CN115057985B - 一种原位聚合的聚合物基电解质及电池的制备方法和电池 - Google Patents

一种原位聚合的聚合物基电解质及电池的制备方法和电池 Download PDF

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CN115057985B
CN115057985B CN202210880064.XA CN202210880064A CN115057985B CN 115057985 B CN115057985 B CN 115057985B CN 202210880064 A CN202210880064 A CN 202210880064A CN 115057985 B CN115057985 B CN 115057985B
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diisocyanate
battery
parts
glycol
situ
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CN115057985A (zh
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滑晨
许靖磊
李培文
袁丽只
朱小宁
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Abstract

本发明公开一种原位聚合的聚合物基电解质及电池的制备方法和电池，将锂盐、双异氰酸酯基化合物、双羟基化合物、硅氧烷组分、扩链剂与催化剂溶解在可聚合溶剂中，得到原位聚合电解质前驱体溶液；将所述原位聚合电解质前驱体溶液注入到干电芯中，进行浸润；将浸润后的电芯进行原位聚合反应，生成聚合物基电解质。本发明采用的硅氧烷组分，能够显著降低原位聚合电解质前驱体溶液的粘度，提升电池材料的浸润，有助于电池的性能发挥。本发明以双异氰酸酯基化合物和双羟基化合物的缩合聚合以及可聚合溶剂的开环聚合为基础反应，反应效率高，无液体残余，聚合反应同时进行，将浸润到电芯内部的溶液转变为固体，电解质为固体，提高电池安全性能。

Description

一种原位聚合的聚合物基电解质及电池的制备方法和电池
技术领域
本发明涉及电池技术领域，尤其涉及一种原位聚合的聚合物基电解质及电池的制备方法和电池。
背景技术
由于电动车长续航，高安全的市场需求，促使电池向高能量密度，高安全性方向发展。在高能量密度电池体系，相比于液态电解质的易挥发易燃不安全，固态电解质本身为固态，具有较高的安全性能，从而使得采用固态电解质组装的固态电池兼具有高能量密度和较高的安全性能。
目前，原位聚合制备的聚合物基固态电池采用的单体主要包括环醚单体、烯烃双键单体(含醚基或碳酸酯或羧酸酯基官能团)、双异氰酸酯单体和双羟基单体，其分别通过开环聚合、自由基聚合和缩合聚合反应原位聚合生成聚合物基电解质，制备固态电池。但是，聚合溶液本身粘度大，不能进行电池材料的浸润，阻碍电池性能发挥，即便添加溶液降低粘度，但溶液不能转变为固体，多生成凝胶电解质，生成半固态电解质，导致电池的安全性能大大降低。同时制备的聚合物基电解质离子电导率较低，耐氧化性较差，导致电池倍率性能和循环性能较差。
发明内容
为克服现有技术中原位聚合方法制备的聚合物基电解质的前驱体溶液粘度大，不易浸润电极材料，阻碍电池性能发挥，同时体系不能全固化，生成凝胶电解质，降低电池安全性能，并且聚合物基电解质离子电导率较低，耐氧化性较差的问题，本发明的目的是提供一种原位聚合的聚合物基电解质及电池的制备方法和电池，该方法解决全固态电池的前驱体溶液粘度大，不易浸润电极材料的制备问题，能够提升全固态电池倍率、循环性能和安全性。
为实现上述目的，本发明采用的技术方案如下：
