WO2020107857A1 - 固态聚合物电解质制备方法及其固态二次电池 - Google Patents

固态聚合物电解质制备方法及其固态二次电池 Download PDF

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WO2020107857A1
WO2020107857A1 PCT/CN2019/090624 CN2019090624W WO2020107857A1 WO 2020107857 A1 WO2020107857 A1 WO 2020107857A1 CN 2019090624 W CN2019090624 W CN 2019090624W WO 2020107857 A1 WO2020107857 A1 WO 2020107857A1
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carbonate
polymer electrolyte
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韦伟峰
马骋
陈敏健
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Central South University
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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
    • 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

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  • the invention relates to a method for preparing a secondary battery electrolyte and a secondary battery, in particular to a method for preparing a solid polymer electrolyte and a solid secondary battery.
  • the electrolyte not only controls the internal ion transport dynamics of the battery, but also fundamentally determines the working mechanism of the battery, affecting the specific energy of the battery, rate charge and discharge performance, cycle life, safety performance and Production costs, etc.
  • the traditional organic liquid electrolyte is volatile, flammable, and explosive, which is the root cause of poor safety performance of secondary batteries.
  • the intrinsic brittleness of the inorganic solid electrolyte is large, and the heterogeneous interface with the electrode material is difficult to control, and it shows a high interface impedance, which cannot cope with the complex application environment of secondary batteries.
  • the all-solid polymer electrolyte is light in weight, easy to form a film, and has good viscoelasticity.
  • the present invention aims to provide a method for preparing a solid polymer electrolyte with greatly improved room temperature ion conductivity, and a solid secondary battery using the polymer electrolyte and a method for preparing the same.
  • the present invention is achieved by the following scheme.
  • a method for preparing a solid polymer electrolyte includes the following steps:
  • (I) In an environment with a protective atmosphere and a water content and an oxygen content of less than 1 ppm, mix the ethylenic boron monomer, ethylenic carbonate monomer, metal salt and radical initiator compound to obtain a precursor solution;
  • the metal salt is selected from one or more of alkali metal salt, calcium salt, magnesium salt, zinc salt or aluminum salt;
  • the olefinic boron monomer has a structure of one of formula 1 to formula 6 and contains at least one ethylene Base, organic compounds with molecular weight below 2000g/mol,
  • R1 ⁇ R9 are hydrogen atom, benzene ring, alkyl chain or benzene ring group, etheroxy group, ester group, cyano group, borooxy group or siloxy group or/and phosphorus One or more of the alkyl segments of the oxygen group;
  • step II In an environment with a protective atmosphere and a water content and oxygen content of less than 1 ppm, coat the precursor solution prepared in step I on the surface of the porous support material or metal negative electrode used in the secondary battery.
  • the solid-state polymer electrolyte is obtained by polymerization reaction for a certain period of time by light, heat or electricity.
  • the porous support material can use materials used in existing polymer solid electrolytes, such as polyethylene, polypropylene, polyacrylonitrile, polyvinylidene fluoride, poly(vinylidene fluoride-hexafluoroethylene), polymethyl methacrylate,
  • the porous membrane composed of single or multiple components in polyimide, polyetherimide, aramid and cellulose and the porous composite membrane in which inorganic ceramic particles modify the surface of the above polymer matrix.
  • the vinyl carbonate monomer is vinylene carbonate, ethylene ethylene carbonate, ethyl propylene carbonate, allyl methyl carbonate, allyl phenyl carbonate, cis-3-hexenol methyl carbonate Ester, allyl succinimidyl carbonate, tert-butyl 4-vinylphenyl carbonate, allyl tert-butyl peroxycarbonate, diallyl pyrocarbonate, allyl diethylene glycol One or more of dicarbonate and bis(2-methylallyl) carbonate.
  • the ratio of the mass of the radical initiator compound to the sum of the mass of the ethylenic boron monomer and the mass of the vinylene carbonate monomer is 0.05 to 1 wt%.
