WO2021098685A1 - 一种固态聚合物电解质、其制备方法及锂电池 - Google Patents

一种固态聚合物电解质、其制备方法及锂电池 Download PDF

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WO2021098685A1
WO2021098685A1 PCT/CN2020/129495 CN2020129495W WO2021098685A1 WO 2021098685 A1 WO2021098685 A1 WO 2021098685A1 CN 2020129495 W CN2020129495 W CN 2020129495W WO 2021098685 A1 WO2021098685 A1 WO 2021098685A1
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polymer electrolyte
electrolyte
solid polymer
solid
solution
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French (fr)
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刘国华
陆子恒
陈佳华
羿井司
杨铮
李�诚
杨春雷
钟国华
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01M10/052—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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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 the technical field of lithium battery electrolyte preparation, in particular to a solid polymer electrolyte, a preparation method thereof and a lithium battery.
  • lithium-ion batteries have a wide range of application markets.
  • High-energy-density lithium-ion batteries are the main direction pursued by researchers, which require lithium-ion batteries with high-capacity electrodes and stable electrolytes.
  • lithium-ion batteries there are great safety hazards due to the growth of lithium dendrites, the leakage of liquid electrolyte, and combustion.
  • gel polymer electrolytes and solid electrolytes have become a hot research field for more and more scholars.
  • solid electrolytes have received more extensive research due to their higher mechanical strength and ionic conductivity. Higher mechanical strength can inhibit the growth of lithium dendrites, and good ion conductivity is conducive to ion transmission.
  • the in-situ polymerization method is: use an initiator on the electrode to directly polymerize the nanoparticles and organic molecules, reducing the electrode and the solid electrolyte. The interface resistance between them improves the performance of the battery.
  • the solid electrolyte obtained by the current in-situ polymerization method still has the problem of low electrochemical window.
  • the present invention provides a solid polymer electrolyte with an electrochemical window greater than 5 V and a preparation method thereof, and further provides A lithium battery including the solid polymer electrolyte.
  • the present invention provides a solid polymer electrolyte, including in-situ polymerized basic electrolyte, inorganic powder and initiator, wherein the basic electrolyte is a mixture of lithium salt, polymerized monomer and additives.
  • the inorganic powder is selected from at least one of conductive ceramic powder, Al 2 O 3 , SiO 2 and TiO 2.
  • the conductive ceramic powder is at least one of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 , Li 7 La 3 Zr 2 O 12 , Li 10 GeP 2 S 12 and Li 1.5 Al 0.5 Ge 1.5 P 3 O 12 One kind.
  • the lithium salt is selected from at least one of lithium bis(fluorosulfonyl)imide, lithium bistrifluoromethanesulfonimide, and lithium bisoxalate;
  • the polymerized monomer is selected from ether groups Polymeric monomers;
  • the additives are selected from carbonates.
  • the polymerized monomer is selected from 1,3-dioxolane or ethylene glycol dimethyl ether; the additive is selected from at least one of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate .
  • the initiator is selected from at least one of Al(OTF) 3 , Al(CF 3 SO 3 ) 3 , LiPF 6 , diethyl aluminum chloride and ethyl aluminum dichloride.
  • the mass fraction of the base electrolyte is 15% to 95%
  • the mass fraction of the inorganic powder is 5% to 57%
  • the mass fraction of the initiator is 0.2% to 44%.
  • the amount concentration of the lithium salt is 1-7 mol/L.
  • the present invention also provides a method for preparing the above solid polyelectrolyte, which includes the steps:
  • step S3 it specifically includes: first adding an initiator to the first solution, stirring and mixing to obtain a second solution, and allowing the second solution to perform in-situ polymerization reaction at 25°C to 70°C.
  • the present invention further provides a lithium battery including a positive electrode, a negative electrode, and an electrolyte arranged between the positive electrode and the negative electrode, and the electrolyte adopts the above-mentioned solid polymer electrolyte.
  • the preparation method of the solid polymer electrolyte provided by the present invention takes inorganic powder, initiator, lithium salt, polymer monomer and additives as raw materials for polymerization reaction.
  • the preparation method is simple and can be prepared to obtain a stable electrochemical window higher than 5 V. Solid polymer electrolyte with excellent performance.
