CN110854437A - A lithium-sulfur battery electrolyte containing multifunctional additives and its application - Google Patents

A lithium-sulfur battery electrolyte containing multifunctional additives and its application Download PDF

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CN110854437A
CN110854437A CN201911248701.6A CN201911248701A CN110854437A CN 110854437 A CN110854437 A CN 110854437A CN 201911248701 A CN201911248701 A CN 201911248701A CN 110854437 A CN110854437 A CN 110854437A
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张强
张学强
金奇
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    • HELECTRICITY
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Abstract

本发明公开了属于可充放的高比能二次电池技术领域的一种含有多功能添加剂的锂硫电池电解液及其应用。本发明电解液包括有机溶剂、锂盐和多功能添加剂,所述多功能添加剂为具有R1‑O‑R2化学结构式的化合物中的一种或多种;所述R1、R2相同或不同,R1或R2选自C1‑C8烷烃基、C2‑C8烯烃基、C3‑C8环烷基、C3‑C8杂环烷基或部分不饱和C3‑C8环烃基;所述C3‑C8环烷基、C3‑C8杂环烷基或部分不饱和C3‑C8环烃基的环结构含或不含取代基。本发明通过引入多功能醚类添加剂,减少了活性物质硫和锂的流失,增强了电池的循环稳定性,抑制了电解液中的多硫化物与金属锂之间的化学反应,提升电池的库伦效率。

Figure 201911248701

The invention discloses a lithium-sulfur battery electrolyte containing multifunctional additives and its application, belonging to the technical field of rechargeable high specific energy secondary batteries. The electrolyte of the present invention comprises an organic solvent, a lithium salt and a multifunctional additive, wherein the multifunctional additive is one or more of compounds having the chemical structural formula of R 1 -O-R 2 ; the R 1 and R 2 are the same or Different, R 1 or R 2 is selected from C1-C8 alkane, C2-C8 alkene, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl or partially unsaturated C3-C8 cycloalkyl; the C3-C8 The ring structure of cycloalkyl, C3-C8 heterocycloalkyl or partially unsaturated C3-C8 cycloalkyl group may or may not be substituted. The invention reduces the loss of active material sulfur and lithium by introducing multifunctional ether additives, enhances the cycle stability of the battery, inhibits the chemical reaction between the polysulfide in the electrolyte and the metal lithium, and improves the coulomb of the battery. efficiency.

Figure 201911248701

Description

一种含有多功能添加剂的锂硫电池电解液及其应用A lithium-sulfur battery electrolyte containing multifunctional additives and its application

技术领域technical field

本发明属于可充放的高比能二次电池技术领域,特别涉及一种含有多功能添加剂的锂硫电池电解液及其应用。The invention belongs to the technical field of rechargeable high specific energy secondary batteries, and particularly relates to a lithium-sulfur battery electrolyte containing multifunctional additives and its application.

背景技术Background technique

随着新能源技术的不断发展,特别是随着智能通讯设备和电动汽车领域对于高能量密度二次电池的迫切需求。对高能量密度储能以及转换装置的研究具有实际意义。相比于传统锂离子电池依靠锂离子的嵌入和脱出进行储能,从电化学角度来说,多电子反应材料体系是构建高比能二次电池的基础。其中,锂硫电池因具有非常高的理论比容量(1672mAh/g)和理论能量密度(2570Wh/kg),且硫价格低廉,储量丰富,已经成为下一代新锂二次电池的重点研究对象。With the continuous development of new energy technologies, especially with the urgent demand for high energy density secondary batteries in the fields of intelligent communication equipment and electric vehicles. The research on high energy density energy storage and conversion devices has practical significance. Compared with traditional lithium-ion batteries, which rely on the intercalation and deintercalation of lithium ions for energy storage, from an electrochemical point of view, multi-electron reactive material systems are the basis for building high specific energy secondary batteries. Among them, lithium-sulfur batteries have become the key research objects of next-generation new lithium secondary batteries because of their very high theoretical specific capacity (1672mAh/g) and theoretical energy density (2570Wh/kg), low price of sulfur and abundant reserves.