  • a solid secondary battery includes a positive electrode, a solid electrolyte and a negative electrode, wherein the positive electrode and the negative electrode both use the positive electrode and the negative electrode of the existing secondary battery, for example, the positive electrode uses a lithium iron phosphate active material, the negative electrode uses a metal lithium sheet, and the solid electrolyte
  • the positive electrode uses a lithium iron phosphate active material
  • the negative electrode uses a metal lithium sheet
  • the solid electrolyte The solid polymer electrolyte prepared by the above method is used.
  • a solid electrolyte is prepared on the surface of the metal negative electrode that can be used for secondary batteries prepared by the above-mentioned solid-liquid decomposition method, and then the positive electrode is used directly in an environment with a protective atmosphere and the water content and oxygen content are both less than 1 ppm
  • the metal negative electrode on which the solid electrolyte membrane is formed is directly assembled into a battery.
  • the solid polymer electrolyte prepared by the present invention contains a variety of organic groups that can complex with ions, which is beneficial to improve the dissociation rate of metal salts and the uniformity of ion distribution. Higher ion conductivity and high ion migration number can effectively reduce the concentration polarization in the secondary battery.
  • Solid-state secondary batteries based on such solid electrolytes exhibit excellent cycle stability, thanks to the in-situ polymerization method used to ensure the close integration of the polymer electrolyte and electrode materials, and achieve a better electrolyte/electrode heterogeneous interface Stability and compatibility.
  • a preparation method of polymer solid electrolyte adopts the following steps:
  • the metal lithium sheet is used as the electrode, and the precursor solution prepared in step I of Example 1 is injected into a porous cellulose membrane in a glove box protected by argon gas and the water content and oxygen content are both less than 1 ppm to seal and assemble the lithium metal symmetry
  • the battery was placed at 60°C and heated for 24 hours to cause the precursor to polymerize in situ to form a solid electrolyte.
  • the above-mentioned lithium metal symmetric battery cell was subjected to steady-state current polarization test and impedance spectrum test before and after polarization, and the measured lithium ion migration number was 0.68.
  • a lithium metal symmetrical battery assembled using an in situ polymer solid electrolyte containing only vinylene carbonate and no olefinic boron-containing monomer was tested, and its lithium ion migration number was only 0.43.
  • the positive electrode of lithium iron phosphate was selected, and the lithium metal sheet was used as the negative electrode.
  • the precursor solution prepared in step I of Example 1 was injected into the porous cellulose membrane in a glove box protected by argon and having a water content and oxygen content of less than 1 ppm. Sealed, assembled into a lithium iron phosphate/lithium metal battery, and heated at 60 °C for 24h to in-situ polymerization of the precursor to obtain a solid lithium iron phosphate/lithium metal battery.
  • a liquid lithium iron phosphate/lithium metal battery was assembled using an organic electrolyte, and the two assembled lithium iron phosphate/lithium metal batteries described above were subjected to constant current charging and discharging tests at a rate of 1C.
  • the test voltage range was 2.5-4V.
  • the solid lithium iron phosphate/lithium metal battery has an initial discharge specific capacity of 141.2mAh/g, which can be circulated stably for 600 cycles, while the initial discharge capacity of the assembled liquid lithium iron phosphate/lithium metal battery reaches 146mAh/g, but after 350 cycles There was a short circuit.
  • a preparation method of polymer solid electrolyte adopts the following steps:
  • step II In a glove box protected by argon and having a water content and oxygen content of less than 1 ppm, inject the precursor solution prepared in step I into a polypropylene film modified on the surface of inorganic ceramic particles, and select two stainless steel sheets as The blocking electrode was assembled into a symmetrical button cell made of stainless steel, and then the cell was placed at 80°C and heated for 12 hours for in-situ polymerization. An electrochemical workstation was used to perform impedance spectroscopy testing on the assembled stainless steel symmetrical battery, and the measured sodium ion conductivity was 1.82 ⁇ 10 -4 S/cm.
