CN104752755B - 硫化物固体电解质的制备方法 - Google Patents

硫化物固体电解质的制备方法 Download PDF

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CN104752755B
CN104752755B CN201510196872.4A CN201510196872A CN104752755B CN 104752755 B CN104752755 B CN 104752755B CN 201510196872 A CN201510196872 A CN 201510196872A CN 104752755 B CN104752755 B CN 104752755B
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solid electrolyte
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sulfide
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CN104752755A (zh
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韦伟峰
曾小慧
丁正平
柳佳图
陈立宝
张大同
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Guangdong Jusheng Technology Co.,Ltd.
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Central South University
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    • H—ELECTRICITY
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    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract

本发明提供了一种硫化物固体电解质的制备方法在密闭容器中向金属M1的氢氧化物水溶液中先通入H2S气体或加入可溶于水的硫化物反应一定时间后，再向其中加入包含有金属M2元素的水溶液；通入保护气体继续反应再向加入有机试剂后，置于低温环境中，析出的晶体经干燥后，再经热处理去除结晶水后得到产物。本发明采用新颖的湿法工艺制备全固态电解质，相比于传统固相合成的显著优点是反应时间短、可以控制产物形貌。

Description

硫化物固体电解质的制备方法
技术领域
本发明涉及一种全固体锂离子电池用固体电解质的制备方法，特别涉及一种硫化物固体电解质的制备方法。
背景技术
目前市场上锂离子电池使用的有机电解液，存在漏液,腐蚀电极甚至发生氧化燃烧等安全性问题。锂离子无机固体电解质可以很好的避免上述问题，且具有锂离子导电率高(最高可达10-2S/cm)、化学稳定性好、电位窗口大(5～10V)等优点，并且可与高比能量的储能材料硫电极配合，极有希望开发出高比能量、安全、可高温使用的新型锂离子电池。作为全固体锂离子电池用的硫化物固体电解质是目前研究得较多的一种电解质材料，如申请人丰田自动车株式会社在专利申请201380007092X中已公开了这种电解质材料。但目前制备这种材料的方法均为固相合成方法，如在上述专利申请中也公开了这种制备方法。
发明内容
本发明旨在提供一种完全区别于固相合成法的湿法工艺方法来制备硫化物固体电解质材料。本发明通过以下方案实现：
第一步：在密闭容器中，向金属M1的氢氧化物水溶液中先通入H2S气体或加入可溶于水的硫化物反应一定时间后，再向其中加入包含有金属M2元素的水溶液进行反应至沉淀完全溶解；所述金属M1选自碱金属Li、Na、K中的至少一种，所述金属M2选自第IIIA族B、Al、第IVA族Si、Ge、Sn或第VA族P、As、Sb中的至少一种；
第二步：在保持溶液呈碱性的条件下，向第一步反应后得到的产物中通入保护气体继续反应一定时间或使第一步的反应在完全密封条件下继续反应一定时间；再向其中加入可与水互溶的有机试剂如丙酮、乙醇、甲醇等，之后置于低温环境中，直至析出晶体；所述保护气体选自氮气、氨分解气或惰性气体的至少一种。
第三步：第二步析出的晶体经干燥后，再于300℃以上且低于晶体分解温度以下的温度环境中保温一定时间，得到产物。
试验发现，第一步中的硫化物选自碱金属硫化物或硫化铵中的至少一种较优。
为缩短析晶时间，第二步的低温环境的温度不高于0℃。
为降低杂质，第二步的析出晶体先经有机溶剂洗涤后再干燥,有机溶剂可采用丙酮、乙醇、甲醇。
本发明采用新颖的湿法工艺制备全固态电解质，相比于传统固相合成的显著优点是反应时间短、可以控制产物形貌。
具体实施方式
实施例1
一种无机固态电解质Li4SnS4的制备方法如下：
在三口烧瓶中，将LiOH·H2O搅拌溶于水，向其中通入H2S气体25分钟后，多余的H2S气体用KOH溶液吸收，再将SnCl4·5H2O溶水后，加入至三口烧瓶中，待生成的黄色沉淀全部溶解。调节溶液的pH在11～12之间，通入氮气气氛条件下，水浴45℃反应8h后，再向烧瓶中加入丙酮，再置于0℃的环境中48h，至有白色晶体析出。过滤提取析出物，并用丙酮冲洗多次，将晶体析出物于真空干燥12h，得到淡灰色粉末，之后于350℃环境中保温12h以脱去粉末产物的结晶水，得到结晶态的无机固态电解质Li4SnS4。
实施例2
无机固态电解质Li4-xNaxSnS4(x＝0～4)的湿法制备：
将LiOH·H2O与NaOH按一定化学计量于三口烧瓶中搅拌溶于水后，在加入Na2S。再将SnCl4·5H2O溶于水后，加入三口烧瓶中，待生成的黄色沉淀全部溶解。调节溶液的pH在11～12之间，完全密封条件下反应水浴45℃10h后，加入乙醇后再置于0℃冰箱中48h，至有白色晶体析出。过滤提取析出物，并用丙酮冲洗多次，将晶体析出物真空干燥12h，得到淡灰色粉末。之后于350℃保温12h以脱去粉末产物的结晶水，得到结晶态Li4-xNaxSnS4。
实施例3
无机固态电解质Li4SeS4的湿法制备：
将LiOH·H2O于三口烧瓶中搅拌溶于水后，加入(NH4)2S。再将SeCl4溶于水后，加入三口烧瓶中，待生成的黄色沉淀全部溶解。调节溶液的pH在11～12之间，完全密封10h后，向三口烧瓶中加入丙酮后再置于0℃冰箱中至有白色晶体析出。过滤提取析出物，并用乙醇冲洗多次，将晶体析出物真空干燥12h，得到白色粉末。之后于450℃保温12h以脱去粉末产物的结晶水，得到结晶态Li3SeS4。

Claims (3)

1.一种硫化物固体电解质的制备方法，其特征在于：按以下步骤进行，
第一步：在密闭容器中向金属M1的氢氧化物水溶液中先通入H2S气体或加入可溶于水的硫化物反应一定时间后，再向其中加入包含有金属M2元素的水溶液进行反应至沉淀完全溶解；所述金属M1选自碱金属Li、Na、K中的至少一种，所述金属M2选自第IIIA族B、Al、第IVA族Si、Ge、Sn或第VA族P、As、Sb中的至少一种；
第二步：在保持溶液呈碱性的条件下，向第一步反应后得到的产物中通入保护气体继续反应一定时间或使第一步的反应在完全密封条件下继续反应一定时间；再向其中加入可与水互溶的有机试剂后，置于温度不高于0℃的环境中，直至析出晶体；所述保护气体选自氮气或惰性气体的至少一种；
第三步：第二步析出的晶体经干燥后，再于300℃以上且低于晶体分解温度以下的温度环境中保温一定时间，得到产物。
2.如权利要求1所述的硫化物固体电解质的制备方法，其特征在于：所述第一步中的硫化物选自碱金属硫化物或硫化铵中的至少一种。
3.如权利要求1或2所述的硫化物固体电解质的制备方法，其特征在于：所述第二步的析出晶体先经有机溶剂洗涤后再干燥。
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CN105098228A (zh) * 2014-05-05 2015-11-25 中国科学院宁波材料技术与工程研究所 硫化物固体电解质材料及其制备方法

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