锂硫电池虽然具有很多优点,但是目前仍然没有实现商业化,其主要原因是在锂硫电池充放电过程中中间产物多硫化锂会溶解在传统醚类电解液中,在电场和浓度场的双重作用下在正负极之间迁移即“穿梭效应”。一方面,穿梭效应会降低活性物质的利用率;另一方面,多硫化锂还会与金属锂负极发生不可逆的化学反应,腐蚀金属锂,造成严重的锂枝晶问题和锂负极的快速失效,严重影响锂硫电池的库伦效率和循环寿命。目前对锂硫电池的研究进展主要集中在正极材料部分,通过正极结构的设计和引入化学的吸附作用,可以有效抑制多硫化锂的穿梭反应。但是,一方面,这样会造成成本的增加,另一方面还需要复杂的电极材料设计,不利于锂硫电池的大范围应用和推广。通过引入功能性添加剂在金属锂表面形成稳定的SEI是一种有效保护金属锂负极的方法,但是由于添加剂的量较少,且在循环过程中的不断消耗造成较差的长期循环稳定性。Although lithium-sulfur batteries have many advantages, they have not yet been commercialized. The main reason is that during the charging and discharging process of lithium-sulfur batteries, the intermediate product lithium polysulfide will dissolve in traditional ether electrolytes. The migration between the positive and negative electrodes under the action is the "shuttle effect". On the one hand, the shuttle effect will reduce the utilization rate of active materials; on the other hand, lithium polysulfides will also have irreversible chemical reactions with the metal lithium anode, corroding the metal lithium, causing serious lithium dendrite problems and rapid failure of the lithium anode. It seriously affects the coulombic efficiency and cycle life of lithium-sulfur batteries. At present, the research progress of lithium-sulfur batteries mainly focuses on the cathode material part. Through the design of the cathode structure and the introduction of chemical adsorption, the shuttle reaction of lithium polysulfides can be effectively inhibited. However, on the one hand, this will increase the cost, and on the other hand, it requires complex electrode material design, which is not conducive to the wide-scale application and promotion of lithium-sulfur batteries. The formation of stable SEI on the surface of metallic lithium by introducing functional additives is an effective method to protect metallic lithium anodes, but the poor long-term cycling stability is caused by the small amount of additives and the continuous consumption during cycling.

通过改变电解液的溶剂组成以缓解金属锂的腐蚀和大幅度提升锂硫电池的循环稳定和库伦效率,是一种简单、经济、长期有效的方法。因此,研发能显著提高和电池循环寿命的锂硫电池电解液成为当下的研究热点。但是,受制于多电子转化机制的复杂性和多硫化物的不稳定性,锂硫电解液的研发面临极大的挑战。It is a simple, economical and long-term effective method to alleviate the corrosion of metal lithium and greatly improve the cycle stability and Coulomb efficiency of lithium-sulfur batteries by changing the solvent composition of the electrolyte. Therefore, the development of lithium-sulfur battery electrolytes that can significantly improve battery cycle life has become a current research hotspot. However, due to the complexity of the multi-electron conversion mechanism and the instability of polysulfides, the research and development of lithium-sulfur electrolytes faces great challenges.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种含有多功能添加剂的锂硫电池电解液及其应用,具体技术方案如下:The object of the present invention is to provide a kind of lithium-sulfur battery electrolyte and application thereof containing multifunctional additive, and the concrete technical scheme is as follows:

一种含有多功能添加剂的锂硫电池电解液,包括有机溶剂、锂盐和多功能添加剂,所述多功能添加剂为具有R1-O-R2化学结构式的化合物中的一种或多种;A lithium-sulfur battery electrolyte containing a multifunctional additive, comprising an organic solvent, a lithium salt and a multifunctional additive, wherein the multifunctional additive is one or more of compounds with the chemical structural formula of R 1 -OR 2 ;

所述R1、R2相同或不同,R1或R2选自C1-C8烷烃基、C2-C8烯烃基、C3-C8环烷基、C3-C8杂环烷基或部分不饱和C3-C8环烃基;The R 1 and R 2 are the same or different, and R 1 or R 2 are selected from C1-C8 alkane, C2-C8 alkenyl, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl or partially unsaturated C3- C8 cyclic hydrocarbon group;

本发明所述自C1-C8烷烃基、C2-C8烯烃基为直链或支链烃基。The self-C1-C8 alkane group and C2-C8 alkene group described in the present invention are straight-chain or branched-chain hydrocarbon groups.

本发明所述C3-C8环烷基、C3-C8杂环烷基或部分不饱和C3-C8环烃基的环结构含或不含取代基。The ring structure of the C3-C8 cycloalkyl group, the C3-C8 heterocycloalkyl group or the partially unsaturated C3-C8 cycloalkyl group of the present invention contains or does not contain a substituent.