  • the precursor solution prepared in step I of Example 4 was injected into polypropylene modified on the surface of inorganic ceramic particles in a glove box protected by argon and having a water content and oxygen content of less than 1 ppm. And assembled into a metallic sodium symmetrical battery. After that, the battery was placed at 80°C and heated for 12 hours for in-situ polymerization. An electrochemical workstation was used to conduct the steady-state current polarization test and the impedance spectroscopy test before and after the polarization of the metal sodium symmetric battery, and the measured sodium ion migration number was 0.56.
  • the precursor solution prepared in step I of Example 4 was injected into the surface of the inorganic ceramic particles in a glove box protected by argon gas and the water content and oxygen content were both less than 1 ppm.
  • a polypropylene film and sealed to form a sodium vanadium phosphate/sodium metal battery, and placed at 80 °C heating 12h to make the precursor in situ polymerization reaction to obtain a solid sodium vanadium phosphate/sodium metal battery.
  • the assembled battery was subjected to constant current charging and discharging test at a rate of 1C.
  • the test voltage range was 2.5-4V, and the initial discharge specific capacity was measured to be 98.6mAh/g.
  • a preparation method of polymer solid electrolyte adopts the following steps:
  • step I In a glove box protected by argon and having a water content and oxygen content of less than 1 ppm, the precursor solution prepared in step I is coated on a polyethylene film modified with inorganic ceramic particles and placed at 80°C Heating for 12 hours for in-situ polymerization can obtain solid polymer electrolyte.