  • Figure 1 is a physical diagram of a solid polymer electrolyte in an embodiment of the present invention
  • Example 2 is an SEM image of the solid polymer electrolyte in Example 1;
  • Example 3 is a graph of electrochemical impedance of the solid polymer electrolyte in Example 2.
  • Example 4 is a graph of cyclic voltammetry of the solid polymer electrolyte in Example 2.
  • Fig. 5 is a graph of the charge-discharge cycle test curve of the lithium battery sample in Example 2 at a rate of 1 C.
  • the inventor of the present invention Based on the problem that the electrochemical window of the solid electrolyte obtained by the in-situ polymerization method in the prior art is not high, the inventor of the present invention provides a solid polymer electrolyte with an electrochemical window greater than 5V and a preparation method thereof, and further provides Lithium battery with material electrolyte.
  • the lithium salt is added to the polymerized monomer and additives, and mixed to form a basic electrolyte.
  • the lithium salt may be the lithium salt used in the preparation of lithium batteries in the prior art, for example, it may be selected from (LiFSI), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium bisoxalate borate (LiBOB), and the like.
  • the concentration of the lithium salt is 1-7 mol/L.
  • the polymerization monomer is an ether-based polymerization monomer, which can be selected from 1,3-dioxolane (DOL) or ethylene glycol dimethyl ether (DME).
  • DOL 1,3-dioxolane
  • DME ethylene glycol dimethyl ether
  • Additives can help effectively increase the electrochemical window of the electrolyte, and can be selected from carbonates. It is further selected from at least one of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • stirring can be carried out at a temperature of 15°C ⁇ 25°C, and the stirring time can be 0.5 ⁇ 3h.
  • the inorganic powder is added to the basic electrolyte and mixed to form a first solution.
  • the inorganic powder is selected from at least one of conductive ceramic powder, Al 2 O 3 , SiO 2 and TiO 2.
  • the conductive ceramic powder is Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), Li 7 La 3 Zr 2 O 12 (LLZO), Li 10 GeP 2 S 12 (LGPS) and Li 1.5 Al 0.5 Ge 1.5 P 3 At least one of O 12 (LAGP).
  • the addition of inorganic powder helps maintain the solid state of the electrolyte.
  • stirring can be carried out at a temperature of 15°C ⁇ 25°C, and the stirring time can be 0.5 ⁇ 3h.
  • the initiator is selected from at least one of Al(OTF) 3 , Al(CF 3 SO 3 ) 3 , LiPF 6 , diethyl aluminum chloride and ethyl aluminum dichloride, and the purpose of the initiator is to initiate polymerization of the monomer Carry out in-situ ring-opening polymerization.
  • the initiator usually needs to be heated to polymerize with the polymerized monomer, but for different initiators, the required heating temperature is different, so it is inconvenient to uniformly limit the heating temperature.
  • the preferred way is to keep the temperature of the first solution lower than the initiation temperature required by the initiator.
  • a further preferred way is: first add the initiator to the first solution, obtain a second solution after mixing, and make the second solution perform in-situ polymerization at a temperature of 25°C to 70°C.
  • the mass fraction of the base electrolyte is 15%-95%
  • the mass fraction of the inorganic powder is 5%-57%
  • the mass fraction of the initiator is 0.2%-44%.
  • embodiments of the present invention also provide the above solid polyelectrolyte, which includes in-situ polymerized inorganic powder, initiator, lithium salt, polymerized monomer and additives.
  • the lithium salt can be selected from (LiFSI), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium bisoxalate borate (LiBOB), and the like.
  • the concentration of the lithium salt is 1-7 mol/L.
  • the polymerization monomer is an ether-based polymerization monomer, which can be selected from 1,3-dioxolane (DOL) or ethylene glycol dimethyl ether (DME).
  • DOL 1,3-dioxolane
  • DME ethylene glycol dimethyl ether
  • the additives may be selected from carbonates. It is further selected from at least one of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC).
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • the inorganic powder is selected from at least one of conductive ceramic powder, Al 2 O 3 , SiO 2 and TiO 2.
  • the conductive ceramic powder is at least one of LLZTO, LLZO, LGPS and LAGP.
  • the in-situ polymerization reaction realizes the soft contact between the solid electrolyte and the electrode material, the obtained battery structure is uniform, and the interface impedance between the electrode and the solid electrolyte is reduced.
  • the solid polymer electrolyte prepared by the present invention has high ionic conductivity. At the same time, it also has high mechanical strength, and its electrochemical window can reach 5.5V.
