WO2018218390A1 - 一种锂电池用基于离子液体的准固态电解质及其制备方法 - Google Patents

一种锂电池用基于离子液体的准固态电解质及其制备方法 Download PDF

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WO2018218390A1
WO2018218390A1 PCT/CN2017/000400 CN2017000400W WO2018218390A1 WO 2018218390 A1 WO2018218390 A1 WO 2018218390A1 CN 2017000400 W CN2017000400 W CN 2017000400W WO 2018218390 A1 WO2018218390 A1 WO 2018218390A1
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ionic liquid
solid electrolyte
quasi
lithium
salt
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French (fr)
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陈人杰
陈楠
吴锋
王丽莉
戴玉娟
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北京理工大学
陈人杰
陈楠
吴锋
王丽莉
戴玉娟
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Priority to JP2020517245A priority Critical patent/JP6951806B2/ja
Publication of WO2018218390A1 publication Critical patent/WO2018218390A1/zh
Priority to US16/699,729 priority patent/US11631886B2/en

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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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • 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 invention relates to an ionic liquid-based quasi-solid electrolyte for a lithium battery and a preparation method thereof, and belongs to the technical field of lithium secondary batteries.
  • Metal lithium has the highest theoretical capacity (3860 mAh/g) and extremely low reduction potential, making it an ideal negative electrode.
  • the use of metallic lithium as a negative electrode is essential for the development of Li-S batteries and Li-O 2 batteries.
  • the stable metal lithium/electrolyte interface is a prerequisite for ensuring the safety and long cycle life of metal lithium batteries.
  • One of the improvement strategies is to replace the liquid electrolyte with a solid electrolyte, mainly to avoid the occurrence of continuous side reactions of the liquid electrolyte, and to suppress the formation of lithium dendrites by utilizing the mechanical and electrochemical properties of the solid electrolyte.
  • the ionic liquid has the characteristics of good thermal stability, high electrical conductivity, wide electrochemical window and low vapor pressure, and has great application potential in lithium secondary battery electrolyte materials.
  • ionic liquids exist in liquid form at room temperature, and there is a risk of liquid leakage during long-term use of the battery. Therefore, the quasi-solid electrolyte obtained by curing the ionic liquid will effectively improve the problem of leakage.
  • the materials for curing ionic liquids can be divided into two categories: one is an organic polymer matrix and the other is an inorganic matrix. These materials have a porous network structure that is primarily responsible for mechanical strength while providing a large adsorption space for the loaded ionic liquid. Chen Renjie's group reported a quasi-solid electrolyte with ionic liquid supported by mesoporous SiO 2 or TiO 2 (Chem. Mater. 2016, 28, 848-856, Adv. Mater.
  • Patent CN 106058312 A discloses a solid-state ionic liquid electrolyte, a preparation method thereof and an application thereof, which is an epoxy ether-modified silica skeleton as a material for curing an ionic liquid, and is suitable for use in the field of lithium secondary batteries. .
  • the COC group on the epoxy ether group has a lone pair of electrons and has a strong coordination with lithium ions.
  • the present invention aims to provide an ionic liquid-based quasi-solid electrolyte for a lithium battery and a preparation method thereof, in view of problems such as lithium dendrite formation and low coulombic efficiency existing in a lithium battery during a charge and discharge cycle, and the preparation method thereof.
  • the electrolyte has high ionic conductivity, and can stabilize the metal lithium stripping/deposition process and inhibit the growth of lithium dendrites; the method is simple in process, easy to obtain raw materials, safe and pollution-free, and suitable for mass production.
  • An ionic liquid-based quasi-solid electrolyte for a lithium battery being a porous network structure prepared by a condensation reaction of a lithium salt, an ionic liquid, a silane coupling agent and a catalyst.
  • the lithium salt is one or more of LiN(SO 2 CF 3 ) 2 , LiCF 3 SO 3 and LiC(SO 2 CF 3 ) 3 .
  • the ionic liquid is preferably an ionic liquid in which the anion is a bistrifluoromethanesulfonimide salt, more preferably 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, 1-propyl-3-methyl Imidazole bistrifluoromethanesulfonimide salt, 1-butyl-3-methylimidazolium bistrifluoromethanesulfonimide salt, N-methyl, propyl piperidine bistrifluoromethanesulfonimide salt , N-methyl, butyl piperidine bistrifluoromethanesulfonimide salt, N-methyl, propyl pyrrolidine bistrifluoromethanesulfonimide salt, and N-methyl, butyl pyrrolidine double More than one of trifluoromethanesulfonimide salts.