一种原位聚合的聚合物基电解质，由以下原料制得，按质量份数计，锂盐5-30份，双异氰酸酯基化合物5-50份，双羟基化合物10-70份，硅氧烷组分5-30份，扩链剂组分2-30份，催化剂0.1-5份，可聚合溶剂组分40-95份。
一种电池的制备方法，包括以下步骤：
将锂盐、双异氰酸酯基化合物、双羟基化合物、硅氧烷组分、扩链剂与催化剂溶解在可聚合溶剂中，得到原位聚合电解质前驱体溶液；
将所述原位聚合电解质前驱体溶液注入到干电芯中，进行浸润，然后进行原位聚合反应形成原位聚合的聚合物基电解质，从而得到电池。
本发明进一步的改进在于，硅氧烷组分为氨丙基双封端聚二甲基硅氧烷、羟丙基双封端聚二甲基硅氧烷、羟烃基双封端聚二甲基硅氧烷、六甲基环三硅氧烷、八甲基环四硅氧烷、环氧丙氧基丙基双封端的聚二甲基硅氧烷与环氧环己基乙基封端的聚二甲基硅氧烷中的一种或多种；
可聚合溶剂为环醚或环碳酸酯。
本发明进一步的改进在于，环醚为含有环氧乙烷基的有机单体、四氢呋喃、1,3-环氧戊烷与1,3,5-三氧六环中的一种或多种；
环碳酸酯为碳酸乙烯酯与氟代碳酸乙烯酯中的一种或多种。
本发明进一步的改进在于，含有环氧乙烷基的有机单体为环氧乙烷、环氧丙烷、环氧氯丙烷、环氧环己烷、1,2-环氧己烷、丙基环氧乙烷、甲基环氧丙烷、环氧丙基甲基醚、2,3-环氧丙酸乙酯或2,3-环氧丙酸甲酯。
本发明进一步的改进在于，按质量份数计，锂盐5-30份，双异氰酸酯基化合物5-50份，双羟基化合物10-70份，硅氧烷组分5-30份，扩链剂组分2-30份，催化剂0.1-5份，可聚合溶剂组分40-95份。
本发明进一步的改进在于，原位聚合反应的温度为25-130℃，时间为2-24h，压力为0.1-60MPa。
本发明进一步的改进在于，扩链剂为小分子二元醇、二元胺与乙醇胺中的一种或多种；
双异氰酸酯基化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、萘二异氰酸酯、对苯二异氰酸酯、二甲基联苯二异氰酸酯、多亚甲基多苯基异氰酸酯，1,6-六亚甲基二异氰酸酯、三甲基-1,6-六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯，异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环已基二异氰酸酯、环己烷二亚甲基二异氰酸酯与降冰片烷二异氰酸酯中的一种或多种；
双羟基化合物为聚醚二醇、聚碳酸酯二醇、聚羧酸酯二醇与小分子二醇中的一种或多种；
催化剂为三亚乙基二胺、双(二甲氨基乙基)醚、二甲基乙醇胺、二月桂酸二丁基锡、辛酸亚锡与羧酸钾中的一种或多种；
锂盐为六氟磷酸锂、二氟草酸硼酸锂、四氟硼酸锂、双草酸硼酸锂、双氟磺酰胺锂盐与双三氟甲基磺酸亚酰胺锂中的一种或多种。
本发明进一步的改进在于，聚醚二醇为七聚乙二醇、八聚乙二醇、十聚乙二醇、聚乙二醇400、聚乙二醇600，聚乙二醇1000、一缩二丙二醇、聚丙二醇200、聚丙二醇400、聚丙二醇600或聚丙二醇1000；
聚碳酸酯二醇为聚碳酸酯二元醇1000或聚碳酸酯二元醇2000；
聚羧酸酯二醇为聚己内酯二醇530、聚己内酯二醇1000或聚己内酯二醇2000；
小分子二醇为三乙二醇、1,4-丁二醇、1,3-丁二醇、4-苄氧基-1,3-丁二醇或2-甲基-1,4-丁二醇；
二元胺为乙二胺、1,3-丙二胺、1,4-丁二胺、二甲苯二胺、间苯二胺、对苯二胺、邻苯二胺。
本发明进一步的改进在于，浸润的温度为25-60℃，时间为2-12h。
一种电池，包括正极、负极以及所述的原位聚合的聚合物基电解质。
与现有技术相比，本发明具有的有益效果：