  • the present invention further provides a lithium battery, including a positive electrode, a negative electrode, and an electrolyte arranged between the positive electrode and the negative electrode, and the electrolyte adopts the above-mentioned solid polymer electrolyte.
  • the second solution is first coated on the positive electrode, and then the components are polymerized in situ by heat treatment. So far, the solid polymer electrolyte is directly prepared and formed on the positive electrode. Specifically, the heating temperature is 25-60°C, and the heating time is 0.5-6h.
  • the lithium battery further assembled with solid polymer electrolyte effectively improves the cycle stability of the lithium battery: when the charge-discharge cycle reaches 400 cycles at a rate of 1C, the coulombic efficiency of the battery is still maintained at about 100%.
  • LiTFSI lithium bis(fluorosulfonyl)imide
  • LiPF 6 lithium hexafluorophosphate
  • the second solution is heated to polymerize the components in the second solution in situ to obtain an in-situ polymerized solid polymer electrolyte.
  • the second solution is first coated on the LFP positive electrode, and then the components are polymerized in situ by heat treatment, so that the solid polymer electrolyte is directly prepared. It is formed on the positive electrode, the heating temperature is 60°C, and the heating time is 1.5h.
  • the raw materials for preparing the solid polymer electrolyte in this embodiment include the following components in terms of weight ratio: 53.47% of the base electrolyte, 20.77% of LLZTO powder, and 25.76% of LiPF 6 .
  • LiTFSI LiTFSI
  • DOL solution Dissolve 0.574 g of LiTFSI in 2 mL of DOL solution, and stir at room temperature for 0.5 h until the LiTFSI is completely dissolved to form a high-concentration lithium salt basic electrolyte.
  • the molar concentration of LiTFSI is 1 mol/L .
  • LiPF 6 0.93 g was added to the first solution, and stirred at a temperature of 60° C. for 30 min, until LiPF 6 was uniformly dispersed in the first solution to form a second solution.
  • the second solution is coated on the LFP positive electrode, and then the components are polymerized in situ by heat treatment, so that the solid polymer electrolyte is directly prepared and formed on the LFP positive electrode.
  • the heating temperature of the heat treatment is 60°C, and the heating time It is 1.5h.
  • the raw materials for preparing the solid polymer electrolyte in this embodiment include the following components in terms of weight ratio: 64.28% of the base electrolyte, 12.49% of LLZTO powder, and 23.23% of LiPF 6 .
  • LiTFSI LiTFSI
  • DOL solution Dissolve 0.574 g of LiTFSI in 2 mL of DOL solution, and stir at room temperature for 0.5 h until the LiTFSI is completely dissolved to form a high-concentration lithium salt basic electrolyte.
  • the molar concentration of LiTFSI is 1 mol/L .
  • LiPF 6 0.62 g was added to the first solution, and stirred at a temperature of 60° C. for 30 min, until LiPF 6 was uniformly dispersed in the first solution to form a second solution.
  • the second solution is coated on the LFP positive electrode, and then the components are polymerized in situ by heat treatment, so that the solid polymer electrolyte is directly prepared and formed on the LFP positive electrode.
  • the heating temperature of the heat treatment is 60°C, and the heating time It is 1.5h.
  • the raw materials for preparing the solid polymer electrolyte in this embodiment include the following components in terms of weight ratio: 78.14% of the base electrolyte, 3.04% of LLZTO powder, and 18.82% of LiPF 6 .
  • LiTFSI LiTFSI
  • DOL solution Dissolve 2.296 g of LiTFSI in 2 mL of DOL solution, and stir at room temperature for 0.5 h until the LiTFSI is completely dissolved to form a high-concentration lithium salt basic electrolyte.
  • the molar concentration of LiTFSI is 4 mol/L .
  • LiPF 6 1.24 g was added to the first solution, and stirred at a temperature of 40° C. for 30 min, until LiPF 6 was uniformly dispersed in the first solution to form a second solution.
  • the second solution is coated on the LFP positive electrode, and then the components are polymerized in situ by heat treatment, so that the solid polymer electrolyte is directly prepared and formed on the LFP positive electrode.
  • the heating temperature of the heat treatment is 60°C, and the heating time For 1h.
  • the raw materials for preparing the solid polymer electrolyte in this embodiment include the following components in terms of weight ratio: 65.73% of the base electrolyte, 15.30 of LLZTO powder, and 18.97% of LiPF 6 .
