 WO2018196426 A1 WO 2018196426A1
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compound
lithium
battery
electrolytic solution
reaction
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PCT/CN2017/119155
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English (en)
French (fr)
Inventor
王峰
时二波
秦虎
陈黎
陈俊彩
沈蕾
甘朝伦
袁翔云
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张家港市国泰华荣化工新材料有限公司
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Priority to PL17907067.7T priority Critical patent/PL3618163T3/pl
Priority to EP17907067.7A priority patent/EP3618163B1/en
Publication of WO2018196426A1 publication Critical patent/WO2018196426A1/zh

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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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 present invention relates to the field of electrochemical technology, and in particular to a non-aqueous electrolyte and a secondary battery.
  • lithium ion secondary batteries that realize energy conversion by intercalation and extraction of lithium ions have higher energy density than lead acid batteries and nickel hydrogen batteries, and occupy a dominant position in the small battery market.
  • lithium ion secondary batteries are gradually being promoted in the fields of power tools, electric vehicles, and energy storage power sources.
  • the secondary battery mainly includes a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the electrolyte acts as a medium for the charge and discharge reaction and has an important influence on the performance of the secondary battery.
  • a negative electrode active material In a lithium ion secondary battery using carbon or a silicon material as a negative electrode active material, a negative electrode active material easily reacts with an electrolyte during charge and discharge, resulting in decomposition of the electrolyte, and generally an electrolyte is formed on the surface of the negative electrode by an additive.
  • the interface film (SEI) suppresses the decomposition reaction of solvent molecules in the electrolyte.
  • VC vinylene carbonate
  • a lithium ion secondary battery using a manganese-containing lithium transition metal composite oxide such as LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , etc.
  • a manganese-containing lithium transition metal composite oxide such as LiMn 2 O 4 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , etc.
  • the charge cutoff voltage may be set to 4.3 V or more, and in such a high voltage environment, the electrolyte is liable to occur. Oxidative decomposition reaction. Therefore, the protection of the positive surface of the battery should also be taken seriously.
  • Patent document CN 1280942 C discloses the formation of a passivation layer at the electrode interface of a battery by a cyclic sulfonate, preventing decomposition of the solvent, improving cycle performance of the battery, and suppressing an increase in internal resistance of the battery.
  • the patent document CN 100544108C discloses that by adding a sulfonyl-containing compound to an electrolytic solution, a protective film can be formed on the surface of the positive electrode, and side reactions between the positive electrode and the electrolytic solution can be suppressed, thereby improving the high-temperature storage performance of the battery.
  • the technical problem to be solved by the present invention is to provide a nonaqueous electrolyte and a secondary battery which can better improve the cycle performance of the battery and suppress the increase in internal resistance.
  • An object of the present invention is to provide a nonaqueous electrolytic solution comprising a lithium salt, an organic solvent and an additive, the additive comprising a sulfonyl group-containing compound, and the sulfonyl group-containing compound is a compound (1) and/or a compound ( 2) wherein the structural formula of the compound (1) is:
  • the structural formula of the compound (2) is:
  • the synthetic route of compound (1) is:
  • the preparation method of the compound (1) includes the following steps:
  • Step (1) adding acetone to the fuming sulfuric acid, and then reacting at 65-75 ° C, after cooling to room temperature, adding fuming sulfuric acid to the reaction system, and then adding acetone to the reaction system, at 70- The reaction is carried out at 80 ° C, and after the reaction is finished, the compound b is obtained by post-treatment;
  • Step (2) the compound b is stirred under reflux in the presence of an organic solvent, after the reaction is completed, post-treatment to obtain a compound c;
  • Step (3) the compound c and vinyl magnesium bromide are reacted in the presence of an organic solvent, after the end of the reaction, post-treatment to obtain a compound d;
  • Step (4) the compound d, triethylsilane and boron trifluoride diethyl ether solution in the presence of an organic solvent, reacted at -75--85 ° C for 20-40 min, and then reacted at room temperature for 50-70 min, the reaction After completion, the compound (1) is obtained by post-treatment.
  • step (1) the SO 3 content of the oleum is added in the first 20% -30%, the content of SO 3 fuming sulfuric acid was added to a second 70% -80%.
  • the dropping temperature of acetone is less than 20 °C.
  • the organic solvent in step (2) is thionyl chloride.
  • the organic solvent in the step (3) is tetrahydrofuran.
  • the organic solvent in step (4) is acetonitrile.