  • the anion is a bistrifluoromethanesulfonimide salt, more
  • the silane coupling agent is an organosilicon compound containing an acryloyl group, preferably 3-methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropylmethyldimethoxysilane, and One or more of 3-methacryloxypropyltriethoxysilane.
  • the catalyst is formic acid, acetic acid or water.
  • a method for preparing an ionic liquid-based quasi-solid electrolyte for a lithium battery according to the present invention the method steps are as follows:
  • the lithium salt is first dissolved in the ionic liquid and stirred uniformly to obtain an ionic liquid electrolyte; then the silane coupling agent is added and uniformly mixed, and finally the catalyst is added. Mixing uniformly to obtain a reaction system;
  • reaction system obtained in the step (1) is removed from the glove box and placed in a vacuum drying oven having a relative vacuum of -70 KPa to -100 KPa, and dried at 25 ° C to 90 ° C to obtain the quasi-solid electrolyte.
  • the concentration of the lithium salt is 0.35 mol/L to 2 mol/L; the mass ratio of the silane coupling agent to the ionic liquid electrolyte is 0.15 to 0.6:1; the molar amount of the catalyst and the silane coupling agent The molar ratio is preferably 5.5 to 8.5:1.
  • the shielding gas is nitrogen or argon having a purity of not less than 99%.
  • the quasi-solid electrolyte of the present invention can stabilize the process of stripping/deposition of metallic lithium, inhibit the growth of lithium dendrites, and exhibit low overpotential and long-term cycle stability during constant current polarization.
  • the interfacial impedance of the lithium metal sheet and the quasi-solid electrolyte is small, and hardly increases with the increase of the battery standing time; the quasi-solid electrolyte has good high temperature resistance, and the thermal decomposition temperature is greater than 340 ° C, so that the battery can be Works within a wide temperature range.
  • Example 1 is a surface scanning electron microscope (SEM) image of a quasi-solid electrolyte prepared in Example 1.
  • FIG 2 is a acryloyloxy prepared in Example 1 in a modified scanning electron microscope of the embodiment of FIG SiO 2.
  • Example 3 is a cross-sectional scanning electron micrograph of the quasi-solid electrolyte prepared in Example 1.
  • FIG. 4 is a graph showing a constant current plating/peeling of a lithium symmetrical battery prepared using the quasi-solid electrolyte prepared in Example 1 at a current density of 0.1 mA/cm 2 .
  • Lithium-symmetric battery assembly in a glove box filled with argon gas with a purity of 99% or more, a lithium metal sheet, a quasi-solid electrolyte prepared in the embodiment, and a lithium metal sheet are sequentially placed in a button battery case of model 2032, and then The two battery cases were compacted by a tableting machine to obtain a metal lithium symmetrical battery.
  • the assembled lithium-symmetrical battery was allowed to stand at 30 ° C for 48 h, and then tested for electrochemical performance: AC impedance test was performed on an electrochemical workstation (CHI660D, Shanghai Chenhua Instrument Co., Ltd.), and the test frequency ranged from 10 Hz to 105 Hz. The AC amplitude is 5mV and the test temperature is 30°C.
  • the LAND battery test system (model CT2001A, Wuhan Jinnuo Electronics Co., Ltd.) is used for metal lithium deposition/peel test. The constant current density is 0.1mA/cm 2 and the deposition capacity is 0.1 mAh.
  • Thermogravimetric analyzer Model TG209F1, Netzsch, Germany.
  • reaction system obtained in the step (1) was removed from the glove box and placed in a vacuum drying oven having a relative vacuum of -80 KPa, and dried at 50 ° C for 7 days to obtain an ionic liquid-based quasi-solid electrolyte for a lithium battery.
  • the quasi-solid electrolyte prepared in this example has a smooth surface without cracks.