  • LiTFSI Dissolve 4.018 g of LiTFSI in 2 mL of DOL solution, and stir at room temperature for 0.5 h until the LiTFSI is completely dissolved to form a high-concentration lithium salt basic electrolyte.
  • the molar concentration of LiTFSI is 7 mol/L .
  • LiPF 6 LiPF 6 was added to the first solution, and stirred at room temperature for 30 min, until LiPF 6 was uniformly dispersed in the first solution to form a second solution.
  • the second solution is coated on the LFP positive electrode, and then the components are polymerized in situ by heat treatment, so that the solid polymer electrolyte is directly prepared and formed on the LFP positive electrode.
  • the heating temperature of the heat treatment is 60°C, and the heating time For 1h.
  • the raw materials for preparing the solid polymer electrolyte in this embodiment include the following components in terms of weight ratio: 72.87% of the base electrolyte, 12.11% of LLZTO powder, and 15.02% of LiPF 6 .
  • FIG. 1 for the physical diagram of the solid polymer electrolyte prepared in the embodiment of the present invention.
  • a scanning electron microscope (SEM) was used to scan the solid polymer electrolytes of Example 1 and the obtained scanning results are shown in FIG. 2. It can be seen from the figure that the inorganic powder and the organic polymer are combined with each other.
  • the electrochemical impedance spectrum of the solid polymer electrolyte in Example 2 obtained by the test is shown in FIG. 3. As can be seen from the figure, the resistance of the prepared electrolyte is 110 ⁇ , and the conductivity is about 10 -3 S cm -1 .
  • the lithium battery assembled using the solid polyelectrolyte in Example 2 was subjected to a charge-discharge cycle test at a rate of 1C, and the result obtained is shown in FIG. 5.
  • the cycle reaches 400 cycles the coulombic efficiency of the battery still remains at about 100%.