  • the specific preparation method of the compound (1) is:
  • Step (1) adding 23% of SO 3 fuming sulfuric acid to a round bottom flask, slowly adding acetone to the reaction system, keeping the reaction temperature below 20 ° C, and stirring at 65-75 ° C after the dropwise addition is completed 10 -20 min, after cooling to room temperature, add 75% SO 3 fuming sulfuric acid, then slowly add acetone to the reaction system, react at 70-80 ° C for 50-70 min, after the reaction is finished, cool to room temperature, and let stand After a few hours, the pale yellow solid gradually precipitated, filtered, washed with nitromethane to obtain a crude product, and then recrystallized from nitromethane to give a white solid as compound b;
  • Step (2) the compound b and thionyl chloride were separately added to the reaction vessel, stirred under reflux for 20-30h, cooled to room temperature, filtered to obtain a crude product, and then washed with a small amount of toluene several times, dried to obtain a compound c;
  • Step (3) adding compound c to tetrahydrofuran, slowly adding vinyl magnesium bromide at -5 to 5 ° C, after the completion of the dropwise addition, the temperature is raised to room temperature, the reaction is continued for 20-30 hours, and saturated ammonium chloride is added after the reaction is completed.
  • the aqueous solution and the acetonitrile solution are separated, the aqueous layer is extracted with acetonitrile, the organic phase is combined, dried over anhydrous magnesium sulfate and concentrated to give compound d;
  • Step (4) adding compound d to acetonitrile, adding triethylsilane to the reaction system, and slowly adding boron trifluoride diethyl ether solution to the reaction system at -45--55 ° C, at -75-- Stir at 85 ° C for 20-40 min, warm to room temperature and continue to stir for 50-70 min.
  • After the reaction is finished add saturated sodium bicarbonate slowly to the reaction system to quench the reaction, separate the liquid, extract the aqueous phase with acetonitrile, and combine the organic phases. The organic layer was dried over sodium sulfate and evaporated to dryness crystals crystals
  • the compound (2) is prepared by reacting the compound A, HgSO 4 , H 2 SO 4 and water at 90-110 ° C to obtain a compound B, and the compound B, methane disulfonyl chloride in the presence of an organic solvent in ice The reaction was carried out in a water bath for 50-70 min, and then the reaction was stirred at room temperature for 4-6 h to give the compound (2).
  • the room temperature is 0 to 40 ° C, preferably 10 to 35 ° C, and more preferably 15 to 25 ° C.
  • the sulfonyl-containing compound is added in an amount of from 0.01 to 10% by mass based on the total mass of the non-aqueous electrolyte.
  • the sulfonyl group-containing compound is added in an amount of from 0.1 to 5% by mass based on the total mass of the nonaqueous electrolyte, more preferably from 1 to 5%, most preferably from 4 to 5%.
  • the additive further comprises vinylene carbonate (VC).
  • VC vinylene carbonate
  • the ethylene carbonate is added in an amount of 0.5 to 5% by mass based on the total mass of the nonaqueous electrolyte, more preferably 0.5 to 2%.
  • the total mass of the additive added is from 0.01 to 10%, more preferably from 0.1 to 5%, most preferably from 4 to 5%, based on the total mass of the nonaqueous electrolyte.
  • the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), anhydrous lithium perchlorate (LiClO 4 ), and two (three) Lithium fluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 ), lithium dioxalate borate (LiC 2 O 4 BC 2 O 4 ), One or more of lithium oxalate difluoroborate (LiF 2 BC 2 O 4 ), lithium bisfluorosulfonimide (LiN(SO 2 F) 2 ).
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiAsF 6 lithium hexafluoroars
  • the lithium salt has a concentration of from 0.9 to 1.1 mol/L.
  • the organic solvent is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), ⁇ -butyrolactone (GBL), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
  • Ethyl methyl carbonate (EMC) methyl propyl carbonate (MPC), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB), sulfolane, diethylene glycol dimethyl ether, triethylene glycol One or more of methyl ether.
  • the organic solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a mass ratio of 1:0.9-1.1:0.9-1.1.
  • the organic solvent is a mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in a mass ratio of 1:0.9-1.1:0.9-1.1.
  • Another object of the present invention is to provide a secondary battery comprising the nonaqueous electrolytic solution.
  • the secondary battery is a lithium ion secondary battery.
  • both the positive electrode and the negative electrode of the secondary battery are capable of absorbing and desorbing lithium ions.
  • the positive electrode active material of the secondary battery is LiCoO 2 or LiMn 2 O 4
  • the negative electrode active material of the secondary battery is graphite or Li 4 Ti 5 O 12 .
  • the present invention has the following advantages over the prior art:
  • the invention adopts a compound containing a vinyl group containing a sulfonyl group as an additive, and the additive of the two structures contributes to forming a protective film on the surface of the battery electrode, and the protective film has high stability during charge and discharge cycles and high temperature storage of the battery.
  • the property can inhibit the decomposition of solvent molecules in the electrolyte, reduce the internal resistance of the battery caused by the accumulation of decomposition products on the surface of the electrode, and improve the storage performance of the battery.