本发明采用的硅氧烷组分，能够显著降低原位聚合电解质前驱体溶液的粘度，提升电池材料的浸润，有助于电池的性能发挥。本发明以双异氰酸酯基化合物和双羟基化合物的缩合聚合以及可聚合溶剂的开环聚合为基础反应，反应效率高，无液体残余，聚合反应同时进行，将浸润到电芯内部的溶液转变为固体，电解质为固体，提高电池安全性能。本发明中通过原位聚合反应，生成的固体聚合物基电解质，具有较高的离子电导率和较高的耐正极氧化能力，保障电芯优异的倍率性能和循环能力。本发明采用含有硅氧化学键的硅氧烷组分和含有异氰酸酯基团的双异氰酸酯基化合物打破双羟基化合物的结晶性，增加了分子的运动能力，从而减小离子迁移阻力，提升离子迁移速度，进而提升离子电导率；采用的含有硅氧化学键的硅氧烷组分和含有异氰酸酯基团的双异氰酸酯基化合物比仅仅采用可聚合溶剂形成的聚合物具有更高耐氧化性能。当电解质的离子电导率提升，锂离子迁移传输速率快，电池的倍率性能得到提升；电解质耐氧化性能好，不易于正极材料发生副反应，正极容量发挥稳定，所以电池的循环能力提升。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
固态电池：生成的聚合物基电解质为硬质固体，没有液体残余，称为全固态电池。
本发明的一种全固态电池的制备方法，包括如下步骤：
原位聚合的聚合物基电解质包括溶质和溶剂，溶剂为环醚或环碳酸酯，溶质包括硅氧烷组分、双异氰酸酯基化合物、双羟基化合物、扩链剂与催化剂与锂盐。具体制备过程如下：
按质量份数计，称取锂盐5-30份，双异氰酸酯基化合物5-50份，双羟基化合物10-70份，硅氧烷组分5-30份，扩链剂组分2-30份，催化剂0.1-5份，可聚合溶剂组分40-95份。
将锂盐、双异氰酸酯基化合物、双羟基化合物、硅氧烷组分、扩链剂与催化剂溶解在可聚合溶剂中，得到原位聚合电解质前驱体溶液；
相比于没有加入硅氧键组分的电解质前驱体溶液，本发明中加入硅氧键组分，并控制各个组分之间的用量比例，使得制备的原位聚合电解质前驱体溶液具有更好的流动性，从而说明粘度低，并且能够浸润电极，发挥电极性能。
没有加入硅氧键物质的电解质前驱体溶液，不能浸润电极，电极容量不能发挥，电池循环性能差。
其中，所述锂盐为六氟磷酸锂、二氟草酸硼酸锂、四氟硼酸锂、双草酸硼酸锂、双氟磺酰胺锂盐与双三氟甲基磺酸亚酰胺锂中的一种或多种。
双异氰酸酯基化合物为甲苯二异氰酸酯(TDD)、二苯基甲烷二异氰酸酯(MDI)、萘二异氰酸酯(NDD)、对苯二异氰酸酯(PPDD)、二甲基联苯二异氰酸酯(TODI)、多亚甲基多苯基异氰酸酯(PAPD)，1,6-六亚甲基二异氰酸酯(HDD)、三甲基-1,6-六亚甲基二异氰酸酯(TMHDI)、苯二亚甲基二异氰酸酯(XDI)、四甲基间苯二亚甲基二异氰酸酯(m-TMXDI)，异佛尔酮二异氰酸酯(IPDI)、1,4-环己烷二异氰酸酯(CHDI)、二环己基甲烷二异氰酸酯(HMDI)、甲基环已基二异氰酸酯(HTDI)、环己烷二亚甲基二异氰酸酯(HXDI)与降冰片烷二异氰酸酯(NB-DI)中的一种或多种。
双羟基化合物为聚醚二醇(聚醚二醇为七聚乙二醇、八聚乙二醇、十聚乙二醇、聚乙二醇400、聚乙二醇600、聚乙二醇1000、一缩二丙二醇、聚丙二醇200、聚丙二醇400、聚丙二醇600或聚丙二醇1000)、聚碳酸酯二醇(聚碳酸酯二醇为聚碳酸酯二元醇1000或聚碳酸酯二元醇2000)、聚羧酸酯二醇(聚羧酸酯二醇：聚己内酯二醇530、聚己内酯二醇1000或聚己内酯二醇2000)与小分子二醇(小分子二醇为三乙二醇、1,4-丁二醇、1,3-丁二醇、4-苄氧基-1,3-丁二醇或2-甲基-1,4-丁二醇)中的一种或多种。
硅氧烷组分为氨丙基双封端聚二甲基硅氧烷、羟丙基双封端聚二甲基硅氧烷、羟烃基双封端聚二甲基硅氧烷、六甲基环三硅氧烷、八甲基环四硅氧烷、环氧丙氧基丙基双封端的聚二甲基硅氧烷与环氧环己基乙基封端的聚二甲基硅氧烷中的一种或多种。
所述扩链剂为小分子二元醇(小分子二元醇为三乙二醇、1,4-丁二醇、1,3-丁二醇、4-苄氧基-1,3-丁二醇或2-甲基-1,4-丁二醇)、二元胺(二元胺为乙二胺、1,3-丙二胺、1,4-丁二胺、二甲苯二胺、间苯二胺、对苯二胺或邻苯二胺)与乙醇胺中的一种或多种。