  • the obtained quasi-solid electrolyte was washed three times with an acetonitrile solvent to remove the ionic liquid, and then vacuum dried at 70 ° C for 12 h to obtain acryl-modified SiO 2 , which was characterized by SEM morphology. It is seen that the acryl-modified SiO 2 has a porous network structure which is advantageous for carrying a large amount of ionic liquid.
  • the quasi-solid electrolyte prepared in the present embodiment the ionic liquid is filled into the porous network structure.
  • the quasi-solid electrolyte prepared in this example and the lithium sheet were assembled into a lithium symmetrical battery, and the electrochemical performance test was performed. According to the test results of FIG. 4, the overpotential of the lithium symmetrical battery at a current density of 0.1 mV/cm 2 was 70mV, stable cycle 600h and no short circuit occurred; no lithium dendrites appeared on the lithium wafer interface after 600h cycle.
  • reaction system obtained in the step (1) was removed from the glove box and placed in a vacuum drying oven having a relative vacuum of -100 KPa, and dried at 70 ° C for 7 days to obtain an ionic liquid-based quasi-solid electrolyte for a lithium battery.
  • the prepared quasi-solid electrolyte has a smooth surface without cracks, and the ionic liquid is filled into the porous network structure.
  • the quasi-solid electrolyte prepared in this example has a conductivity of 25 ° C of 1.02 ⁇ 10 -3 s/cm, an electrochemical window of 0-5.0 V (vs Li/Li + ), and an initial thermal decomposition temperature of 340 ° C.
  • the quasi-solid electrolyte prepared in this example and the lithium sheet were assembled into a lithium symmetrical battery, and the electrochemical performance test was performed. According to the test results, the overpotential of the lithium symmetrical battery at a current density of 0.032 mV/cm 2 was 60 mV, which was stable. The cycle was 1000h and no short circuit occurred; no lithium dendrites appeared on the lithium wafer interface after 1000h of cycle.
  • reaction system obtained in the step (1) was removed from the glove box, and placed in a vacuum drying oven having a relative vacuum of -90 KPa, and dried at 90 ° C for 5 d to obtain an ionic liquid-based quasi-solid electrolyte for a lithium battery.
  • the prepared quasi-solid electrolyte has a smooth surface without cracks, and the ionic liquid is filled into the porous network structure. It has been tested that the quasi-solid electrolyte prepared in this example has a conductivity of 25 ⁇ C of 1.8 ⁇ 10 -3 s/cm, an electrochemical window of 0-5.0 V (vs Li/Li + ), and an initial thermal decomposition temperature of 340 ° C.
  • reaction system obtained in the step (1) was removed from the glove box and placed in a vacuum drying oven having a relative vacuum of -100 KPa, and dried at 80 ° C for 7 days to obtain an ionic liquid-based quasi-solid electrolyte for a lithium battery.
  • the prepared quasi-solid electrolyte surface is smooth and free of cracks, and the ionic liquid is filled into the porous network structure.
  • the quasi-solid electrolyte prepared in this example has a conductivity of 25 ° C of 1.02 ⁇ 10 -5 s/cm, an electrochemical window of 0-5.0 V (vs Li/Li + ), and an initial thermal decomposition temperature of 340 ° C.
  • reaction system obtained in the step (1) was removed from the glove box and placed in a vacuum drying oven having a relative vacuum of -100 KPa, and dried at 70 ° C for 7 days to obtain an ionic liquid-based quasi-solid electrolyte for a lithium battery.
  • the prepared quasi-solid electrolyte surface is smooth and free of cracks, and the ionic liquid is filled into the porous network structure.
  • the quasi-solid electrolyte prepared in this example has a conductivity of 1.22 ⁇ 10 -3 s/cm at 25 ° C, an electrochemical window of 0 to 5.0 V (vs Li/Li + ), and an initial thermal decomposition temperature of 340 ° C.
  • the quasi-solid electrolyte prepared in this example and the lithium sheet were assembled into a lithium symmetrical battery, and the electrochemical performance test was performed. According to the test results, the overpotential of the lithium symmetrical battery at a current density of 0.5 mV/cm 2 was 0.4 mV. Stable cycle 1000h and no short circuit occurred; no lithium dendrite appeared on the lithium wafer interface after 1000h cycle.