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Abstract

本发明公开了一种固态聚合物电解质、其制备方法及锂电池，该固态聚合物电解质由锂盐、聚合单体、添加剂、无机粉末和引发剂原位聚合而成。本发明提供的固态聚合物电解质的制备方法包括：将锂盐加入到聚合单体和添加剂中，混合形成基础电解质；将无机粉末加入到所述基础电解质中，混合形成第一溶液；将引发剂加入到所述第一溶液中，使各个组分原位聚合，获得固态聚合物电解质。本发明提供的固态聚合物电解质具有很好的电化学稳定性，其电化学窗口达到5.5V，同时也有效解决了电极与固态电解质之间的界面电阻过高的问题；本发明提供的固态聚合物电解质制备方法简单高效，可很好地应用于工业生产。

Description

一种固态聚合物电解质、其制备方法及锂电池 技术领域
本发明涉及锂电池电解质制备技术领域，具体涉及一种固态聚合物电解质、其制备方法及锂电池。
 背景技术
社会的发展和科技的进步使得锂离子电池具有广泛的应用市场。高能量密度的锂离子电池是研究者们追求的主要方向，它要求锂离子电池具有高容量的电极和稳定的电解质。但是锂离子电池在应用的过程中，由于存在锂枝晶的生长、液态电解液的漏液、燃烧等问题而存在很大的安全隐患。
目前，凝胶聚合物电解质和固态电解质成为越来越多学者研究的热门领域，其中固态电解质由于其具有较高的机械强度和离子电导率而受到更广泛的研究。较高的机械强度可以抑制锂枝晶的生长，良好的离子电导率有利于离子的传输。但是固态电解质与电极之间存在严重的界面问题，原位聚合的策略也因此被提出，原位聚合方法就是：在电极上使用引发剂将纳米粒子和有机物分子直接聚合，减少了电极与固态电解质之间的界面电阻，提高了电池的性能。但是目前原位聚合方法获得的固态电解质，仍然具有电化学窗口不高的问题。
 技术问题
为解决上述现有技术中的原位聚合方法获得的固态电解质电化学窗口不高的问题，本发明提供了一种电化学窗口大于5 V的固态聚合物电解质及其制备方法，并进一步提供了包括该固态聚合物电解质的锂电池。
 技术解决方案
为了达到上述发明目的，本发明提供一种固态聚合物电解质，包括原位聚合的：基础电解质、无机粉末和引发剂，其中，基础电解质是由锂盐、聚合单体以及添加剂混合而成的。
进一步地，所述无机粉末选自导电陶瓷粉末、Al 2O 3、SiO 2和TiO 2中的至少一种。
更进一步地，所述导电陶瓷粉末为Li 6.4La 3Zr 1.4Ta 0.6O 12、Li 7La 3Zr 2O 12、Li 10GeP 2S 12和Li 1.5Al 0.5Ge 1.5P 3O 12中的至少一种。
进一步地，所述锂盐选自双(氟磺酰)亚胺锂、双三氟甲烷磺酰亚胺锂和双乙二酸硼酸锂中的至少一种；所述聚合单体选自醚基聚合单体；所述添加剂选自碳酸酯类。
进一步地，所述聚合单体选自1,3-二氧戊环或乙二醇二甲醚；所述添加剂选自碳酸二甲酯、碳酸甲乙酯和碳酸二乙酯中的至少一种。
进一步地，所述引发剂选自Al(OTF) 3、Al(CF 3SO 3) 3、LiPF 6、二乙基氯化铝以及乙基二氯化铝中的至少一种。
进一步地，所述基础电解质的质量分数为15%~95%，所述无机粉末的质量分数为5%~57%，所述引发剂的质量分数为0.2%~44%。
更进一步地，在所述基础电解质中，所述锂盐的物质的量浓度为1~7mol/L。
基于上述的固态聚合电解质，本发明还提供一种上述固态聚合电解质的制备方法，包括步骤：
S1、将锂盐加入到聚合单体和添加剂中，混合形成基础电解质；
S2、将无机粉末加入到所述基础电解质中，混合形成第一溶液；
S3、将引发剂加入到所述第一溶液中，使各个组分原位聚合，获得所述固态聚合物电解质。
进一步地，在步骤S3中，具体包括，先将引发剂加入到所述第一溶液中，进行搅拌混合获得第二溶液，使第二溶液在25℃~70℃下进行原位聚合反应。
本发明进一步提供一种锂电池，包括正极、负极以及设置在所述正极与负极之间的电解质，所述电解质采用的是上述的固态聚合物电解质。
 有益效果
本发明提供的固态聚合物电解质的制备方法是以无机粉末、引发剂、锂盐、聚合单体以及添加剂为原料进行聚合反应，该制备方法简单，能制备获得电化学窗口高于5 V的稳定性极好的固态聚合物电解质。
 附图说明
图1为本发明实施例中固态聚合物电解质的实物图；