本发明所述C3-C8杂环烷基中杂原子为氮原子、硫原子或氧原子;所述部分不饱和C3-C8环烃基包括C3-C8环烯基、苯基、取代苯基。The heteroatom in the C3-C8 heterocycloalkyl group of the present invention is a nitrogen atom, a sulfur atom or an oxygen atom; the partially unsaturated C3-C8 cycloalkyl group includes a C3-C8 cycloalkenyl group, a phenyl group, and a substituted phenyl group.

所述C3-C8环烷基、C3-C8杂环烷基或部分不饱和C3-C8环烃基环结构上的取代基为C1-C6烷基、C1-C6烯烃基、氨基、苯基、卤素。The substituents on the C3-C8 cycloalkyl, C3-C8 heterocycloalkyl or partially unsaturated C3-C8 cyclohydrocarbyl ring structure are C1-C6 alkyl, C1-C6 alkenyl, amino, phenyl, halogen .

所述有机溶剂为1,3-二氧五环、1,4-二氧六环、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、四氢呋喃、乙基甲基砜、环丁砜、异丙基甲基砜、二甲基亚砜、二甲基三硫醚、二甲基二硫醚、二甲基硫醚中的一种或多种。The organic solvent is 1,3-dioxane, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol One of dimethyl ether, tetrahydrofuran, ethyl methyl sulfone, sulfolane, isopropyl methyl sulfone, dimethyl sulfoxide, dimethyl trisulfide, dimethyl disulfide, dimethyl sulfide or more.

所述锂盐为六氟磷酸锂、二草酸硼酸锂、双三氟甲烷磺酰亚胺锂(LiTFSI)、双氟磺酰亚胺锂、高氯酸锂、二氟草酸硼酸锂、硝酸锂和三氟甲磺酸锂中的一种或多种。The lithium salt is lithium hexafluorophosphate, lithium bis-oxalate borate, lithium bis-trifluoromethanesulfonimide (LiTFSI), lithium bis-fluorosulfonimide, lithium perchlorate, lithium difluorooxalate borate, lithium nitrate and trifluoromethane One or more of lithium sulfonates.

所述锂盐在锂硫电池电解液中的浓度为0.1~4mol/L,多功能添加剂体积为锂硫电池电解液体积的5-80%。The concentration of the lithium salt in the lithium-sulfur battery electrolyte is 0.1-4 mol/L, and the volume of the multifunctional additive is 5-80% of the volume of the lithium-sulfur battery electrolyte.

所述锂硫电池电解液还含有辅助添加剂,所述辅助添加剂为硝酸锂、多硫化锂、硝酸钾、硝酸铯、溴化锂中的一种或多种。The lithium-sulfur battery electrolyte also contains auxiliary additives, and the auxiliary additives are one or more of lithium nitrate, lithium polysulfide, potassium nitrate, cesium nitrate, and lithium bromide.

所述辅助添加剂为锂硫电池电解液质量的0.1%~5%。The auxiliary additive is 0.1% to 5% of the mass of the lithium-sulfur battery electrolyte.

将所述锂硫电池电解液用于制备锂硫电池。所述锂硫电池包括正极、负极、隔膜和所述锂硫电池电解液;所述正极的活性物质为单质硫、含硫聚合物、硫化锂、多硫化锂中的一种或多种;所述负极为金属锂箔、锂片、锂合金中的任意一种。The lithium-sulfur battery electrolyte is used to prepare a lithium-sulfur battery. The lithium-sulfur battery includes a positive electrode, a negative electrode, a separator, and an electrolyte for the lithium-sulfur battery; the active material of the positive electrode is one or more of elemental sulfur, sulfur-containing polymer, lithium sulfide, and lithium polysulfide; The negative electrode is any one of metal lithium foil, lithium sheet, and lithium alloy.

本发明的有益效果为:The beneficial effects of the present invention are:

(1)本发明提供的含有多功能添加剂的锂硫电池电解液,一方面抑制了电解液中的多硫化物与金属锂之间的化学反应;另一方面,改变金属锂的沉积形貌,增强金属锂沉积的均匀性,有效的避免了金属锂负极的快速消耗、死锂的产生和枝晶的生长等问题调控金属锂的沉积行为,避免锂负极被高浓度的多硫化物腐蚀,降低电解液中多硫化物的浓度。即本发明通过引入多功能醚类添加剂,减少了活性物质——硫和锂的流失,提升电池的库伦效率,增强了电池的循环稳定性。(1) The lithium-sulfur battery electrolyte containing multifunctional additives provided by the present invention, on the one hand, inhibits the chemical reaction between polysulfides in the electrolyte and metal lithium; on the other hand, changes the deposition morphology of metal lithium, Enhance the uniformity of metal lithium deposition, effectively avoid the rapid consumption of metal lithium anode, the generation of dead lithium and the growth of dendrites, etc. Regulate the deposition behavior of metal lithium, avoid the corrosion of lithium anode by high concentration of polysulfides, reduce electrolysis The concentration of polysulfides in the liquid. That is, the present invention reduces the loss of active substances—sulfur and lithium, by introducing multifunctional ether additives, improves the coulombic efficiency of the battery, and enhances the cycle stability of the battery.

(2)本发明提供的含有多功能添加剂的锂硫电池电解液成分简单、成本低,可应用于高硫载量的硫正极,是一种非常具有研究价值和产业化潜力的锂硫电池电解液。(2) The lithium-sulfur battery electrolyte containing multifunctional additives provided by the present invention is simple in composition and low in cost, and can be applied to a sulfur positive electrode with high sulfur loading, and is a lithium-sulfur battery electrolyte with great research value and industrialization potential. liquid.

附图说明Description of drawings

附图1为本发明实施例2锂硫电池的循环性能与库伦效率;Accompanying drawing 1 is the cycle performance and Coulomb efficiency of lithium-sulfur battery in Example 2 of the present invention;

附图2为本发明对比例2锂硫电池的循环性能与库伦效率。Figure 2 shows the cycle performance and Coulomb efficiency of the lithium-sulfur battery in Comparative Example 2 of the present invention.

具体实施方式Detailed ways

本发明提供了一种含有多功能添加剂的锂硫电池电解液及其应用,下面结合实施例和附图对本发明做进一步的说明。The present invention provides a lithium-sulfur battery electrolyte containing multifunctional additives and its application. The present invention will be further described below with reference to the embodiments and accompanying drawings.

本发明所述锂硫电池包括正极、负极、隔膜和电解液。本发明所述的正极包括正极集流体以及复合在正极集流体表面的正极材料;所述正极集流体为本领域具有优异导电性的集流器,如铝箔。The lithium-sulfur battery of the present invention includes a positive electrode, a negative electrode, a separator and an electrolyte. The positive electrode of the present invention includes a positive electrode current collector and a positive electrode material compounded on the surface of the positive electrode current collector; the positive electrode current collector is a current collector with excellent conductivity in the field, such as aluminum foil.

所述的正极材料由正极活性材料与导电剂、粘结剂和溶剂的浆料固化得到,其中导电剂、粘结剂和溶剂均为本领域常用材料。The positive electrode material is obtained by solidifying the slurry of the positive electrode active material, a conductive agent, a binder and a solvent, wherein the conductive agent, the binder and the solvent are all commonly used materials in the art.

本发明实施例选用锂硫电池常规使用的碳纳米管作为正极活性物质硫的载体,与导电剂乙炔黑、粘结剂聚偏氟乙烯和溶剂NMP制备正极材料,具体操作为:In the embodiment of the present invention, carbon nanotubes commonly used in lithium-sulfur batteries are used as the carrier of positive active material sulfur, and the positive electrode material is prepared with conductive agent acetylene black, binder polyvinylidene fluoride and solvent NMP, and the specific operations are as follows:

(1)取30g多壁碳纳米管(MWCNT)与70g商业硫粉混合,在600rpm的转速下球磨6h得到均匀混合的粉末MWCNT/S;将球磨混合物MWCNT/S,乙炔黑和聚偏氟乙烯按照8:1:1的比例在N-甲基吡咯烷酮(NMP)溶液中混合均匀,得到制备好的浆料;(1) Mix 30g of multi-walled carbon nanotubes (MWCNTs) with 70g of commercial sulfur powder, and ball-mill at 600rpm for 6h to obtain a uniformly mixed powder MWCNT/S; ball-mill the mixture of MWCNT/S, acetylene black and polyvinylidene fluoride Mix uniformly in N-methylpyrrolidone (NMP) solution according to the ratio of 8:1:1 to obtain the prepared slurry;

(2)将浆料均匀涂布于铝箔上,60℃下烘干12h后,剪裁成直径为13mm的极片,放入手套箱中除水待用。(2) The slurry was evenly coated on aluminum foil, dried at 60°C for 12h, cut into pole pieces with a diameter of 13mm, and put into a glove box to remove water for use.