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Abstract

一种锂电池用基于离子液体的准固态电解质及其制备方法，属于锂二次电池技术领域。所述准固态电解质是由锂盐、离子液体、硅烷偶联剂和催化剂发生缩合反应制备得到的多孔网络结构，具有高的离子电导率；所述准固态电解质能够稳定金属锂的剥离/沉积的过程，抑制锂枝晶的生长，而且在恒电流极化过程中展现出较低的过电势和长期的循环稳定性；金属锂片与所述准固态电解质界面阻抗较小，且几乎不随着电池放置时间的增加而增大。准固态电解质的制备过程简单，所使用的都是常规设备，原材料易得，且安全无污染，适合大规模批量生产。

Description

一种锂电池用基于离子液体的准固态电解质及其制备方法 技术领域
本发明涉及一种锂电池用基于离子液体的准固态电解质及其制备方法，属于锂二次电池技术领域。
背景技术
金属锂具有最高的理论容量(3860mAh/g)和极低的还原电位，是十分理想的负极。采用金属锂作为负极对发展Li-S电池和Li-O2电池至关重要。然而电池充放电循环过程锂枝晶的形成和低的库伦效率等问题严重阻碍金属锂电池的商业化。稳定的金属锂/电解质界面是保障金属锂电池安全性和长循环寿命的前提。改善策略之一是采用固态化电解质等替代液态电解液，主要是避免液体电解质的持续副反应的发生，同时利用固态电解质的力学和电化学特性抑制锂枝晶的形成。
离子液体具有热稳定性好、电导率高、电化学窗口宽、蒸汽压低等特点，在锂二次电池电解质材料方面具有很大的应用潜力。通常离子液体在室温下以液态的形式存在，在电池长时间使用过程中存在液体泄漏的风险。因此，将离子液体固化后得到的准固态电解质，将有效改善泄漏的问题。
固化离子液体的材料可以分为两类：一类是有机聚合物基体，另一类无机基体。这类材料具有多孔网络结构，主要负责机械强度，同时为负载离子液体提供大的吸附空间。陈人杰课题组报道了以介孔SiO2或TiO2负载离子液体的准固态电解质(Chem.Mater.2016，28，848-856，Adv.Mater.2011，23，5081-5085)，但是由于TiO2和SiO2在电池工作的电压区间为电化学惰性物质，不具备离子传导功能，阻碍了离子液体的离子传导，使得固化后的离子液体电解质的电导率降低。专利CN 106058312 A中报道了一种固态化离子液体电解质、其制备方法及应用，该电解质是由环氧醚基修饰的二氧化硅骨架作为固化离子液体的材料，适合应用在锂二次电池领域。环氧醚基上的C-O-C基团具有孤对电子，与锂离子具有较强的配位作用，环氧醚基的引入有效的促进了锂盐的解离和锂离子的迁移。因此，二氧化硅骨架上链接的官能团在很大程度上决定了体系的物理化 学性质，进而对电解质的性能产生较大的影响。然而，目前对于有机修饰的二氧化硅负载离子液体得到的准固态电解质在金属锂电池上的应用尚无研究报道。
发明内容
针对现有锂电池在充放电循环过程中存在的锂枝晶形成和低库伦效率等问题，本发明的目的在于提供一种锂电池用基于离子液体的准固态电解质及其制备方法，所述的电解质具有高的离子电导率，而且能够稳定金属锂的剥离/沉积过程，抑制锂枝晶的生长；所述方法过程简单，原料易得且安全无污染，适合大规模批量生产。
本发明的目的是通过以下技术方案实现的。
一种锂电池用基于离子液体的准固态电解质，所述准固态电解质是由锂盐、离子液体、硅烷偶联剂和催化剂发生缩合反应制备得到的多孔网络结构。
所述锂盐为LiN(SO2CF3)2、LiCF3SO3和LiC(SO2CF3)3中的一种以上。
所述离子液体优选阴离子为双三氟甲磺酰亚胺盐的离子液体，更优选1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-丙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐、N-甲基，丙基哌啶双三氟甲磺酰亚胺盐、N-甲基，丁基哌啶双三氟甲磺酰亚胺盐、N-甲基，丙基吡咯烷双三氟甲磺酰亚胺盐，和N-甲基，丁基吡咯烷双三氟甲磺酰亚胺盐中的一种以上。