  • a preparation method of polymer solid electrolyte adopts the following steps:

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Abstract

本发明公开了一种固态聚合物电解质的制备方法及其在二次电池中应用，通过在多孔支撑材料注入包含硼杂环的烯类单体和烯类碳酸酯聚合物单体、金属盐和引发剂的前驱体溶液后，再以热、微波等方式进行原位聚合反应得到。本发明制备的固态聚合物电解质中酯基、醚氧及含硼官能团能够与碱金属盐产生较强的交互作用，改善了链段微观运动、碱金属盐解离度及离子在电解质中的不均匀分布，获得了较高的离子电导率及离子迁移数，同时原位聚合法改善了电解质/电极异质界面相容性和稳定性，对负极材料具有较好的保护效果，可应用于多尺度柔性储能器件并实现优越的循环稳定性和高安全性。

Description

固态聚合物电解质制备方法及其固态二次电池 技术领域
本发明涉及一种二次电池电解质的制备方法及二次电池，特别涉及一种固态聚合物电解质制备方法及固态二次电池。
背景技术
作为新型二次电池的重要组成部分，电解质不仅控制着电池内部离子传输动力学过程，而且从根本上决定着电池的工作机制，影响电池的比能量、倍率充放电性能、循环寿命、安全性能及生产成本等。传统的有机液态电解质易挥发、易燃、易爆，是二次电池安全性能差的根本原因。无机固体电解质的本征脆性大，与电极材料间的异质界面难以控制，表现为高的界面阻抗，无法应对二次电池的复杂应用环境。而全固态聚合物电解质质量轻、易成膜、粘弹性好，在提高电池能量密度、拓宽工作温度区间、延长使用寿命、提高安全性能及多功能结构和形状设计灵活性等方面也都有很大的优势，但其室温离子电导率尚较低(<10 -4S/cm)，电解质/电极异质界面稳定性较差，导致电极材料循环利用率下降。
发明内容
本发明旨在提供一种室温离子传导能力有较大改善的固态聚合物电解质制备方法及采用该聚合物电解质的固态二次电池及制备方法。本发明通过以下方案实现。
一种固态聚合物电解质的制备方法，包括以下步骤：
(Ⅰ)在具有保护气氛且水含量和氧含量均小于1ppm的环境下，将烯类硼单体、烯类碳酸酯单体、金属盐和自由基引发剂化合物混合得到前驱体溶液；所述的金属盐选自碱金属盐、钙盐、镁盐、锌盐或铝盐中一种或多种；所述烯类硼单体为具有式1～式6之一的结构且至少含有一个乙烯基，分子量在2000g/mol以下的有机化合物，
Figure PCTCN2019090624-appb-000001
其中，R1～R9为氢原子、苯环、烷基链或含有苯环基团、醚氧基团、酯类基团、 氰类基团、硼氧基团或硅氧基团或/和磷氧基团的烷基链段中的一种或多种；
(Ⅱ)在具有保护气氛且水含量和氧含量均小于1ppm的环境下，将第Ⅰ步制得的前驱体溶液覆于多孔支撑材料或用于二次电池的金属负极的表面，以微波、光、热或通电方式聚合反应一定时间得到固态聚合物电解质。多孔支撑材料可采用现有聚合物固态电解质所使用的材料，例如聚乙烯、聚丙烯、聚丙烯腈、聚偏氟乙烯、聚(偏氟乙烯-六氟乙烯)、聚甲基丙烯酸甲酯、聚酰亚胺、聚醚酰亚胺、芳纶和纤维素中单一或多种成分组成的多孔膜以及无机陶瓷颗粒对上述聚合物基体表面改性的多孔复合膜。
所述烯类碳酸酯单体为碳酸亚乙烯酯，碳酸乙烯亚乙酯，碳酸丙烯乙酯、烯丙基甲基碳酸酯、碳酸烯丙基苯酯、顺式-3-己烯醇碳酸甲酯、烯丙基琥珀酰亚胺基碳酸酯、叔丁基4-乙烯基苯基碳酸酯、烯丙基叔丁基过氧碳酸酯、焦碳酸二烯丙基酯、烯丙基二甘醇二碳酸酯、双(2-甲基烯丙基)碳酸酯中的一种或多种。
所述自由基引发剂化合物的质量与烯类硼单体质量和烯类碳酸酯单体质量之和的比例为0.05～1wt％。
一种固态二次电池，包括正极、固态电解质和负极，其中正极、负极均采用现有二次电池的正极和负极，例如，正极采用磷酸铁锂活性材料、负极采用金属锂片，而固态电解质则采用通过上述方法制备得到的固态聚合物电解质。在制备固态电池时，有以下三种方式：
1.在具有保护气氛且水含量和氧含量均小于1ppm的环境下，在壳体内依此放入正极、多孔支撑材料、负极后，向内腔中注入上述前驱体溶液，封装后再以微波、光、热或通电方式聚合反应一定时间。