本发明实施例选用型号Celgard 2400的聚丙烯微孔膜作为隔膜。In the embodiment of the present invention, a polypropylene microporous membrane of model Celgard 2400 is used as the diaphragm.

实施例Example

电解液配置:在充满氩气的手套箱内(O2,H2O含量均<0.1ppm),将乙二醇二甲醚(DME)、1,3-二氧五环(DOL)、二乙二醇二甲醚(G2)、三乙二醇二甲醚(G3)、四乙二醇二甲醚(G4)、四氢呋喃(THF)、二甲基亚砜(DMSO)、二甲基三硫醚(DMTS)中两种或两种以上的混合液作为有机溶剂。加入电解液总质量的0.1-5%的辅助添加剂,加入电解液总体积5-80%的多功能添加剂,加入锂盐,并使得锂盐在电解液中浓度为1.0mol/L(M),充分搅拌均匀,即得到锂硫电池电解液。Electrolyte configuration: in a glove box filled with argon (O 2 , H 2 O content are both < 0.1ppm), ethylene glycol dimethyl ether (DME), 1,3-dioxane (DOL), dioxane Ethylene glycol dimethyl ether (G2), triethylene glycol dimethyl ether (G3), tetraethylene glycol dimethyl ether (G4), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethyl trimethyl ether The mixed solution of two or more kinds of sulfide (DMTS) is used as the organic solvent. Add auxiliary additives of 0.1-5% of the total mass of the electrolyte, add multifunctional additives of 5-80% of the total volume of the electrolyte, add lithium salt, and make the concentration of lithium salt in the electrolyte to be 1.0mol/L (M), Fully stirring, the lithium-sulfur battery electrolyte is obtained.

在氩气气氛中,以金属锂片为负极,隔膜选用型号Celgard 2400的聚丙烯微孔膜,电解液用量为15μL/mg S,按次序组装成CR2025锂硫电池。In an argon atmosphere, a metal lithium sheet was used as the negative electrode, a polypropylene microporous membrane of type Celgard 2400 was used as the diaphragm, and the electrolyte dosage was 15 μL/mg S, and CR2025 lithium-sulfur batteries were assembled in sequence.

以不同组分含量的电解液组装锂硫电池,得到实施例1-10;以不加入辅助添加剂的电解液组装锂硫电池,得到实施例11-15;以不同的有机溶剂组成,添加与实施例1-3相同的功能性添加剂和辅助添加剂的电解液组装锂硫电池,得到了实施例16-18。Lithium-sulfur batteries were assembled with electrolytes with different component contents to obtain Examples 1-10; Lithium-sulfur batteries were assembled with electrolytes without auxiliary additives to obtain Examples 11-15; composed of different organic solvents, added and implemented Examples 1-3 The same functional additives and auxiliary additives were used to assemble a lithium-sulfur battery, and Examples 16-18 were obtained.

对比例1Comparative Example 1

以不加入多功能添加剂和辅助添加剂配制的电解液,即含有有机溶剂和锂盐的电解液作为对比例1,具体操作为:在充满氩气的手套箱内(O2,H2O含量均<0.1ppm),将体积比为1:1的乙二醇二甲醚(DME)和1,3-二氧五环(DOL)的混合液作为有机溶剂,加入锂盐,并使得锂盐在电解液中浓度为1.0M,充分搅拌均匀,即得到锂硫电池电解液。 The electrolyte prepared without adding multifunctional additives and auxiliary additives, namely the electrolyte containing organic solvent and lithium salt, was taken as Comparative Example 1 . <0.1ppm), using the mixture of ethylene glycol dimethyl ether (DME) and 1,3-dioxane (DOL) with a volume ratio of 1:1 as an organic solvent, adding lithium salt, and making the lithium salt in The concentration of the electrolyte is 1.0M, and the electrolyte is fully stirred to obtain a lithium-sulfur battery electrolyte.

在氩气气氛中,以金属锂片为负极,隔膜选用型号Celgard 2400的聚丙烯微孔膜,电解液用量为15μL/mg S,按次序组装成锂硫电池。In an argon atmosphere, a lithium metal sheet was used as the negative electrode, a polypropylene microporous membrane of type Celgard 2400 was used as the diaphragm, and the electrolyte dosage was 15 μL/mg S, and the lithium-sulfur batteries were assembled in sequence.