所述硅烷偶联剂为含有丙烯酰基的有机硅化合物，优选3-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷，和3-甲基丙烯酰氧丙基三乙氧基硅烷中的一种以上。
所述催化剂为甲酸、乙酸或水。
一种本发明所述的锂电池用基于离子液体的准固态电解质的制备方法，所述方法步骤如下：
(1)在充满保护气体且水分含量小于1ppm的手套箱中，先将锂盐溶于离子液体中并搅拌均匀，得到离子液体电解液；再加入硅烷偶联剂并混合均匀，最后加入催化剂，混合均匀，得到反应体系；
(2)将步骤(1)得到的反应体系移出手套箱，并置于相对真空度为-70KPa～-100KPa的真空干燥箱中，在25℃～90℃下干燥，得到所述准固态电解质。
离子液体电解液中，锂盐的浓度为0.35mol/L～2mol/L；硅烷偶联剂的质量与离子液体电解液的质量比为0.15～0.6∶1；催化剂的摩尔量与硅烷偶联剂的摩尔量比优选5.5～8.5∶1。
所述保护气体为纯度不小于99％的氮气或氩气。
有益效果：
(1)本发明所述的准固态电解质具有多孔网络结构，能够负载大量的离子液体；另外，丙烯酸官能团上的C＝O和C-O-C的孤对电子能够与锂离子配位，促进锂盐的解离，提高电解质中自由Li+的数量，因此，本发明所述的准固态电解质具有高的离子电导率(10-3S/cm～10-2S/cm，0℃～100℃)。
(2)本发明所述的准固态电解质能够稳定金属锂的剥离/沉积的过程，抑制锂枝晶的生长，而且在恒电流极化过程中展现出较低的过电势和长期的循环稳定性；金属锂片与所述准固态电解质界面阻抗较小，且几乎不随着电池放置时间的增加而增大；所述准固态电解质耐高温性能好，热分解温度大于340℃，从而可以使电池在宽温度范围内正常工作。
(3)本发明所述准固态电解质的制备过程简单，所使用的都是常规设备，原材料易得，且安全无污染，适合大规模批量生产。
附图说明
图1为实施例1中制备的准固态电解质的表面扫描电子显微镜(SEM)图。
图2为实施例1中制备的丙烯酰修饰的SiO2的扫描电子显微镜图。
图3为实施例1中制备的准固态电解质的截面扫描电子显微镜图。
图4为采用实施例1制备的准固态电解质制备的锂对称电池在0.1mA/cm2电流密度下测得的恒电流电镀/剥离图。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步说明。
以下实施例中：
锂对称电池的组装：在充满纯度大于等于99％氩气的手套箱中，将金属锂片、实施例中制备的准固态电解质、金属锂片依次放入型号为2032的纽扣电池壳中，然后用压片机将两片电池壳压实扣紧，得到金属锂对称电池。
组装好的锂对称电池在30℃下静置48h后，进行电化学性能测试：在电化学工作站(CHI660D，上海晨华仪器有限公司)上进行交流阻抗的测试，测试频率范围为10Hz～105Hz，交流振幅为5mV，测试温度为30℃；采用LAND电池测试***(型号CT2001A，武汉金诺电子有限公司)进行金属锂的沉积/剥离测试，测试恒电流密度为0.1mA/cm2，沉积容量为0.1mAh。
扫描电子显微镜：型号Quanta 600，荷兰FEI公司；
热重分析仪：型号TG209F1，德国Netzsch公司。
实施例1
(1)在充满纯度大于等于99％氩气且水分含量小于1ppm的手套箱中，先将0.91g LiN(SO2CF3)2溶于4.6g N-甲基，丙基吡咯烷双三氟甲磺酰亚胺盐中，并搅拌24h，得到离子液体电解液；再加入2.8g 3-甲基丙烯酰氧基丙基三甲氧基硅烷并混合均匀；最后加入2.5mL纯度大于98％的甲酸，继续搅拌8min，得到反应体系；
(2)将步骤(1)得到的反应体系移出手套箱，并置于相对真空度为-80KPa的真空干燥箱中，在50℃下干燥7d，得到锂电池用基于离子液体的准固态电解质。