催化剂为三亚乙基二胺、双(二甲氨基乙基)醚、二甲基乙醇胺、二月桂酸二丁基锡、辛酸亚锡与羧酸钾中的一种或多种。
可聚合溶剂为环醚或环碳酸酯；
具体的，环醚为含有环氧乙烷基的有机单体(含有环氧乙烷基的有机单体为环氧乙烷、环氧丙烷、环氧氯丙烷、环氧环己烷、1,2-环氧己烷、丙基环氧乙烷、甲基环氧丙烷、环氧丙基甲基醚、2,3-环氧丙酸乙酯或2,3-环氧丙酸甲酯)、四氢呋喃、1,3-环氧戊烷与1,3,5-三氧六环等环状醚类溶剂中的一种或多种；
环碳酸酯为碳酸乙烯酯与氟代碳酸乙烯酯等环状碳酸酯溶剂中的一种或多种。
将所述原位聚合电解质前驱体溶液注入到干电芯中，进行浸润；
将浸润后的电芯置于一定压力和温度下，同时进行溶质、溶剂的缩合聚合和开环聚合，原位聚合生成聚合物基电解质，同时制备全固态电池。其中，压力范围为0.1-60MPa，温度范围为25-130℃，时间范围为2-24h。
实施例1
本发明实施例提供一种全固态电池的制备方法，包括：
按质量份数计，在氩气手套箱中将六氟磷酸锂5份，二苯基甲烷二异氰酸酯10份，聚乙二醇600 15份，羟丙基双封端聚二甲基硅氧烷10份，六甲基环三硅氧烷8份，1,3-丁二醇1份以及二月桂酸二丁基锡1份溶解在1,3-二氧戊环50份中，充分搅拌形成原位聚合电解质前驱体溶液；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将原位聚合电解质前驱体溶液注入干电芯，进行电极和隔膜的浸润，在抽真空条件下进行浸润，温度为25℃，时间为2h；
然后，注液浸润电芯在压力为30MPa、温度为40℃下聚合5h，制得原位固化电解质，即聚合物即电解质，同时得到固态电池。
固态电池在常温无压力负载下测试，测试电压为2.8-4.2V，测试倍率为1C，进行循环测试，测试固态电池(即NCM811-SiO@C450电池)结果：电解质为硬质固体，电池容量1.8Ah，倍率84％@1C，循环80％@400圈。
实施例2
按质量份数计，在氩气手套箱中将二氟草酸硼酸锂6份，双三氟甲基磺酸亚酰胺锂8份，对苯二异氰酸酯10份，聚碳酸酯二醇20份，氨丙基双封端聚二甲基硅氧烷10份，环氧丙氧基丙基双封端的聚二甲基硅氧烷5份，乙二胺5份以及三亚乙基二胺1份溶解在四氢呋喃溶剂35份中，充分搅拌形成原位聚合电解质前驱体溶液；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过叠片组装制备干电芯，将原位聚合电解质前驱体溶液注入干电芯，进行电极和隔膜的浸润，在常压条件下，温度为40℃，时间为6h；
然后，注液浸润电芯在压力为60MPa，温度为60℃下聚合12h，制得原位固化电解质即聚合物即电解质，及其固态电池。
固态电池在常温无压力负载下测试，测试电压为2.8-4.2V，测试倍率为1C，进行循环测试，测试固态电池(即NCM811-SiO@C450电池)结果：电解质为硬质固体，电池容量1.9Ah，倍率80％@1C，循环80％@300圈。
实施例3
按质量份数计，在氩气手套箱中将四氟硼酸锂1份，双氟磺酰胺锂9份，1,6-六亚甲基二异氰酸酯15份，聚四氢呋喃二醇30份，羟烃基双封端聚二甲基硅氧烷15份，乙醇胺3份，辛酸亚锡2份溶解在四氢呋喃15份和氟代碳酸乙烯酯溶剂20份的混合溶液中，充分搅拌形成原位聚合电解质前驱体溶液；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将原位聚合电解质前驱体溶液注入干电芯，进行电极和隔膜的浸润，在常压条件下，温度为60℃，时间为12h；
然后，注液浸润电芯在压力为50MPa，温度为90℃下聚合24h，制得原位固化电解质即聚合物即电解质，及其固态电池。
固态电池在常温无压力负载下测试，测试电压为2.8-4.2V，测试倍率为1C，进行循环测试，测试固态电池(即NCM811-SiO@C450电池)结果：电解质为硬质固体，电池容量1.8Ah，倍率75％@1C，循环80％@350圈。