对比例2Comparative Example 2

以不加入多功能添加剂配制的电解液,即含有有机溶剂、锂盐和辅助添加剂的电解液作为对比例2,具体操作为:在充满氩气的手套箱内(O2,H2O含量均<0.1ppm),将体积比为1:1的乙二醇二甲醚(DME)和1,3-二氧五环(DOL)的混合液作为有机溶剂;加入电解液总质量2%无水硝酸锂(LiNO3)作为辅助添加剂;加入锂盐,并使得锂盐在电解液中浓度为1.0M,充分搅拌均匀,即得到锂硫电池电解液。 The electrolyte prepared without adding multifunctional additives, that is, the electrolyte containing organic solvent, lithium salt and auxiliary additives, was taken as Comparative Example 2 . <0.1ppm), the mixed solution of ethylene glycol dimethyl ether (DME) and 1,3-dioxane (DOL) with a volume ratio of 1:1 was used as the organic solvent; 2% anhydrous electrolyte was added to the total mass of the electrolyte Lithium nitrate (LiNO 3 ) is used as an auxiliary additive; lithium salt is added, and the concentration of the lithium salt in the electrolyte is 1.0M, and the electrolyte is fully stirred to obtain a lithium-sulfur battery electrolyte.

在氩气气氛中,以金属锂片为负极,隔膜选用型号Celgard 2400的聚丙烯微孔膜,电解液用量为15μL/mg S,按次序组装成锂硫电池。In an argon atmosphere, a lithium metal sheet was used as the negative electrode, a polypropylene microporous membrane of type Celgard 2400 was used as the diaphragm, and the electrolyte dosage was 15 μL/mg S, and the lithium-sulfur batteries were assembled in sequence.

实施例1-18、对比例1、对比例2锂硫电池电解液中组分种类及其含量如表1所示:Examples 1-18, Comparative Example 1, Comparative Example 2 The types of components and their contents in the lithium-sulfur battery electrolyte are shown in Table 1:

表1Table 1

Figure BDA0002308412260000071
Figure BDA0002308412260000071

Figure BDA0002308412260000081
Figure BDA0002308412260000081

将实施例1-18、对比例1、对比例2制备好的电池置于25℃的恒温室中静置12h后,在蓝电测试充放电测试仪上进行充放电循环测试,测试条件为恒流0.5C(1C=1672mAh/g)充放,电位区间为1.7~2.6V,循环200圈。The batteries prepared in Examples 1-18, Comparative Example 1, and Comparative Example 2 were placed in a constant temperature room at 25°C for 12 hours, and then a charge-discharge cycle test was performed on a blue-electric test charge-discharge tester. The test conditions were constant. Flow 0.5C (1C=1672mAh/g) charge and discharge, the potential range is 1.7 ~ 2.6V, cycle 200 times.

实施例1-18、对比例1、对比例2电池的循环性能和库伦效率如表2所示:The cycle performance and Coulomb efficiency of the batteries of Examples 1-18, Comparative Example 1 and Comparative Example 2 are shown in Table 2:

表2Table 2

Figure BDA0002308412260000091
Figure BDA0002308412260000091

对比分析实施例11-15和对比例1,实施例11-15电池的首圈放电比容量与对比例1无明显区别,200圈循环容量保持率达到72.6%~75.2%,库伦效率达到91.5%~93.4%,远高于对比例1中200圈循环容量保持率40.5%、库伦效率64.2%。说明本发明多功能添加剂的单独使用能够大幅度提升电池的容量保持率和库伦效率。Comparative analysis of Example 11-15 and Comparative Example 1 shows that the first cycle discharge specific capacity of the battery of Example 11-15 is not significantly different from that of Comparative Example 1, the 200-cycle cycle capacity retention rate reaches 72.6% to 75.2%, and the coulombic efficiency reaches 91.5% ~93.4%, much higher than the 200-cycle capacity retention rate of 40.5% and the Coulomb efficiency of 64.2% in Comparative Example 1. It shows that the single use of the multifunctional additive of the present invention can greatly improve the capacity retention rate and Coulomb efficiency of the battery.