2.采有上述固态电池解质方法制备得到在多孔支撑材料原位聚合的固态电解质，之后在具有保护气氛且水含量和氧含量均小于1ppm的环境下，直接用正极、上述固态电解质、负极装配成电池。
3.采有上述固态电池解质方法制备得到在可用于二次电池的金属负极表面原位聚合的固态电解质，之后在具有保护气氛且水含量和氧含量均小于1ppm的环境下，直接用正极和上述形成了固态电解质膜的金属负极直接装配成电池。
与现有固态聚合物电解质相比，采用本发明制备得到的固态聚合物电解质含有多种能与离子发生络合作用的有机基团，有利于提升金属盐的离解率和离子分布均匀性，具有较高的离子电导率和高的离子迁移数，可有效降低二次电池中浓差极化。基于此类固态电解质的固态二次电池表现出优异的循环稳定性，得益于采用的原位聚合法保证了聚合物电解质与电极材料的紧密结合，实现了较好的电解质/电极异质界面稳定性和相容性。
具体实施方式
实施例1
一种聚合物固态电解质的制备方法，采用以下步骤：
(Ⅰ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中，将0.4g碳酸亚乙烯酯和0.1g烯类含硼单体化合物
Figure PCTCN2019090624-appb-000002
及0.1g双三氟甲烷磺酰亚胺锂混合后，再加入0.0025mg的偶氮二异丁腈作为引发剂，制得前驱体溶液；
(Ⅱ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中，将第Ⅰ步制得的前驱体溶液注入多孔纤维素膜，并选取两个不锈钢片为阻塞电极装配成扣式电池，之后将电池置于60℃下加热24h进行原位聚合。采用电化学工作站对上述装配的不锈钢片对称电池进行阻抗谱测试，测得锂离子电导率为9.11×10 -4S/cm。采用碳酸亚乙烯酯而不含烯类含硼单体的原位聚合物固态电解质装配的电池作为对比其电导率仅为8.99×10 -4S/cm。
实施例2
选用金属锂片为电极，在氩气保护且水含量和氧含量均小于1ppm的手套箱中将实施例1的第Ⅰ步制得的前驱体溶液注入多孔纤维素膜中封口装配成锂金属对称电池，并置于60℃下加热24h使前驱体原位聚合反应形成固态电解质。采用电化学工作站对上述锂金属对称电池电池进行稳态电流极化测试以及极化前后阻抗谱测试，测得锂离子迁移数为0.68。作为对比，只采用碳酸亚乙烯酯而不含烯类含硼单体的原位聚合物固态电解质装配的锂金属对称电池进行了测试，其锂离子迁移数仅0.43。
实施例3
选用磷酸铁锂的正极，金属锂片为负极，在氩气保护且水含量和氧含量均小于1ppm的手套箱中将实施例1的第Ⅰ步制得的前驱体溶液注入多孔纤维素膜中封口，装配成磷酸铁锂/锂金属电池，并置于60℃下加热24h使前驱体原位聚合反应得到固态磷酸铁锂/锂金属电池。作为对比，采用有机电解液装配液态磷酸铁锂/锂金属电池，将上述装配的两种磷酸铁锂/锂金属电池在1C倍率下进行恒电流充放测试，测试电压区间为2.5-4V，测得固态磷酸铁锂/锂金属电池初始放电 比容量为141.2mAh/g，能够稳定循环600圈，而装配液态磷酸铁锂/锂金属电池初始放电容量虽然达到146mAh/g，但在循环350圈后就发生了短路。
实施例4
一种聚合物固态电解质的制备方法，采用以下步骤：
(Ⅰ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中将0.4g碳酸乙烯亚乙酯和0.1g烯类含硼单体化合物
Figure PCTCN2019090624-appb-000003
及0.049g高氯酸钠和0.0015mg引发剂偶氮二异丁腈混合，制得前驱体溶液；
(Ⅱ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中，将第Ⅰ步制得的前驱体溶液注入无机陶瓷颗粒表面改性的聚丙烯膜，并选取两个不锈钢片为阻塞电极装配成不锈钢片对称的扣式电池，之后将电池置于80℃下加热12h进行原位聚合。采用电化学工作站对上述装配的不锈钢片对称电池进行阻抗谱测试，测得钠离子电导率为1.82×10 -4S/cm。
实施例5