实施例4
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为六氟磷酸锂。
双异氰酸酯基化合物为甲苯二异氰酸酯(TDD)。
双羟基化合物为七聚乙二醇。
硅氧烷组分为氨丙基双封端聚二甲基硅氧烷。
扩链剂为三乙二醇。
催化剂为三亚乙基二胺。
可聚合溶剂为甲基环氧丙烷；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在25℃下进行浸润12h；
将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例5
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为二氟草酸硼酸锂。
双异氰酸酯基化合物为二苯基甲烷二异氰酸酯(MDI)。
双羟基化合物为聚碳酸酯二元醇1000。
硅氧烷组分为羟丙基双封端聚二甲基硅氧烷。
扩链剂为乙二胺。
催化剂为双(二甲氨基乙基)醚。
可聚合溶剂为四氢呋喃。
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在30℃下进行浸润11h；
将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例6
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为四氟硼酸锂。
双异氰酸酯基化合物为萘二异氰酸酯(NDD)。
双羟基化合物为聚己内酯二醇530。
硅氧烷组分为羟烃基双封端聚二甲基硅氧烷。
扩链剂为乙醇胺。
催化剂为二甲基乙醇胺。
可聚合溶剂为1,3-环氧戊烷；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过叠片组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在35℃下进行浸润10h；
将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例7
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为双草酸硼酸锂。
双异氰酸酯基化合物为对苯二异氰酸酯(PPDD)。
双羟基化合物为三乙二醇。
硅氧烷组分为六甲基环三硅氧烷。
扩链剂为1,4-丁二醇。
催化剂为二月桂酸二丁基锡。
可聚合溶剂为1,3,5-三氧六环；
将所述原位聚合电解质前驱体溶液注入到干电芯中，进行浸润；
将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例8
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为双氟磺酰胺锂盐与双三氟甲基磺酸亚酰胺锂任意比例的混合物。
双异氰酸酯基化合物为对苯二异氰酸酯(PPDD)与二甲基联苯二异氰酸酯(TODI)任意比例的混合物。
双羟基化合物为聚乙二醇400与聚碳酸酯二元醇2000的任意比例的混合物；
硅氧烷组分为八甲基环四硅氧烷、环氧丙氧基丙基双封端的聚二甲基硅氧烷与环氧环己基乙基封端的聚二甲基硅氧烷任意比例的混合物。
扩链剂为4-苄氧基-1,3-丁二醇与1,3-丙二胺任意比例的混合物。
催化剂为辛酸亚锡与羧酸钾任意比例的混合物。
可聚合溶剂环氧氯丙烷与四氢呋喃任意比例的混合物；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在60℃下进行浸润2h；将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例9