  • the compound d (60 g) was added to 500 mL of acetonitrile, and triethylsilane (60.5 g) was added to the reaction system, and a boron trifluoride diethyl ether solution (500 g) was slowly added dropwise to the reaction system at -50 ° C. After stirring at 78 ° C for 30 min, the temperature was raised to room temperature and stirring was continued for 1 h. After the reaction was completed, saturated sodium hydrogencarbonate was slowly added dropwise to the reaction system to quench the reaction, and the aqueous phase was separated, and the organic phase was combined and dried over anhydrous sodium sulfate. The crude product was concentrated to give the title compound (1) (33 g, yield: 60%).
  • LiCoO 2 , conductive carbon black and PVDF were weighed according to a mass ratio of 90:5:5, and an appropriate amount of NMP was added thereto, followed by thorough stirring to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on an aluminum foil, dried, and then rolled and cut to obtain a positive electrode.
  • Graphite, styrene-butadiene rubber and carboxymethylcellulose were weighed according to a mass ratio of 95:3:2, and an appropriate amount of deionized water was added thereto, followed by thorough stirring to obtain a negative electrode slurry.
  • the negative electrode slurry was applied onto a copper foil, dried, and then rolled and cut to obtain a negative electrode.
  • a mixed solvent of ethylene carbonate (EC), diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) was mixed at a mass ratio of 1:1:1, and lithium hexafluorophosphate was dissolved therein at a concentration of 1 mol/liter. Adding the additive compound prepared in Example 1 (1) The electrolytic solution containing 1% by weight of the compound (1) was obtained.
  • a PE separator having a thickness of 20 ⁇ m was selected, and a soft pack battery was manufactured by a winding process, and the model number was 053048.
  • the battery charge and discharge test was carried out at 25 ° C with a voltage range of 3.0-4.4V. After the battery was formed at a rate of 0.1 C, it was pre-circulated at a rate of 0.2 C for 5 weeks. Then perform loop performance or storage performance testing.
  • the cycle performance test is to charge and discharge the battery at a rate of 1 C, and to test the capacity retention rate after 500 cycles.
  • the battery was fabricated in the same manner as in Example 3 except that the electrolytic solution contained 3 wt% of the compound (1).
  • the battery performance test was conducted in the same manner as in Example 3.
  • the battery was fabricated in the same manner as in Example 3 except that the electrolytic solution contained 5 wt% of the compound (1).
  • the battery performance test was conducted in the same manner as in Example 3.
  • Example 3 In addition to the compound (1), the compound obtained in Example 2 (2) instead of the battery, the battery was fabricated in the same manner as in Example 3. The battery performance test was conducted in the same manner as in Example 3.
  • a battery was fabricated in the same manner as in Example 3 except that the electrolytic solution contained 2% by weight of the compound (1) obtained in Example 1 and 2% by weight of the compound (2) obtained in Example 2. The battery performance test was conducted in the same manner as in Example 3.
  • a battery was fabricated in the same manner as in Example 3 except that the electrolytic solution contained 2% by weight of the compound (1) obtained in Example 1, 2% by weight of the compound (2) obtained in Example 2, and 1% of VC.
  • the battery performance test was conducted in the same manner as in Example 3.
  • the battery was fabricated in the same manner as in Example 3 except that the compound (1) was not added to the electrolytic solution.
  • the battery performance test was conducted in the same manner as in Example 3.
  • a battery was fabricated in the same manner as in Example 3 except that the compound (1) was replaced with VC.
  • the battery performance test was conducted in the same manner as in Example 3.
  • the batteries of Examples 3-8 Compared with Comparative Examples 1 and 2, the batteries of Examples 3-8 have an improved capacity retention ratio and a lower internal resistance increase rate, that is, the battery has better cycle performance and storage performance.
  • the combination of the compounds (1) and (2) has a synergistic effect.
  • LiMn 2 O 4 , conductive carbon black and PVDF were weighed according to a mass ratio of 90:5:5, and an appropriate amount of NMP was added thereto, followed by thorough stirring to obtain a positive electrode slurry.
  • the positive electrode slurry was coated on an aluminum foil, dried, and then rolled and cut to obtain a positive electrode.
  • Li 4 Ti 5 O 12 , styrene-butadiene rubber and carboxymethyl cellulose were weighed according to a mass ratio of 95: 3 : 2 , and an appropriate amount of deionized water was added thereto, followed by thorough stirring to obtain a negative electrode slurry.
  • the negative electrode slurry was applied onto a copper foil, dried, and then rolled and cut to obtain a negative electrode.
  • a mixed solvent of ethylene carbonate (EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) was mixed at a mass ratio of 1:1:1, and lithium hexafluorophosphate was dissolved therein at a concentration of 1 mol/liter.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • a PE separator having a thickness of 20 ⁇ m was selected, and a cylindrical battery was fabricated by a winding process, and the model number was 18650.