对比分析实施例1-10和对比例2,实施例1-10在0.5C的放电倍率下,首圈放电比容量与对比例2无明显区别,200圈循环容量保持率达到78.6%~90.3%,库伦效率94.6%~99.5%,均远高于对比例2中200圈循环容量保持率57.5%,库伦效率89.6%。说明本发明多功能添加剂还适用于大幅提升电解液中含有硝酸锂、溴化锂等非溶剂性物质的电池的循环性能和库伦效率。Comparative analysis of Example 1-10 and Comparative Example 2, Example 1-10 at a discharge rate of 0.5C, the first cycle of discharge specific capacity and Comparative Example 2 have no significant difference, 200 cycles of capacity retention rate reached 78.6% ~ 90.3% , the Coulombic efficiency is 94.6% to 99.5%, which are much higher than the 200-cycle capacity retention rate of 57.5% in Comparative Example 2, and the Coulombic efficiency is 89.6%. It shows that the multifunctional additive of the present invention is also suitable for greatly improving the cycle performance and Coulombic efficiency of batteries containing non-solvent substances such as lithium nitrate and lithium bromide in the electrolyte.

对比分析实施例1-10和对比例1,实施例1-10在0.5C的放电倍率下,首圈放电比容量与对比例1无明显区别,200圈循环容量保持率达到78.6%~90.3%,库伦效率94.6%~99.5%,均远高于对比例1中40.5%的200圈循环容量保持率、64.2%的库伦效率。可见,同时添加本发明的辅助添加剂和多功能添加剂,可以显著提升循环容量保持率和库伦效率。Comparative analysis of Example 1-10 and Comparative Example 1, Example 1-10 at a discharge rate of 0.5C, the first cycle of discharge specific capacity and Comparative Example 1 have no significant difference, the 200-cycle cycle capacity retention rate reaches 78.6% ~ 90.3% , the Coulombic efficiency is 94.6%-99.5%, which are much higher than the 200-cycle capacity retention rate of 40.5% and the Coulombic efficiency of 64.2% in Comparative Example 1. It can be seen that adding the auxiliary additive and the multifunctional additive of the present invention at the same time can significantly improve the cycle capacity retention rate and the coulombic efficiency.

对比实施例11-15、实施例1-10可以发现,实施例1-10的200圈循环容量保持率、库伦效率均大于实施例11-15。说明本发明的辅助添加剂和多功能添加剂能产生协同效果,可以进一步提升电池循环性能和库伦效率。Comparing Examples 11-15 and Example 1-10, it can be found that the 200-cycle capacity retention rate and Coulomb efficiency of Example 1-10 are higher than those of Example 11-15. It shows that the auxiliary additive and the multifunctional additive of the present invention can produce synergistic effect, and can further improve the battery cycle performance and Coulomb efficiency.

对比实施例1-3、实施例16-18可以发现,首圈放电容量、200圈循环容量保持率、平均库伦效率均无明显区别。说明本发明的多功能添加剂适用于不同体系有机溶剂。Comparing Examples 1-3 and Examples 16-18, it can be found that there is no significant difference in the discharge capacity of the first cycle, the retention rate of the 200-cycle cycle capacity, and the average Coulomb efficiency. It is indicated that the multifunctional additive of the present invention is suitable for organic solvents of different systems.

Claims (10)