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为四氟硼酸锂、双草酸硼酸锂、双氟磺酰胺锂盐与双三氟甲基磺酸亚酰胺锂任意比例的混合物。
双异氰酸酯基化合物为1,6-六亚甲基二异氰酸酯(HDD)、三甲基-1,6-六亚甲基二异氰酸酯(TMHDI)、苯二亚甲基二异氰酸酯(XDI)、四甲基间苯二亚甲基二异氰酸酯(m-TMXDI)任意比例的混合物。
双羟基化合物为一缩二丙二醇、聚己内酯二醇530与2-甲基-1,4-丁二醇任意比例的混合物；
硅氧烷组分为六甲基环三硅氧烷、八甲基环四硅氧烷与环氧丙氧基丙基双封端的聚二甲基硅氧烷任意比例的混合物。
扩链剂为4-苄氧基-1,3-丁二醇、1,3-丙二胺与乙醇胺的任意比例的混合物。
催化剂为三亚乙基二胺与双(二甲氨基乙基)醚的任意比例的混合物。
可聚合溶剂为环氧丙基甲基醚、四氢呋喃、1,3-环氧戊烷的任意比例的混合物；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过叠片组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在50℃下进行浸润4h；将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例10
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为六氟磷酸锂。
双异氰酸酯基化合物为异佛尔酮二异氰酸酯(IPDI)、1,4-环己烷二异氰酸酯(CHDI)、二环己基甲烷二异氰酸酯(HMDI)的任意比例的混合物。
双羟基化合物为聚丙二醇1000、聚碳酸酯二元醇1000与聚己内酯二醇2000任意比例的混合物；
硅氧烷组分为氨丙基双封端聚二甲基硅氧烷。
扩链剂为对苯二胺。
催化剂为羧酸钾。
可聚合溶剂为碳酸乙烯酯与氟代碳酸乙烯酯任意比例的混合物。
将所述原位聚合电解质前驱体溶液注入到干电芯中，在40℃下进行浸润8h；
将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例11
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为双草酸硼酸锂。
双异氰酸酯基化合物为甲基环已基二异氰酸酯(HTDI)、环己烷二亚甲基二异氰酸酯(HXDI)与降冰片烷二异氰酸酯(NB-DI)的任意比例的混合物。
双羟基化合物为聚己内酯二醇530与2-甲基-1,4-丁二醇的任意比例的混合物。
硅氧烷组分为环氧丙氧基丙基双封端的聚二甲基硅氧烷与环氧环己基乙基封端的聚二甲基硅氧烷的任意比例的混合物。
扩链剂为邻苯二胺与乙醇胺的任意比例的混合物。
催化剂为辛酸亚锡。
可聚合溶剂为氟代碳酸乙烯酯。
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在35℃下进行浸润7h；将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
实施例12
按质量份数计，在氩气手套箱中将锂盐5份，双异氰酸酯基化合物10份，双羟基化合物30份，硅氧烷组分10份，扩链剂组分2份，催化剂0.1份加入到可聚合溶剂组分50份中，得到原位聚合电解质前驱体溶液；
其中，锂盐为双三氟甲基磺酸亚酰胺锂。
双异氰酸酯基化合物为苯二亚甲基二异氰酸酯(XDI)、1,4-环己烷二异氰酸酯(CHDI)与二环己基甲烷二异氰酸酯(HMDI)的任意比例的混合物。
双羟基化合物为聚丙二醇200、聚碳酸酯二元醇2000、聚己内酯二醇2000与1,4-丁二醇的任意比例的混合物。
硅氧烷组分为八甲基环四硅氧烷。
扩链剂为对苯二胺。
催化剂为二甲基乙醇胺。
可聚合溶剂为1,3,5-三氧六环和四氢呋喃的混合物；