图2为实施例1中固态聚合物电解质的SEM图；
图3为实施例2中固态聚合物电解质的电化学阻抗图；
图4为实施例2中固态聚合物电解质的循环伏安曲线图；
图5为实施例2中锂电池样品在1 C倍率下充放电循环测试曲线图。
 本发明的最佳实施方式
以下，将参照附图来详细描述本发明的实施例。然而，可以以许多不同的形式来实施本发明，并且本发明不应该被解释为限制于这里阐述的具体实施例。相反，提供这些实施例是为了解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。
本发明的发明人基于现有技术中原位聚合方法获得的固态电解质电化学窗口不高的问题，提供了电化学窗口大于5V的固态聚合物电解质及其制备方法，并进一步提供了包括该固态聚合物电解质的锂电池。
本发明实施例提供的固态聚合物电解质的制备方法，包括步骤：
S1、将锂盐加入到聚合单体和添加剂中，混合形成基础电解质。
锂盐可采用现有技术中制备锂电池时使用的锂盐，比如可以选自（LiFSI）、双三氟甲烷磺酰亚胺锂（LiTFSI）、双乙二酸硼酸锂（LiBOB）等。
更进一步地，在基础电解质中，锂盐的物质的量浓度为1~7mol/L。
聚合单体为醚基聚合单体，可以选自1,3-二氧戊环（DOL）或乙二醇二甲醚（DME）。
添加剂可以帮助有效提高电解质的电化学窗口，可以选自碳酸酯类。进一步选自碳酸二甲酯（DMC）、碳酸甲乙酯（EMC）和碳酸二乙酯（DEC）中的至少一种。
为促进上述物质的混合，可以在15℃~25℃的温度下进行搅拌，搅拌时间可以是0.5~3h。
S2、将无机粉末加入到基础电解质中，混合形成第一溶液。
进一步地，无机粉末选自导电陶瓷粉末、Al 2O 3、SiO 2和TiO 2中的至少一种。其中，导电陶瓷粉末为Li 6.4La 3Zr 1.4Ta 0.6O 12（LLZTO）、Li 7La 3Zr 2O 12（LLZO）、Li 10GeP 2S 12（LGPS）和Li 1.5Al 0.5Ge 1.5P 3O 12（LAGP）中的至少一种。无机粉末的加入有助于电解质的固体形态的维持。
为促进无机粉末和基础电解质的混合，可以在15℃~25℃的温度下进行搅拌，搅拌时间可以是0.5~3h。
S3、将引发剂加入到第一溶液中，使各个组分原位聚合，获得固态聚合物电解质。
引发剂选自Al(OTF) 3、Al(CF 3SO 3) 3、LiPF 6、二乙基氯化铝以及乙基二氯化铝中的至少一种，引发剂的目的在于引发聚合单体进行原位的开环聚合反应。引发剂通常需要在加热条件下才能与聚合单体聚合，但针对不同的引发剂，所需的加热温度是不同的，因此不便对加热温度进行统一的限定。为避免引发剂在刚加入第一溶液时就发生自聚反应，优选的方式是保持第一溶液的温度低于引发剂所需的引发温度，此时可以进行搅拌，搅拌时间可以是0.5~3h；进一步优选的方式是：先将引发剂加入到第一溶液中，进行混合后获得第二溶液，使第二溶液在25℃~70℃温度条件下进行原位聚合反应。
进一步地，基础电解质的质量分数为15%~95%，无机粉末的质量分数为5%~57%，引发剂的质量分数为0.2%~44%。
基于上述的固态聚合电解质的制备方法，本发明实施例还提供一种上述固态聚合电解质，其包括原位聚合的：无机粉末、引发剂、锂盐、聚合单体以及添加剂。
锂盐可以选自（LiFSI）、双三氟甲烷磺酰亚胺锂（LiTFSI）、双乙二酸硼酸锂（LiBOB）等。
在基础电解质中，锂盐的物质的量浓度为1~7mol/L。
聚合单体为醚基聚合单体，可以选自1,3-二氧戊环（DOL）或乙二醇二甲醚（DME）。
添加剂可以选自碳酸酯类。进一步选自碳酸二甲酯（DMC）、碳酸甲乙酯（EMC）和碳酸二乙酯（DEC）中的至少一种。
无机粉末选自导电陶瓷粉末、Al 2O 3、SiO 2和TiO 2中的至少一种。其中，导电陶瓷粉末为LLZTO、LLZO、LGPS和LAGP中的至少一种。
原位聚合反应实现了固态电解质与电极材料之间的软接触，获得的电池结构均匀，降低了电极与固态电解质之间的界面阻抗，本发明制得的固态聚合物电解质具有高的离子电导率的同时还具有高的机械强度，其电化学窗口可达到5.5V。
本发明进一步提供一种锂电池，包括正极、负极以及设置在正极与负极之间的电解质，电解质采用的是上述的固态聚合物电解质。
为了方便后续进行电池组装，首先将所述第二溶液涂覆到正极上，然后加热处理使其中的各个组分原位聚合，至此，固态聚合物电解质被直接制备形成在正极上。具体来说，加热温度为25~60℃，加热时间为0.5~6h。