选用金属钠片为电极，在氩气保护且水含量和氧含量均小于1ppm的手套箱中将实施例4的第Ⅰ步制得的前驱体溶液注入无机陶瓷颗粒表面改性的聚丙烯中，并装配成金属钠对称电池。之后将电池置于80℃下加热12h进行原位聚合。采用电化学工作站对上述金属钠对称电池进行稳态电流极化测试以及极化前后 阻抗谱测试，测得钠离子迁移数为0.56。
实施例6
选用磷酸钒钠为正极，金属钠片为负极，在氩气保护且水含量和氧含量均小于1ppm的手套箱中将实施例4的第Ⅰ步制得的前驱体溶液注入无机陶瓷颗粒表面改性的聚丙烯膜中，并封口装配成磷酸钒钠/钠金属电池，并置于80℃下加热12h使前驱体原位聚合反应得到固态磷酸钒钠/钠金属电池。将装配的电池在1C倍率下进行恒电流充放测试，测试电压区间为2.5-4V，测得初始放电比容量为98.6mAh/g。
实施例7
一种聚合物固态电解质的制备方法，采用以下步骤：
(Ⅰ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中将0.4g碳酸丙烯乙酯和0.1g烯类含硼单体化合物
Figure PCTCN2019090624-appb-000004
及0.078g高氯酸镁混合后加入0.0025mg的偶氮二异丁腈作为引发剂，制得前驱体溶液；
(Ⅱ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中，将第Ⅰ步制得的前驱体溶液覆于经无机陶瓷颗粒表面改性的聚乙烯膜，置于80℃下加热12h进行原位聚合，可得到固态聚合物电解质。
实施例8
一种聚合物固态电解质的制备方法，采用以下步骤：
(Ⅰ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中将0.4g烯丙基甲基碳酸酯和0.1g烯类含硼单体化合物
Figure PCTCN2019090624-appb-000005
及0.22g双(三氟甲磺酰基)酰亚胺锌，混合后加入0.005g的偶氮二异丁腈作为引发剂，制得前驱体溶液；(Ⅱ)在氩气保护且水含量和氧含量均小于1ppm的手套箱中，将第Ⅰ步制得的前驱体溶液覆于聚偏氟乙烯，选取两个不锈钢片为阻塞电极装配成不锈钢片对称的扣式电池，之后将电池置于80℃下加热12h进行原位聚合，制得固态聚合物电池。

Claims (4)

  1. 一种固态聚合物电解质的制备方法，其特征在于：包括以下步骤，
    (Ⅰ)在具有保护气氛且水含量和氧含量均小于1ppm的环境下，将烯类硼单体、烯类碳酸酯单体、金属盐和自由基引发剂化合物混合，得到前驱体溶液；所述的金属盐选自碱金属盐、钙盐、镁盐、锌盐或铝盐中一种或多种；所述烯类硼单体为具有式1～式6之一的结构且至少含有一个乙烯基，分子量在2000g/mol以下的有机化合物，
    Figure PCTCN2019090624-appb-100001
    其中，R1～R9为氢原子、苯环、烷基链或含有苯环基团、醚氧基团、酯类基团、氰类基团、硼氧基团或硅氧基团或/和磷氧基团的烷基链段中的一种或多种；
    (Ⅱ)在具有保护气氛且水含量和氧含量均小于1ppm的环境中将第Ⅰ步制得的前驱体溶液覆于多孔支撑材料或用于二次电池的金属负极材料的表面，以微波、光、热或通电方式聚合反应一定时间得到固态聚合物电解质。
  2. 如权利要求1所述的固态聚合物电解质的制备方法，其特征在于：所述烯类碳酸酯单体为碳酸亚乙烯酯，碳酸乙烯亚乙酯，碳酸丙烯乙酯、烯丙基甲基碳酸酯、碳酸烯丙基苯酯、顺式-3-己烯醇碳酸甲酯、烯丙基琥珀酰亚胺基碳酸酯、叔丁基4-乙烯基苯基碳酸酯、烯丙基叔丁基过氧碳酸酯、焦碳酸二烯丙基酯、烯丙基二甘醇二碳酸酯、双(2-甲基烯丙基)碳酸酯中的一种或多种。
  3. 如权利要求1或2所述的固态聚合物电解质的制备方法，其特征在于：所述自由基引发剂化合物的质量与烯类硼单体质量和烯类碳酸酯单体质量之和的比例为0.05～1wt％。
  4. 一种固态二次电池，包括正极、固态电解质和负极，其特征在于：所述固态电解质为权利要求1～3之一所述的方法制备得到的固态聚合物电解质。
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