从图1中的SEM图可以看出，本实施例所制备的准固态电解质表面光滑没有裂纹。将所得到的准固态电解质用乙腈溶剂清洗三次，以去除离子液体，然后再在70℃下真空干燥12h，得到丙烯酰修饰的SiO2，并对其进行SEM形貌表征，从图2中可以看出，丙烯酰修饰的SiO2具有多孔网络结构，该结构有利于承载大量的离子液体。结合图2和图3可知，本实施例所制备的准固态电解质中，离子液体填充到了多孔的网络结构中。经过测试可知，本实施例所制备的准固态电解质的25℃电导率为1.37×10-3s/cm，电化学窗口为0～4.5V(vs Li/Li+)，起始热分解温度为340℃。
将本实施例所制备的准固态电解质与锂片组装成锂对称电池，并进行电化学性能测试：根据图4的测试结果可知，锂对称电池在0.1mV/cm2电流密度下的过电势为70mV，稳定循环600h且无短路发生；循环600h后锂片界面上无锂枝晶出现。
实施例2
(1)在充满纯度大于等于99％氩气且水分含量小于1ppm的手套箱中，先将1.82g LiN(SO2CF3)2溶于4.6g N-甲基，丙基吡咯烷双三氟甲磺酰亚胺盐中，并搅拌24h，得到离子液体电解液；再加入0.7g 3-甲基丙烯酰氧基丙基三甲氧基硅烷和0.82g 3-甲基丙烯酰氧丙基三乙氧基硅烷并混合均匀；最后加入1.25mL纯度大于98％的甲酸，继续搅拌8min，得到反应体系；
(2)将步骤(1)得到的反应体系移出手套箱，并置于相对真空度为-100KPa的真空干燥箱中，在70℃下干燥7d，得到锂电池用基于离子液体的准固态电解质。
从本实施例所制备的准固态电解质的SEM图中可以得知，所制备的准固态电解质表面光滑没有裂纹，离子液体填充到了多孔的网络结构中。经过测试可知，本实施例所制备的准固态电解质的25℃电导率为1.02×10-3s/cm，电化学窗口为0～5.0V(vs Li/Li+)，起始热分解温度为340℃。
将本实施例所制备的准固态电解质与锂片组装成锂对称电池，并进行电化学性能测试：根据测试结果可知，锂对称电池在0.032mV/cm2电流密度下的过电势为60mV，稳定循环1000h且无短路发生；循环1000h后锂片界面上无锂枝晶出现。
实施例3
(1)在充满纯度大于等于99％氩气且水分含量小于1ppm的手套箱中，先将4.368g LiN(SO2CF3)2溶于4.6g N-甲基，丙基吡咯烷双三氟甲磺酰亚胺盐和10.1g N-甲基，丙基哌啶双三氟甲磺酰亚胺盐中，并搅拌24h，得到离子液体电解液；再加入1.4g 3-甲基丙烯酰氧基丙基三甲氧基硅烷、0.82g 3-甲基丙烯酰氧丙基三乙氧基硅烷和0.65gγ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷并混合均匀；最后加入1.62g的高纯水，继续搅拌15min，得到反应体系；
(2)将步骤(1)得到的反应体系移出手套箱，并置于相对真空度为-90KPa的真空干燥箱中，在90℃下干燥5d，得到锂电池用基于离子液体的准固态电解质。
从本实施例所制备的准固态电解质的SEM图中可以得知，所制备的准固态电解质表面光滑没有裂纹，离子液体填充到了多孔的网络结构中。经过测试可 知，本实施例所制备的准固态电解质的25℃电导率为1.8×10-3s/cm，电化学窗口为0～5.0V(vs Li/Li+)，起始热分解温度为340℃。
实施例4
(1)在充满纯度大于等于99％氩气且水分含量小于1ppm的手套箱中，先将0.182g LiN(SO2CF3)2和0.100g LiCF3SO3溶于2.3g N-甲基，丙基吡咯烷双三氟甲磺酰亚胺盐和2.3g N-甲基，丁基吡咯烷双三氟甲磺酰亚胺盐中，并搅拌24h，得到离子液体电解液；再加入2.8g 3-甲基丙烯酰氧基丙基三甲氧基硅烷并混合均匀；最后加入3.6mL纯度大于98％的甲酸，继续搅拌8min，得到反应体系；
(2)将步骤(1)得到的反应体系移出手套箱，并置于相对真空度为-100KPa的真空干燥箱中，在80℃下干燥7d，得到锂电池用基于离子液体的准固态电解质。