  • the battery charge and discharge test was carried out at 25 ° C with a voltage range of 1.5-2.7V. After the battery was formed at a rate of 0.1 C, it was pre-circulated at 0.2 C for 5 weeks. Then perform loop performance or storage performance testing.
  • the cycle performance test was performed by charging and discharging the battery at a rate of 1 C, and testing the capacity retention rate after the 800-week cycle.
  • a battery was fabricated in the same manner as in Example 9 except that the electrolytic solution contained 3 wt% of the compound (2) obtained in Example 2.
  • the battery performance test was conducted in the same manner as in Example 9.
  • the battery was fabricated in the same manner as in Example 9 except that the electrolytic solution contained 5 wt% of the compound (2) obtained in Example 2.
  • the battery performance test was conducted in the same manner as in Example 9.
  • a battery was fabricated in the same manner as in Example 9 except that the compound (2) was replaced with the compound (1) obtained in Example 1.
  • the battery performance test was conducted in the same manner as in Example 9.
  • a battery was fabricated in the same manner as in Example 9 except that the electrolytic solution contained 2% by weight of the compound (1) obtained in Example 1 and 2% by weight of the compound (2) obtained in Example 2. The battery performance test was conducted in the same manner as in Example 9.
  • the battery was fabricated in the same manner as in Example 9 except that the compound (2) was not added to the electrolytic solution.
  • the battery performance test was conducted in the same manner as in Example 9.
  • a battery was fabricated in the same manner as in Example 9, except that the compound (2) was replaced with 1,3-propane sultone (1,3-PS). The battery performance test was conducted in the same manner as in Example 9.
  • the batteries of Examples 9-13 Compared with Comparative Examples 3 and 4, the batteries of Examples 9-13 have improved capacity retention and a lower rate of increase in internal resistance, i.e., the battery has superior cycle performance and storage performance.
  • the combination of the compounds (1) and (2) has a synergistic effect.