将作为电池的正极的NCM811，作为负极的SiO@C450，以及隔膜通过卷绕组装制备干电芯，将所述原位聚合电解质前驱体溶液注入到干电芯中，在30℃下进行浸润4h；
将浸润后的电芯置于压力为0.1MPa、温度为130℃下进行原位聚合反应24h，制得聚合物基电解质，同时制得全固态电池。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改和替换。

Claims (4)

1.一种电池的制备方法，其特征在于，包括以下步骤：
将锂盐、双异氰酸酯基化合物、双羟基化合物、硅氧烷组分、扩链剂与催化剂溶解在可聚合溶剂中，得到原位聚合电解质前驱体溶液；
将所述原位聚合电解质前驱体溶液注入到干电芯中，进行浸润，然后进行原位聚合反应形成原位聚合的聚合物基电解质，从而得到电池；
其中，硅氧烷组分为氨丙基双封端聚二甲基硅氧烷、羟丙基双封端聚二甲基硅氧烷、羟烃基双封端聚二甲基硅氧烷、六甲基环三硅氧烷、八甲基环四硅氧烷、环氧丙氧基丙基双封端的聚二甲基硅氧烷与环氧环己基乙基封端的聚二甲基硅氧烷中的一种或多种；
可聚合溶剂为环醚或环碳酸酯；
扩链剂为小分子二元醇、二元胺与乙醇胺中的一种或多种；
环醚为含有环氧乙烷基的有机单体、四氢呋喃、1,3-环氧戊烷与1,3,5-三氧六环中的一种或多种；
环碳酸酯为碳酸乙烯酯与氟代碳酸乙烯酯中的一种或多种；
含有环氧乙烷基的有机单体为环氧乙烷、环氧丙烷、环氧氯丙烷、环氧环己烷、1,2-环氧己烷、丙基环氧乙烷、甲基环氧丙烷、环氧丙基甲基醚、2,3-环氧丙酸乙酯或2,3-环氧丙酸甲酯；
按质量份数计，锂盐5-30份，双异氰酸酯基化合物5-50份，双羟基化合物10-70份，硅氧烷组分5-30份，扩链剂组分2-30份，催化剂0.1-5份，可聚合溶剂组分40-95份；
原位聚合反应的温度为25-130℃，时间为2-24h，压力为0.1-60MPa。
2.根据权利要求1所述的一种电池的制备方法，其特征在于，
双异氰酸酯基化合物为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、萘二异氰酸酯、对苯二异氰酸酯、二甲基联苯二异氰酸酯、多亚甲基多苯基异氰酸酯，1,6-六亚甲基二异氰酸酯、三甲基-1,6-六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯，异佛尔酮二异氰酸酯、1,4-环己烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲基环已基二异氰酸酯、环己烷二亚甲基二异氰酸酯与降冰片烷二异氰酸酯中的一种或多种；
双羟基化合物为聚醚二醇、聚碳酸酯二醇、聚羧酸酯二醇与小分子二醇中的一种或多种；
催化剂为三亚乙基二胺、双(二甲氨基乙基)醚、二甲基乙醇胺、二月桂酸二丁基锡、辛酸亚锡与羧酸钾中的一种或多种；
锂盐为六氟磷酸锂、二氟草酸硼酸锂、四氟硼酸锂、双草酸硼酸锂、双氟磺酰胺锂盐与双三氟甲基磺酸亚酰胺锂中的一种或多种。
3.根据权利要求2所述的一种电池的制备方法，其特征在于，聚醚二醇为七聚乙二醇、八聚乙二醇、十聚乙二醇、聚乙二醇400、聚乙二醇600，聚乙二醇1000、一缩二丙二醇、聚丙二醇200、聚丙二醇400、聚丙二醇600或聚丙二醇1000；
聚碳酸酯二醇为聚碳酸酯二元醇1000或聚碳酸酯二元醇2000；
聚羧酸酯二醇为聚己内酯二醇530、聚己内酯二醇1000或聚己内酯二醇2000；
小分子二醇为三乙二醇、1,4-丁二醇、1,3-丁二醇、4-苄氧基-1,3-丁二醇或2-甲基-1,4-丁二醇；
二元胺为乙二胺、1,3-丙二胺、1,4-丁二胺、二甲苯二胺、间苯二胺、对苯二胺、邻苯二胺。
4.一种电池，其特征在于，包括正极、负极以及权利要求1所述的方法制备的原位聚合的聚合物基电解质。
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