利用固态聚合物电解质进一步组装得到的锂电池，有效地提高了锂电池的循环稳定性：在1C倍率下充放电循环达到400圈时，电池的库伦效率仍然保持在100%左右。
以下将结合具体的实施例来说明本发明的上述固态聚合物电解质、其制备方法以及锂电池，本领域技术人员所理解的是，下述实施例仅是本发明上述固态聚合物电解质、其制备方法以及锂电池的具体示例，而不用于限制其全部。
实施例1
取0.574g的双(氟磺酰)亚胺锂（LiTFSI）溶解于2mL的DOL溶液中，在室温下搅拌0.5h至LiTFSI完全溶解，形成高浓度锂盐的基础电解质，在基础电解质中，LiTFSI的摩尔浓度为1mol/L。
称取1gLLZTO粉末加入到上述基础电解质中，在室温下搅拌0.5h，直至LLZTO粉末均匀混合到基础电解质中，形成第一溶液。
将1.24g六氟磷酸锂（LiPF 6）加入到第一溶液中，在60℃的温度下搅拌30min，直至LiPF 6均匀分散在到第一溶液中，形成第二溶液。
对第二溶液进行加热处理使其中的各个组分原位聚合，获得原位聚合的固态聚合物电解质。
值得说明的是，在本实施例中，为了方便后续进行电池组装，首先将第二溶液涂覆到LFP正极上，然后加热处理使其中的各个组分原位聚合，使固态聚合物电解质直接制备形成在正极上，加热温度为60℃，加热时间为1.5h。
本实施例中的制备固态聚合物电解质的原料包括按照重量比计的以下组分：53.47％的基础电解质、20.77％的LLZTO粉末以及25.76％的LiPF 6。
实施例2
取0.574g的LiTFSI溶解于2mL的DOL溶液中，在室温下搅拌0.5h至所述LiTFSI完全溶解，形成高浓度锂盐的基础电解质，在所述基础电解质中，LiTFSI的摩尔浓度为1mol/L。
称取0.5gLLZTO粉末加入到上述基础电解质中，在室温下搅拌0.5h，直至LLZTO粉末均匀混合到所述基础电解质中，形成第一溶液。
将0.93g LiPF 6加入到所述第一溶液中，在60℃的温度下搅拌30min，直至LiPF 6均匀分散在到所述第一溶液中，形成第二溶液。
将所述第二溶液涂覆到LFP正极上，然后加热处理使其中的各个组分原位聚合，使固态聚合物电解质直接制备形成在LFP正极上，加热处理的加热温度为60℃，加热时间为1.5h。
本实施例中的制备固态聚合物电解质的原料包括按照重量比计的以下组分：64.28％的基础电解质、12.49％的LLZTO粉末以及23.23％的LiPF 6。
实施例3
取0.574g的LiTFSI溶解于2mL的DOL溶液中，在室温下搅拌0.5h至所述LiTFSI完全溶解，形成高浓度锂盐的基础电解质，在所述基础电解质中，LiTFSI的摩尔浓度为1mol/L。
称取0.1 gLLZTO粉末加入到上述基础电解质中，在室温下搅拌0.5h，直至LLZTO粉末均匀混合到所述基础电解质中，形成第一溶液。
将0.62 g LiPF 6加入到所述第一溶液中，在60℃的温度下搅拌30min，直至LiPF 6均匀分散在到所述第一溶液中，形成第二溶液。
将所述第二溶液涂覆到LFP正极上，然后加热处理使其中的各个组分原位聚合，使固态聚合物电解质直接制备形成在LFP正极上，加热处理的加热温度为60℃，加热时间为1.5h。
本实施例中的制备固态聚合物电解质的原料包括按照重量比计的以下组分：78.14％的基础电解质、3.04％的LLZTO粉末以及18.82％的LiPF 6。
实施例4
取2.296 g的LiTFSI溶解于2mL的DOL溶液中，在室温下搅拌0.5h至所述LiTFSI完全溶解，形成高浓度锂盐的基础电解质，在所述基础电解质中，LiTFSI的摩尔浓度为4mol/L。
称取1 gLLZTO粉末加入到上述基础电解质中，在室温下搅拌0.5h，直至LLZTO粉末均匀混合到所述基础电解质中，形成第一溶液。
将1.24 g LiPF 6加入到所述第一溶液中，在40℃的温度下搅拌30min，直至LiPF 6均匀分散在到所述第一溶液中，形成第二溶液。
将所述第二溶液涂覆到LFP正极上，然后加热处理使其中的各个组分原位聚合，使固态聚合物电解质直接制备形成在LFP正极上，加热处理的加热温度为60℃，加热时间为1h。
本实施例中的制备固态聚合物电解质的原料包括按照重量比计的以下组分：65.73％的基础电解质、15.30的LLZTO粉末以及18.97％的LiPF 6。
实施例5