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Abstract

一种非水电解液及二次电池，非水电解液包括锂盐、有机溶剂和添加剂，添加剂包括含磺酰基化合物。通过采用含乙烯基含磺酰基的化合物作为添加剂，该两种结构的添加剂有助于电池电极表面形成保护膜，在电池充放电循环和高温存储过程中，该保护膜具有很高的稳定性，可以抑制电解液中溶剂分子的分解，减少分解产物在电极表面堆积导致的电池内阻升高，改善电池存储性能。

Description

一种非水电解液及二次电池 技术领域
本发明涉及电化学技术领域，具体涉及一种非水电解液及二次电池。
背景技术
近年来，手机、笔记本电脑等便携式电子设备的广泛应用促进了对高能量密度二次电池的需求。在众多二次电池中，以锂离子的嵌入和脱出实现能量转换的锂离子二次电池具有比铅酸电池和镍氢电池更高的能量密度，在小型电池市场中占据了主导地位。随着材料技术和制造工艺的进步，锂离子二次电池在电动工具、电动汽车、储能电源等领域也逐渐得到推广。
二次电池主要包括正极、负极、隔膜和电解液。电解液作为充放电反应的介质，对二次电池的性能有着重要影响。
使用碳、硅材料作为负极活性物质的锂离子二次电池中，在充放电过程中负极活性物质容易与电解液发生反应，导致电解液的分解，一般通过添加剂使电解液在负极表面形成固体电解质界面膜(SEI)，可以抑制电解液中溶剂分子的分解反应。通过向电解液中添加碳酸亚乙烯酯(VC)，可以起到对碳、硅负极表面成膜的作用，然而当电池处于高温环境时，表面膜会发生分解与再生，其保护作用随之减弱，并会导致电池内阻增加。
采用含锰的锂过渡金属复合氧化物(如LiMn 2O 4、LiNi 1/3Co 1/3Mn 1/3O 2等)作为正极活性物质的锂离子二次电池中，由于锰离子的溶出和在负极表面的沉积，会导致电池性能的恶化。采用LiCoO 2或LiNi 0.5Co 0.2Mn 0.3O 2作为正极活性物质时，为了获得更高的电池容量，有时会将充电截止电压设置为4.3V以上，在这种高电压环境下，电解液易发生氧化分解反应。因此，对电池正极表面的保护也应引起重视。
专利文献CN 1280942C公开了通过环状磺酸酯在电池电极界面形成钝化层，阻止溶剂分解，提高电池循环性能，并抑制电池内阻增加。
专利文献CN 100544108C公开了通过在电解液中添加含磺酰基化合物，可以在正极表面形成保护膜，抑制正极和电解液之间的副反应，从而改善电池的高温存储性能。
发明内容
本发明所要解决的技术问题是提供一种能够更好的提高电池的循环性能和抑制内阻增加的非水电解液及二次电池。
为达到上述目的，本发明采用的技术方案是：
本发明的一个目的是提供一种非水电解液，包括锂盐、有机溶剂和添加剂，所述的添加剂包括含磺酰基化合物，所述的含磺酰基化合物为化合物(1)和/或化合物(2)，其中，化合物(1)的结构式为：
Figure PCTCN2017119155-appb-000001
化合物(2)的结构式为：
Figure PCTCN2017119155-appb-000002
化合物(1)的合成路线为：
Figure PCTCN2017119155-appb-000003
化合物(1)的制备方法包括如下步骤：
步骤(1)、向发烟硫酸中滴加丙酮，然后在65-75℃下反应，降温至室温后，向反应体系中加入发烟硫酸，然后再向反应体系中滴加丙酮，在70-80℃下反应，反应结束后经后处理得到化合物b；
步骤(2)、将化合物b在有机溶剂的存在下进行回流搅拌反应，反应结束后，经后处理得到化合物c；
步骤(3)、将化合物c与乙烯基溴化镁在有机溶剂的存在下进行反应，反应结束后经后处理得到化合物d；
步骤(4)、将化合物d、三乙基硅烷和三氟化硼乙醚溶液在有机溶剂的存在下，在-75--85℃下反应20-40min，然后在室温下反应50-70min，反应结束后，经后处理得到化合物(1)。
优选地，步骤(1)中，第一次加入的发烟硫酸的SO 3的含量为20％-30％，第二次加入的发烟硫酸的SO 3的含量为70％-80％。
优选地，步骤(1)中，丙酮的滴加温度小于20℃。
优选地，步骤(2)中的有机溶剂为氯化亚砜。
优选地，步骤(3)中的有机溶剂为四氢呋喃。
优选地，步骤(4)中的有机溶剂为乙腈。
进一步优选地，化合物(1)的具体制备方法为：
步骤(1)、将含23％的SO 3的发烟硫酸加入圆底烧瓶中，将丙酮缓慢滴加至反应体系，保持反应温度低于20℃，滴加完毕后于65-75℃搅拌10-20min，冷至室温后加入含75％的SO 3的发烟硫酸，再将丙酮缓慢滴加至反应体系，于70-80℃下反应50-70min，反应结束后冷却至室温，静置数小时后，浅黄色固体逐渐析出，过滤，用硝基甲烷洗涤滤饼得粗品，然后经硝基甲烷重结晶得白色固体即为化合物b；
步骤(2)、将化合物b和氯化亚砜分别加入反应容器中，回流搅拌20-30h，冷至室温后，过滤得粗产品，然后用少量甲苯洗涤数次，干燥得化合物c；
步骤(3)、将化合物c加入四氢呋喃中，于-5-5℃条件下缓慢加入乙烯基溴化镁，滴加完毕后升至室温，继续反应20-30h，反应结束后加入饱和氯化铵水溶液和乙腈溶液，分液，乙腈萃取水层，合并有机相，无水硫酸镁干燥，浓缩得化合物d；
