CN103560276A - 一种反应性聚合物电解质及其水系锂离子电池膜电极组件 - Google Patents
一种反应性聚合物电解质及其水系锂离子电池膜电极组件 Download PDFInfo
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Abstract
本发明公开了一种具有反应性聚合物电解质膜电极,通过电化学处理后可以显著提高水系锂离子电池比能量,但不限于水系锂离子电池的应用。例如,典型的反应性聚合物电解质组分种类和含量范围如下:杂多酸盐5%-90%,锂盐5%-30%,水性聚合物5%-90%,水10%-300%。将调制均匀后的聚合物电解液用浓氢氧化锂调节至中性,然后均匀涂覆在水系锂电极表面,放置于一定温度和湿度环境中形成膜电极,将正负电极对接组装成电池,最后通过过充电压处理。与铅酸蓄电池、镍氢电池和有机系锂离子电池二次电池相比,本制备工艺操作简单、选取原料基本绿色无污染并可获得与之相媲美的电池比能量特性。
Description
技术领域
本发明涉及锂离子电池,更具体地,涉及一种反应性聚合物电解质及其水系锂离子电池膜电极组件。
背景技术
能量的转储和输出在新能源和节能技术开发和利用占有举足轻重的地位。随着能源日益枯竭的临近和环境污染不断恶化,像风能、地热能、太阳能和生物能等清洁能源的应用研究得到日益广泛的重视。然而,这些所谓的新型能源往往存在季节性、功率输出不稳定性和地域性差异明显等问题,使得离真正实用推广仍有一定距离。一种很好的解决方法就是将这些能量先进行转储后再进行输出,这样就可以从根本上解决能量的开发和利用问题。能量的转储手段一般是通过各种电化学储能器件进行,如二次电池(铅酸蓄电池、镍氢电池和有机系锂离子电池)、电化学超级电容器等,基本结构由电极和电解质组成。不过,这些储能器件的电解质往往含有强酸、强碱、可燃易爆溶剂或有毒有害的金属离子,因而换种角度看,采用此类新型清洁能源意味着需要相应配套的储能设备,这样实质上会变成是对环境污染问题的转嫁。另外,尽管电解质在电化学储能器件中的地位仅次于电极材料,但是作为离子传输的媒介,其重要地位仍不容忽视。为了解决上述矛盾,发展清洁能量转储器件势在必行,而其中基于水系锂离子电池,采用的是水作为电解质的溶剂,对环境基本无污染,被认为是一个很好的研究方向。通过电化学处理以改善聚合物电解质与电极界面的相互作用,亦即反应性聚合物电解质,在抑制电极材料的溶解以及水的分解有突出作用,能够显著改善水系锂离子电池在比能量特性。
发明内容
本发明的目的在于提供一种性能更好的锂电池。
根据需求,先提供一种反应性聚合物电解质,按重量份计,包括以下组分:
杂多酸盐 5~90份,
锂盐 5~90份,
水溶性聚合物 5~90份,
水 10~300份。
所述的杂多酸盐为磷钨酸、硅钨酸与氢氧化锂形成的多金属氧酸锂盐,或通过锂离子置换质子后的杂多酸盐,或将包含杂多酸的聚合物电解质用浓氢氧化锂溶液调节为中性。
所述的锂盐为硫酸锂、硝酸锂、磷酸锂、氯化锂、碘化锂、高氯酸锂或三氟甲基磺酸锂。
所述的水溶性聚合物为聚乙烯醇、聚氧化乙烯、聚丙烯酸、聚四氟乙烯、水溶性橡胶、壳聚糖或淀粉。
更进一步提供一种水系锂离子电池膜电极组件,包括权利要求1所述的反应性聚合物电解质和聚合物电解质膜,所述的聚合物电解质膜经过电化学方法处理。
所述的电化学方法为过充电压充电,所述的过充电压充电为充电电压比电池理论设计的电压高0.2~1V。
还包括正极材料、负极材料、导电剂和粘合剂。
所述的正极材料活性物质为锰酸锂、钴酸锂或磷酸铁锂;负极材料活性物质为磷酸钛锂。
本发明的有益效果在于以下两点:
1. 本发明提供的反应性聚合物电解质的离子导电率高,从而能提高电池性能。
2. 本发明的另外一个发明点在于,通过对电极上的膜进行电化学处理,再结合本发明的反应性聚合物电解质,能够获得性能更好的电极。也就是说,当膜经过电化学处理后,本发明的反应性聚合物电解质的放电容量会大大提高。