取4.018 g的LiTFSI溶解于2mL的DOL溶液中，在室温下搅拌0.5h至所述LiTFSI完全溶解，形成高浓度锂盐的基础电解质，在所述基础电解质中，LiTFSI的摩尔浓度为7mol/L。
称取1 gLLZTO粉末加入到上述基础电解质中，在室温下搅拌0.5h，直至LLZTO粉末均匀混合到所述基础电解质中，形成第一溶液。
将1.24 g LiPF 6加入到所述第一溶液中，在室温下搅拌30min，直至LiPF 6均匀分散在到所述第一溶液中，形成第二溶液。
将所述第二溶液涂覆到LFP正极上，然后加热处理使其中的各个组分原位聚合，使固态聚合物电解质直接制备形成在LFP正极上，加热处理的加热温度为60℃，加热时间为1h。
本实施例中的制备固态聚合物电解质的原料包括按照重量比计的以下组分：72.87％的基础电解质、12.11%的LLZTO粉末以及15.02%的LiPF 6。
测试表征
本发明的实施例制备的固态聚合物电解质的实物图参见图1。
利用扫描电子显微镜（SEM）对实施例1到的固态聚合物电解质进行扫描，得到的扫描结果图如图2所示。从图中可以看出，无机粉末与有机高分子相互结合在一起。
测试得到实施例2中固态聚合物电解质的电化学阻抗谱参见图3，由图中可以看出，所制备的电解质的电阻为110Ω，电导率大约为10 -3S cm -1。
测试得到实施例2中固态聚合物电解质的循环伏安曲线如图4所示，从图中可以看出，该固态聚合物电解质的电化学窗口达到5.5V。
对利用实施例2中的固态聚合电解质组装得到的锂电池，在1C倍率下进行充放电循环测试，得到的结果如图5所示。在循环达到400圈时，电池的库伦效率仍然保持在100%左右。
虽然已经参照特定实施例示出并描述了本发明，但是本领域的技术人员将理解：在不脱离由权利要求及其等同物限定的本发明的精神和范围的情况下，可在此进行形式和细节上的各种变化。

Claims (11)

  1. 一种固态聚合物电解质，其特征在于，包括原位聚合的：基础电解质、无机粉末和引发剂，其中，基础电解质是由锂盐、聚合单体以及添加剂混合而成的。
  2. 根据权利要求1所述的固态聚合物电解质，其特征在于，所述无机粉末选自导电陶瓷粉末、Al 2O 3、SiO 2和TiO 2中的至少一种。
  3. 根据权利要求2所述的固态聚合物电解质，其特征在于，所述导电陶瓷粉末为Li 6.4La 3Zr 1.4Ta 0.6O 12、Li 7La 3Zr 2O 12、Li 10GeP 2S 12和Li 1.5Al 0.5Ge 1.5P 3O 12中的至少一种。
  4. 根据权利要求1所述的固态聚合物电解质，其特征在于，所述锂盐选自双(氟磺酰)亚胺锂、双三氟甲烷磺酰亚胺锂和双乙二酸硼酸锂中的至少一种；所述聚合单体选自醚基聚合单体；所述添加剂选自碳酸酯类。
  5. 根据权利要求4所述的固态聚合物电解质，其特征在于，所述聚合单体选自1,3-二氧戊环或乙二醇二甲醚；所述添加剂选自碳酸二甲酯、碳酸甲乙酯和碳酸二乙酯中的至少一种。
  6. 根据权利要求1所述的固态聚合物电解质，其特征在于，所述引发剂选自Al(OTF) 3、Al(CF 3SO 3) 3、LiPF 6、二乙基氯化铝以及乙基二氯化铝中的至少一种。
  7. 根据权利要求1~6任一所述的固态聚合物电解质，其特征在于，所述基础电解质的质量分数为15%~95%，所述无机粉末的质量分数为5%~57%，所述引发剂的质量分数为0.2%~44%。
  8. 根据权利要求7所述的固态聚合电解质，其特征在于，在所述基础电解质中，所述锂盐的物质的量浓度为1~7mol/L。
  9. 一种如权利要求1~8任一所述的固态聚合电解质的制备方法，其特征在于，包括步骤：
    S1、将锂盐加入到聚合单体和添加剂中，混合形成基础电解质；
    S2、将无机粉末加入到所述基础电解质中，混合形成第一溶液；
    S3、将引发剂加入到所述第一溶液中，使各个组分原位聚合，获得所述固态聚合物电解质。
  10. 根据权利要求9所述的制备方法，其特征在于，在步骤S3中，具体包括，先将引发剂加入到所述第一溶液中，进行搅拌混合获得第二溶液，使第二溶液在25℃~70℃下进行原位聚合反应。
  11. 一种锂电池，包括正极、负极以及设置在所述正极与负极之间的电解质，其特征在于，所述电解质采用的是如权利要求1~8任一所述的固态聚合物电解质。
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