步骤(4)、将化合物d加入乙腈中，再将三乙基硅烷加入反应体系，于-45--55℃条件下将三氟化硼乙醚溶液缓慢滴加至反应体系，于-75--85℃条件下搅拌20-40min，升温至室温继续搅拌50-70min，反应结束后，将饱和碳酸氢钠缓慢滴加入反应体系淬灭反应，分液，用乙腈萃取水相，合并有机相，无水硫酸钠干燥，浓缩得粗品，用乙腈重结晶得目标产物化合物(1)。
化合物(2)的合成路线为：
Figure PCTCN2017119155-appb-000004
化合物(2)的制备方法为：将化合物A、HgSO 4、H 2SO 4和水在90-110℃下反应得到化合物B，将化合物B、甲烷二磺酰氯在有机溶剂的存在下，在冰水浴中反应50-70min，然后在室温下搅拌反应4-6h得到化合物(2)。
本发明中，室温为0-40℃，优选为10-35℃，更优选为15-25℃。
优选地，所述的含磺酰基化合物的添加质量为所述的非水电解液总质量的0.01-10％。
进一步优选地，所述的含磺酰基化合物的添加质量为所述的非水电解液总质量的0.1-5％，更优选为1-5％，最优选为4-5％。
优选地，所述的添加剂还包括碳酸亚乙烯酯(VC)。
进一步优选地，所述的碳酸乙烯酯的添加质量为所述的非水电解液总质量的0.5-5％，更有选为0.5-2％。
进一步优选地，所述的添加剂的添加总质量为所述的非水电解液总质量的 0.01-10％，更有选为0.1-5％，最优选为4-5％。
优选地，所述的锂盐为选自六氟磷酸锂(LiPF 6)、四氟硼酸锂(LiBF 4)、六氟砷酸锂(LiAsF 6)、无水高氯酸锂(LiClO 4)、二(三氟甲基磺酸酰)亚胺锂(LiN(SO 2CF 3) 2)、三氟甲基磺酸锂(LiSO 3CF 3)、二草酸硼酸锂(LiC 2O 4BC 2O 4)、单草酸双氟硼酸锂(LiF 2BC 2O 4)、双氟磺酰亚胺锂(LiN(SO 2F) 2)中的一种或者几种。
进一步优选地，所述的锂盐的浓度为0.9-1.1mol/L。
优选地，所述的有机溶剂为选自碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、γ-丁内酯(GBL)、碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸甲乙酯(EMC)、碳酸甲丙酯(MPC)、丙酸甲酯(MP)、丙酸乙酯(EP)、丙酸丙酯(PP)、乙酸甲酯(MA)、乙酸乙酯(EA)、乙酸丙酯(PA)、丁酸甲酯(MB)、丁酸乙酯(EB)、丁酸丙酯(PB)、环丁砜、二乙二醇二甲醚、三乙二醇二甲醚中的一种或几种。
进一步优选地，所述的有机溶剂为质量比为1∶0.9-1.1∶0.9-1.1的碳酸乙烯酯、碳酸二甲酯和碳酸甲乙酯的混合溶剂。
进一步优选地，所述的有机溶剂为质量比为1∶0.9-1.1∶0.9-1.1的碳酸乙烯酯、碳酸二乙酯和碳酸甲乙酯的混合溶剂。
本发明的另一个目的是提供一种二次电池，包括所述的非水电解液。
优选地，所述的二次电池为锂离子二次电池。
优选地，所述的二次电池的正极和负极均能够吸收和解吸锂离子。
进一步优选地，所述的二次电池的正极活性物质为LiCoO 2或LiMn 2O 4，所述的二次电池的负极活性物质为石墨或Li 4Ti 5O 12。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
本发明通过采用含乙烯基含磺酰基的化合物作为添加剂，该两种结构的添加剂有助于电池电极表面形成保护膜，在电池充放电循环和高温存储过程中，该保护膜具有很高的稳定性，可以抑制电解液中溶剂分子的分解，减少分解产物在电极表面堆积导致的电池内阻升高，改善电池存储性能。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
实施例1：化合物(1)的制备：
将190g发烟硫酸(23％SO 3)加入圆底烧瓶中，将丙酮(17g)缓慢滴加至反应体系，保持反应温度低于20℃。滴加完毕后于70℃搅拌15min，冷至室温后加入50g发烟硫酸(75％SO 3)，再将丙酮(17g)缓慢滴加至反应体系，于75℃下反应1h。反应结束后冷却至室温，静置数小时后，浅黄色固体逐渐 析出，过滤，用硝基甲烷洗涤滤饼得粗品b(120g)，硝基甲烷重结晶得白色固体b(100g，收率为79％)。
将化合物b(100g)和氯化亚砜(500g)分别加入三颈烧瓶中，回流搅拌24h，冷至室温后，过滤得粗产品c，用少量甲苯洗涤数次，干燥得c(73g，收率为80％)。
将化合物c(70g)加入THF(300mL)中，于0℃条件下缓慢加入420mL乙烯基溴化镁的THF溶液，其中，乙烯基溴化镁在THF中的浓度为1.0M，滴加完毕后升至室温，继续反应24h，反应结束后加入饱和氯化铵水溶液(150mL)和乙腈溶液(300mL)，分液，乙腈萃取水层，合并有机相，无水硫酸镁干燥，浓缩得化合物d(64g，收率为80％)。
将化合物d(60g)加入500mL乙腈中，再将三乙基硅烷(60.5g)加入反应体系，于-50℃条件下将三氟化硼乙醚溶液(500g)缓慢滴加至反应体系，于-78℃条件下搅拌30min，升温至室温继续搅拌1h，反应结束后，将饱和碳酸氢钠缓慢滴加入反应体系淬灭反应，分液，用乙腈萃取水相，合并有机相，无水硫酸钠干燥，浓缩得粗品，用乙腈重结晶得目标产物化合物(1)(33g，收率为60％)。