附图说明
图1为一种水系聚合物锂离子电池的组装方式。
图2为正常电压(1.85V)充电和过充电压(2V)充电下Li2MnO4/LiTi(PO4)3锂离子电池充放电曲线比较图。
图3为电化学改性聚合物电解质Li2MnO4/LiTi(PO4)3锂离子电池倍率特性图。
具体实施方式
下面结合附图和具体实施例进一步详细说明本发明。除非特别说明,本发明采用的试剂、设备和方法为本技术领域常规市购的试剂、设备和常规使用的方法。
本发明涉及采用电化学方法处理水系锂离子膜电极,不限于过充电压充电处理,过充电压为比电池理论设计电压高0.2-1V。选用的聚合物电解质具有一定电化学反应活性,包括不限于包含杂多酸盐聚合物电解质。
本发明的一些实施例如下,但不应当受限于本文给出的示例性实施例。
实施例1
正极使用商业级尖晶石型锰酸锂,浆料质量配比按照锰酸锂:乙炔黑:聚四氟乙烯=82:10:8混浆,在不锈钢网上压制成膜,将压制的膜在真空干燥箱中于80℃恒温干燥24h以上。负极材料活性物质磷酸钛锂(LiTi(PO4)3)的制备:往一定量的纳米TiO2粉末中,滴加一定量的聚乙烯醇溶液,依次加入Li2CO3和NH4H2PO4),混合物在90℃下用磁力搅拌搅干形成白色固体。将白色固体放入瓷舟中并转移至管式炉中,在N2气氛保护下900℃煅烧12h。负极制备方法同正极。取0.85g钨硅酸,0.5g聚乙烯醇溶液(0.1g/mL),0.10g硫酸锂混合,加入0.057 g 50% 戊二醛溶液,搅拌成凝胶后,然后用饱和氢氧化锂逐滴滴加搅拌至中性,将调至均匀的溶液浇铸在电极材料表面,在湿度65%、温度32℃下恒重24h,制成膜电极。集流体采用不锈钢压块,顺序将膜正极/绝缘塑料隔片/膜负极组装成纽扣电池,如图1所示,测试电池充放电性能,如图2所示。首次正常充电电压范围在0-1.85V(曲线1)、放电电流0.2C时,电池体系的放电容量为23.1mAh/g;首次过充电压充电范围在0-2V(曲线2)、放电电流0.2C时,电池体系的放电容量为66.7mAh/g,其后在0-1.85V的工作电压下的倍率特性如图3所示。
实施例2
正极使用商业级尖晶石型锰酸锂,浆料质量配比按照锰酸锂:乙炔黑:聚四氟乙烯=82:10:8混浆,在不锈钢网上压制成膜,将压制的膜在真空干燥箱中于80℃恒温干燥24h以上。负极材料活性物质磷酸钛锂(LiTi(PO4)3)的制备:往一定量的纳米TiO2粉末中,滴加一定量的聚乙烯醇溶液,依次加入Li2CO3和NH4H2PO4),混合物在90℃下用磁力搅拌搅干形成白色固体。将白色固体放入瓷舟中并转移至管式炉中,在N2气氛保护下900℃煅烧12h。负极制备方法同正极。取0.80g钨硅酸,1.0g聚乙烯醇溶液(0.1g/mL),0.10g硫酸锂混合,用饱和氢氧化锂逐滴滴加搅拌至中性,将调至均匀的溶液浇铸在电极材料表面,在湿度65%、温度32℃下恒重24h,制成膜电极。集流体采用不锈钢压块,顺序将膜正极/绝缘塑料隔片/膜负极组装成纽扣电池,测试电池充放电性能。在0-2V工作区间,放电电流0.2C时,电池体系的首次放电容量为58.6mAh/g。
实施例3
正极使用商业级尖晶石型锰酸锂,浆料质量配比按照锰酸锂:乙炔黑:聚四氟乙烯=82:10:8混浆,在不锈钢网上压制成膜,将压制的膜在真空干燥箱中于80℃恒温干燥24h以上。负极材料活性物质磷酸钛锂(LiTi(PO4)3)的制备:往一定量的纳米TiO2粉末中,滴加一定量的聚乙烯醇溶液,依次加入Li2CO3和NH4H2PO4),混合物在90℃下用磁力搅拌搅干形成白色固体。将白色固体放入瓷舟中并转移至管式炉中,在N2气氛保护下900℃煅烧12h。负极制备方法同正极。取0.70g钨硅酸,2.0g聚乙烯醇溶液(0.1g/mL),0.10g硫酸锂混合,用饱和氢氧化锂逐滴滴加搅拌至中性,将调至均匀的溶液浇铸在电极材料表面,在湿度65%、温度32℃下恒重24h,制成膜电极。集流体采用不锈钢压块,顺序将膜正极/绝缘塑料隔片/膜负极组装成纽扣电池,测试电池充放电性能。在0-2V工作区间,放电电流0.2C时,电池体系的首次放电容量为50.4mAh/g。