所制备的准固态电解质表面光滑没有裂纹，离子液体填充到了多孔的网络结构中。经过测试可知，本实施例所制备的准固态电解质的25℃电导率为1.02×10-5s/cm，电化学窗口为0～5.0V(vs Li/Li+)，起始热分解温度为340℃。
实施例5
(1)在充满纯度大于等于99％氩气且水分含量小于1ppm的手套箱中，先将0.662g LiC(SO2CF3)3和0.247g LiCF3SO3溶于4.6g N-甲基，丁基吡咯烷双三氟甲磺酰亚胺盐中，并搅拌24h，得到离子液体电解液；再加入2.8g 3-甲基丙烯酰氧基丙基三甲氧基硅烷并混合均匀；最后加入3.6mL纯度大于98％的甲酸，继续搅拌8min，得到反应体系；
(2)将步骤(1)得到的反应体系移出手套箱，并置于相对真空度为-100KPa的真空干燥箱中，在70℃下干燥7d，得到锂电池用基于离子液体的准固态电解质。
所制备的准固态电解质表面光滑没有裂纹，离子液体填充到了多孔的网络结构中。经过测试可知，本实施例所制备的准固态电解质的25℃电导率为1.12×10-3s/cm，电化学窗口为0～5.0V(vs Li/Li+)，起始热分解温度为340℃。
将本实施例所制备的准固态电解质与锂片组装成锂对称电池，并进行电化 学性能测试：根据测试结果可知，锂对称电池在0.5mV/cm2电流密度下的过电势为0.4mV，稳定循环1000h且无短路发生；循环1000h后锂片界面上无锂枝晶出现。
综上所述，以上仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (6)

  1. 一种锂电池用基于离子液体的准固态电解质，其特征在于：所述准固态电解质是由锂盐、离子液体、硅烷偶联剂和催化剂发生缩合反应制备得到的多孔网络结构；
    所述锂盐为LiN(SO2CF3)2、LiCF3SO3和LiC(SO2CF3)3中的一种以上；
    所述硅烷偶联剂为含有丙烯酰基的有机硅化合物；
    所述催化剂为甲酸、乙酸或水。
  2. 根据权利要求1所述的一种锂电池用基于离子液体的准固态电解质，其特征在于：所述离子液体选用阴离子为双三氟甲磺酰亚胺盐的离子液体。
  3. 根据权利要求2所述的一种锂电池用基于离子液体的准固态电解质，其特征在于：所述离子液体为1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-丙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐、N-甲基，丙基哌啶双三氟甲磺酰亚胺盐、N-甲基，丁基哌啶双三氟甲磺酰亚胺盐、N-甲基，丙基吡咯烷双三氟甲磺酰亚胺盐，和N-甲基，丁基吡咯烷双三氟甲磺酰亚胺盐中的一种以上。
  4. 根据权利要求1所述的一种锂电池用基于离子液体的准固态电解质，其特征在于：所述硅烷偶联剂为3-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷，和3-甲基丙烯酰氧丙基三乙氧基硅烷中的一种以上。
  5. 一种如权利要求1至4任一项所述的锂电池用基于离子液体的准固态电解质的制备方法，其特征在于：所述方法步骤如下：
    (1)在充满保护气体且水分含量小于1ppm的手套箱中，先将锂盐溶于离子液体中并搅拌均匀，得到离子液体电解液；再加入硅烷偶联剂并混合均匀，最后加入催化剂，混合均匀，得到反应体系；
    (2)将反应体系移出手套箱，并置于相对真空度为-70KPa～-100KPa的真空干燥箱中，在25℃～90℃下干燥，得到所述准固态电解质；
    所述保护气体为纯度不小于99％的氮气或氩气。
  6. 根据权利要求5所述的一种锂电池用基于离子液体的准固态电解质的制备方法，其特征在于：离子液体电解液中，锂盐的浓度为0.35mol/L～2mol/L；硅烷偶联剂的质量与离子液体电解液的质量比为0.15～0.6∶1；催化剂的摩尔量与硅烷偶联剂的摩尔量比为5.5～8.5∶1。
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