实施例2：化合物(2)的制备：
将化合物A(600g)、HgSO 4(2.5g)、H 2SO 4(98％，3.5g)和50mL水分别加入三颈烧瓶中，100℃搅拌3h，反应结束后减压蒸馏得化合物B(370g，收率为62％)。将甲烷二磺酰氯(746g)加入1L THF中，将化合物B(308g)缓慢滴加至反应体系，滴加完毕后在冰水浴中搅拌1h，升温至室温后继续搅拌5h，反应结束后得白色固体(519g)，用乙腈重结晶得目标产物化合物(2)(480g，收率为60％)
实施例3：
[正极的制造]
按照质量比90∶5∶5称取LiCoO 2、导电炭黑和PVDF，加入适量NMP，充分搅拌，得到正极浆料。将正极浆料涂布在铝箔上，干燥后进行辊压、裁切得到正极。
[负极的制造]
按照质量比95∶3∶2称取石墨、丁苯橡胶和羧甲基纤维素，加入适量去离子水，充分搅拌，得到负极浆料。将负极浆料涂布在铜箔上，干燥后进行辊压、裁切得到负极。
[电解液的制备]
按照质量比1∶1∶1混合碳酸乙烯酯(EC)、碳酸二乙酯(DEC)和碳酸甲乙酯(EMC)得到混合溶剂，将六氟磷酸锂以1摩尔/升的浓度溶解于其中。加入实施例1制备得到的添加剂化合物(1)
Figure PCTCN2017119155-appb-000005
以得到含1wt％的化合物(1)的电解液。
[电池的制造]
使用上述正极、负极、电解液，选择厚度20微米的PE隔膜，采用卷绕工艺制造成软包电池，型号为053048。
[电池性能测试]
电池充放电测试在25℃条件下进行，电压范围是3.0-4.4V。将电池以0.1C倍率化成后，以0.2C倍率预循环5周。然后进行循环性能或存储性能测试。
循环性能测试是将电池按1C倍率进行充放电循环，测试500周循环后的容量保持率。
存储性能测试是将电池充电至4.4V，置于60度的烘箱中，存储7天。测试电池存储前后的内阻。内阻增加率＝[(存储后的内阻-存储前的内阻)/存储前的内阻]*100％。
实施例4：
除了电解液含3wt％的化合物(1)外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
实施例5：
除了电解液含5wt％的化合物(1)外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
实施例6：
除了化合物(1)用实施例2制得的化合物(2)
Figure PCTCN2017119155-appb-000006
来替代外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
实施例7：
除了电解液含2wt％的实施例1制得的化合物(1)和2wt％的实施例2制得的化合物(2)外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
实施例8：
除了电解液含2wt％的实施例1制得的化合物(1)、2wt％的实施例2制得的化合物(2)和1％的VC外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
对比例1：
除了电解液中不加入化合物(1)外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
对比例2：
除了化合物(1)用VC来替代外，电池以与实施例3相同的方式制造。电池性能测试以与实施例3相同的方式进行测试。
实施例1-6和对比例1-2的电池性能测试结果如表1所示。
表1
Figure PCTCN2017119155-appb-000007
与对比例1和2相比，实施例3-8中的电池具备改善的容量保持率、更低的内阻增加率，即电池具有更优的循环性能和存储性能。化合物(1)和(2)联用具有协同作用。
实施例9：
[正极的制造]
按照质量比90∶5∶5称取LiMn 2O 4、导电炭黑和PVDF，加入适量NMP，充 分搅拌，得到正极浆料。将正极浆料涂布在铝箔上，干燥后进行辊压、裁切得到正极。
[负极的制造]
按照质量比95∶3∶2称取Li 4Ti 5O 12、丁苯橡胶和羧甲基纤维素，加入适量去离子水，充分搅拌，得到负极浆料。将负极浆料涂布在铜箔上，干燥后进行辊压、裁切得到负极。
[电解液的制备]
按照质量比1∶1∶1混合碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)得到混合溶剂，将六氟磷酸锂以1摩尔/升的浓度溶解于其中。加入实施例2制得的添加剂化合物(2)
Figure PCTCN2017119155-appb-000008
以得到含1wt％的化合物(2)的电解液。
[电池的制造]
使用上述正极、负极、电解液，选择厚度20微米的PE隔膜，采用卷绕工艺制造成圆柱电池，型号为18650。
[电池性能测试]
电池充放电测试在25℃条件下进行，电压范围是1.5-2.7V。将电池以0.1C倍率化成后，0.2C倍率预循环5周。然后进行循环性能或存储性能测试。
循环性能测试是将电池按1C倍率进行充放电循环，测试800周循环后的容量保持率。
存储性能测试是将电池充电至2.7V，置于60度的烘箱中，存储7天。测试电池存储前后的内阻。内阻增加率＝[(存储后的内阻-存储前的内阻)/存储前的内阻]*100％。