实施例4
正极使用商业级尖晶石型锰酸锂,浆料质量配比按照锰酸锂:乙炔黑:聚四氟乙烯=82:10:8混浆,在不锈钢网上压制成膜,将压制的膜在真空干燥箱中于80℃恒温干燥24h以上。负极材料活性物质磷酸钛锂(LiTi(PO4)3)的制备:往一定量的纳米TiO2粉末中,滴加一定量的聚乙烯醇溶液,依次加入Li2CO3和NH4H2PO4),混合物在90℃下用磁力搅拌搅干形成白色固体。将白色固体放入瓷舟中并转移至管式炉中,在N2气氛保护下900℃煅烧12h。负极制备方法同正极。取0.40g钨硅酸,5.0g聚乙烯醇溶液(0.1g/mL),0.10g硫酸锂混合,用饱和氢氧化锂逐滴滴加搅拌至中性,将调至均匀的溶液浇铸在电极材料表面,在湿度65%、温度32℃下恒重24h,制成膜电极。集流体采用不锈钢压块,顺序将膜正极/绝缘塑料隔片/膜负极组装成纽扣电池,测试电池充放电性能。在0-2V工作区间,放电电流0.2C时,电池体系的首次放电容量为49.0mAh/g。
实施例5
正极使用商业级尖晶石型锰酸锂,浆料质量配比按照锰酸锂:乙炔黑:聚四氟乙烯=82:10:8混浆,在不锈钢网上压制成膜,将压制的膜在真空干燥箱中于80℃恒温干燥24h以上。负极材料活性物质磷酸钛锂(LiTi(PO4)3)的制备:往一定量的纳米TiO2粉末中,滴加一定量的聚乙烯醇溶液,依次加入Li2CO3和NH4H2PO4),混合物在90℃下用磁力搅拌搅干形成白色固体。将白色固体放入瓷舟中并转移至管式炉中,在N2气氛保护下900℃煅烧12h。负极制备方法同正极。取0.20g钨硅酸,7.0g聚乙烯醇溶液(0.1g/mL),0.10g硫酸锂混合,用饱和氢氧化锂逐滴滴加搅拌至中性,将调至均匀的溶液浇铸在电极材料表面,在湿度65%、温度32℃下恒重24h,制成膜电极。集流体采用不锈钢压块,顺序将膜正极/绝缘塑料隔片/膜负极组装成纽扣电池,测试电池充放电性能。在0-2V工作区间,放电电流0.2C时,电池体系的首次放电容量为42.3mAh/g。
Claims (8)
1. 一种反应性聚合物电解质,其特征在于,按重量份计,包括以下组分:
杂多酸盐 5~90份,
锂盐 5~90份,
水溶性聚合物 5~90份,
水 10~300份。
2. 根据权利要求1所述的反应性聚合物电解质,其特征在于,所述的杂多酸盐为磷钨酸、硅钨酸与氢氧化锂形成的多金属氧酸锂盐,或通过锂离子置换质子后的杂多酸盐,或将包含杂多酸的聚合物电解质用浓氢氧化锂溶液调节为中性。
3. 根据权利要求1所述的反应性聚合物电解质,其特征在于,所述的锂盐为硫酸锂、硝酸锂、磷酸锂、氯化锂、碘化锂、高氯酸锂或三氟甲基磺酸锂。
4. 根据权利要求1所述的反应性聚合物电解质,其特征在于,所述的水溶性聚合物为聚乙烯醇、聚氧化乙烯、聚丙烯酸、聚四氟乙烯、水溶性橡胶、壳聚糖或淀粉。
5. 一种水系锂离子电池膜电极组件,其特征在于,包括权利要求1所述的反应性聚合物电解质和聚合物电解质膜,所述的聚合物电解质膜经过电化学方法处理。
6. 根据权利要求5所述的水系锂离子电池膜电极组件,其特征在于,所述的电化学方法为过充电压充电,所述的过充电压充电为充电电压比电池理论设计的电压高0.2~1V。
7. 根据权利要求5所述的水系锂离子电池膜电极组件,其特征在于,还包括正极材料、负极材料、导电剂和粘合剂。
8. 根据权利要求7所述的水系锂离子电池膜电极组件,其特征在于,所述的正极材料活性物质为锰酸锂、钴酸锂或磷酸铁锂;负极材料活性物质为磷酸钛锂。
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