1.一种含有多功能添加剂的锂硫电池电解液,其特征在于,包括有机溶剂、锂盐和多功能添加剂,所述多功能添加剂为具有R1-O-R2化学结构式的化合物中的一种或多种;1. a lithium-sulfur battery electrolyte containing a multifunctional additive, is characterized in that, comprises organic solvent, lithium salt and multifunctional additive, and described multifunctional additive is a kind of in the compound with R 1 -OR 2 chemical structural formula or more; 所述R1、R2相同或不同,R1或R2选自C1-C8烷烃基、C2-C8烯烃基、C3-C8环烷基、C3-C8杂环烷基或部分不饱和C3-C8环烃基;The R 1 and R 2 are the same or different, and R 1 or R 2 are selected from C1-C8 alkane, C2-C8 alkenyl, C3-C8 cycloalkyl, C3-C8 heterocycloalkyl or partially unsaturated C3- C8 cyclic hydrocarbon group; 所述C3-C8环烷基、C3-C8杂环烷基或部分不饱和C3-C8环烃基的环结构含或不含取代基。The ring structure of the C3-C8 cycloalkyl group, the C3-C8 heterocycloalkyl group or the partially unsaturated C3-C8 cycloalkyl group contains or does not contain a substituent. 2.根据权利要求1所述的锂硫电池电解液,其特征在于,所述C3-C8杂环烷基中杂原子为氮原子、硫原子或氧原子;所述部分不饱和C3-C8环烃基包括C3-C8环烯基、苯基、取代苯基。2. The lithium-sulfur battery electrolyte according to claim 1, wherein the heteroatom in the C3-C8 heterocycloalkyl group is a nitrogen atom, a sulfur atom or an oxygen atom; the partially unsaturated C3-C8 ring Hydrocarbyl includes C3-C8 cycloalkenyl, phenyl, substituted phenyl. 3.根据权利要求1所述的锂硫电池电解液,其特征在于,所述C3-C8环烷基、C3-C8杂环烷基或部分不饱和C3-C8环烃基环结构上的取代基为C1-C6烷基、C1-C6烯烃基、氨基、苯基、卤素。3. The lithium-sulfur battery electrolyte according to claim 1, wherein the substituents on the C3-C8 cycloalkyl, C3-C8 heterocycloalkyl or partially unsaturated C3-C8 cyclohydrocarbyl ring structure For C1-C6 alkyl, C1-C6 alkenyl, amino, phenyl, halogen. 4.根据权利要求1所述的锂硫电池电解液,其特征在于,所述有机溶剂为1,3-二氧五环、1,4-二氧六环、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、四乙二醇二甲醚、四氢呋喃、乙基甲基砜、环丁砜、异丙基甲基砜、二甲基亚砜、二甲基三硫醚、二甲基二硫醚、二甲基硫醚中的一种或多种。4. The lithium-sulfur battery electrolyte according to claim 1, wherein the organic solvent is 1,3-dioxane, 1,4-dioxane, ethylene glycol dimethyl ether, dioxane ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethyl methyl sulfone, sulfolane, isopropyl methyl sulfone, dimethyl sulfoxide, dimethyl trisulfoxide One or more of sulfide, dimethyl disulfide and dimethyl sulfide. 5.根据权利要求1所述的锂硫电池电解液,其特征在于,所述锂盐为六氟磷酸锂、二草酸硼酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、高氯酸锂、二氟草酸硼酸锂、硝酸锂和三氟甲磺酸锂中的一种或多种。5. The lithium-sulfur battery electrolyte according to claim 1, wherein the lithium salt is lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethanesulfonimide, lithium bisfluorosulfonimide, lithium One or more of lithium chlorate, lithium difluorooxalate borate, lithium nitrate and lithium trifluoromethanesulfonate. 6.根据权利要求1所述的锂硫电池电解液,其特征在于,所述锂盐在锂硫电池电解液中的浓度为0.1~4mol/L,多功能添加剂体积为锂硫电池电解液体积的5-80%。6 . The lithium-sulfur battery electrolyte according to claim 1 , wherein the concentration of the lithium salt in the lithium-sulfur battery electrolyte is 0.1 to 4 mol/L, and the volume of the multifunctional additive is the volume of the lithium-sulfur battery electrolyte. 7 . 5-80%. 7.根据权利要求1所述的锂硫电池电解液,其特征在于,所述锂硫电池电解液还含有辅助添加剂,所述辅助添加剂为硝酸锂、多硫化锂、硝酸钾、硝酸铯、溴化锂中的一种或多种。7. The lithium-sulfur battery electrolyte according to claim 1, wherein the lithium-sulfur battery electrolyte also contains auxiliary additives, and the auxiliary additives are lithium nitrate, lithium polysulfide, potassium nitrate, cesium nitrate, lithium bromide one or more of. 8.根据权利要求7所述的锂硫电池电解液,其特征在于,所述辅助添加剂为锂硫电池电解液质量的0.1%~5%。8 . The lithium-sulfur battery electrolyte according to claim 7 , wherein the auxiliary additive is 0.1% to 5% of the mass of the lithium-sulfur battery electrolyte. 9 . 9.权利要求1-8任一项所述锂硫电池电解液的应用,其特征在于,所述锂硫电池电解液用于制备锂硫电池。9 . The application of the lithium-sulfur battery electrolyte according to claim 1 , wherein the lithium-sulfur battery electrolyte is used to prepare a lithium-sulfur battery. 10 . 10.根据权利要求9所述的应用,其特征在于,所述锂硫电池包括正极、负极、隔膜和所述锂硫电池电解液;所述正极的活性物质为单质硫、含硫聚合物、硫化锂、多硫化锂中的一种或多种;所述负极为金属锂箔、锂片、锂合金中的任意一种。10. The application according to claim 9, wherein the lithium-sulfur battery comprises a positive electrode, a negative electrode, a separator and an electrolyte for the lithium-sulfur battery; the active material of the positive electrode is elemental sulfur, sulfur-containing polymer, One or more of lithium sulfide and lithium polysulfide; the negative electrode is any one of metal lithium foil, lithium sheet, and lithium alloy.
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