实施例10：
除了电解液含3wt％的实施例2制得的化合物(2)外，电池以与实施例9相同的方式制造。电池性能测试以与实施例9相同的方式进行测试。
实施例11：
除了电解液含5wt％的实施例2制得的化合物(2)外，电池以与实施例9 相同的方式制造。电池性能测试以与实施例9相同的方式进行测试。
实施例12：
除了化合物(2)用实施例1制得的化合物(1)来替代外，电池以与实施例9相同的方式制造。电池性能测试以与实施例9相同的方式进行测试。
实施例13：
除了电解液含2wt％的实施例1制得的化合物(1)和2wt％的实施例2制得的化合物(2)外，电池以与实施例9相同的方式制造。电池性能测试以与实施例9相同的方式进行测试。
对比例3：
除了电解液中不加入化合物(2)外，电池以与实施例9相同的方式制造。电池性能测试以与实施例9相同的方式进行测试。
对比例4：
除了化合物(2)用1，3-丙烷磺内酯(1，3-PS)来替代外，电池以与实施例9相同的方式制造。电池性能测试以与实施例9相同的方式进行测试。
实施例9-13和对比例3-4的电池性能测试结果如表2所示。
表2
Figure PCTCN2017119155-appb-000009
Figure PCTCN2017119155-appb-000010
与对比例3和4相比，实施例9-13中的电池具备改善的容量保持率、更低的内阻增加率，即电池具有更优的循环性能和存储性能。化合物(1)和(2)联用具有协同作用。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (14)

  1. 一种非水电解液，包括锂盐、有机溶剂和添加剂，其特征在于：所述的添加剂包括含磺酰基化合物，所述的含磺酰基化合物为化合物(1)和/或化合物(2)，其中，化合物(1)的结构式为：
    Figure PCTCN2017119155-appb-100001
    化合物(2)的结构式为：
    Figure PCTCN2017119155-appb-100002
  2. 根据权利要求1所述的非水电解液，其特征在于：所述的含磺酰基化合物的添加质量为所述的非水电解液总质量的0.01-10％。
  3. 根据权利要求2所述的非水电解液，其特征在于：所述的含磺酰基化合物的添加质量为所述的非水电解液总质量的0.1-5％。
  4. 根据权利要求1所述的非水电解液，其特征在于：所述的添加剂还包括碳酸亚乙烯酯。
  5. 根据权利要求4所述的非水电解液，其特征在于：所述的碳酸乙烯酯的添加质量为所述的非水电解液总质量的0.5-5％。
  6. 根据权利要求1所述的非水电解液，其特征在于：所述的锂盐为选自六氟磷酸锂、四氟硼酸锂、六氟砷酸锂、无水高氯酸锂、二(三氟甲基磺酸酰)亚胺锂、三氟甲基磺酸锂、二草酸硼酸锂、单草酸双氟硼酸锂、双氟磺酰亚胺锂中的一种或者几种。
  7. 根据权利要求1所述的非水电解液，其特征在于：所述的有机溶剂为选自碳酸乙烯酯、碳酸丙烯酯、γ-丁内酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丁酸乙酯、丁酸丙酯、环丁砜、二乙二醇二甲醚、三乙二醇二甲醚中的一种或几种。
  8. 根据权利要求1所述的非水电解液，其特征在于：所述的化合物(1)的合成路线为：
    Figure PCTCN2017119155-appb-100003
  9. 根据权利要求8所述的非水电解液，其特征在于：所述的化合物(1)由如下步骤制得：
    步骤(1)、向发烟硫酸中滴加丙酮，然后在65-75℃下反应，降温至室温后，向反应体系中加入发烟硫酸，然后再向反应体系中滴加丙酮，在70-80℃下反应，反应结束后经后处理得到化合物b；
    步骤(2)、将化合物b在有机溶剂的存在下进行回流搅拌反应，反应结束后，经后处理得到化合物c；
    步骤(3)、将化合物c与乙烯基溴化镁在有机溶剂的存在下进行反应，反应结束后经后处理得到化合物d；
    步骤(4)、将化合物d、三乙基硅烷和三氟化硼乙醚溶液在有机溶剂的存在下，在-75--85℃下反应20-40min，然后在室温下反应50-70min，反应结束后，经后处理得到化合物(1)。
  10. 根据权利要求1所述的非水电解液，其特征在于：所述的化合物(2)的合成路线为：
    Figure PCTCN2017119155-appb-100004
  11. 根据权利要求10所述的非水电解液，其特征在于：所述的化合物(2)由如下步骤制得：将化合物A、HgSO 4、H 2SO 4和水在90-110℃下反应得到化合物B，将化合物B、甲烷二磺酰氯在有机溶剂的存在下，在冰水浴中反应50-70min，然后在室温下搅拌反应4-6h得到化合物(2)。
  12. 一种二次电池，其特征在于：包括权利要求1至11中任一项所述的非水电解液。
  13. 根据权利要求12所述的二次电池，其特征在于：所述的二次电池为锂离子二次电池。
  14. 根据权利要求12所述的二次电池，其特征在于：所述的二次电池的正极和负极均能够吸收和解吸锂离子。
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