CN106099182B - 一种锂电池细菌纤维素凝胶聚合物电解质的制备方法 - Google Patents
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Abstract
本发明公开了一种锂电池细菌纤维素凝胶聚合物电解质的制备方法,属于聚合物电解质制备技术领域。本发明将西瓜皮蒸煮后,与无水氯化钙等搅拌混合,再利用酵母菌协同沼气液中微生物共同进行发酵,取发酵液表面细菌纤维素膜,经冲洗、碱浸、水浴保温,抽滤得膜片,将膜片水浴处理、冷冻、二次解冻后,与聚乙二醇二甲醚和高氯酸锂混合,在真空条件下,浸渍得锂电池细菌纤维素凝胶聚合物电解质的方法。本发明制备步骤简单,充分利用细菌纤维素制备凝胶聚合物电解质,无须加入增塑剂,针对性强,有效解决了离子导电率低、机械性能差问题。
Description
技术领域
本发明涉及一种锂电池细菌纤维素凝胶聚合物电解质的制备方法,属于聚合物电解质制备技术领域。
背景技术
近年来,锂电池受到广泛关注,作为一种高能环保电池,其具有工作电压高、比能量大、可快速充放电及循环使用寿命长等优点,因此已经被广泛的应用于手机、笔记本电脑以及数码相机等电子产品。纤维素是自然界中分布最广泛、含量最丰富的可再生资源,具有可降解性、成膜性、无毒性、良好的相容性、结构稳定及力学性能优良等众多优点,使得纤维素在造纸、工业加工、建筑、油田化学、医学以及电子产品等领域均有所应用。将纤维素及其衍生物应用于电子产品领域尤其是应用于锂电池开始受到研究者们的关注。凝胶聚合物锂离子电池是在液体锂离子电池基础上发展起来的新一代锂离子电池。凝胶聚合物锂离子电池的关键是制备凝胶聚合物电解质,它的性能优劣直接影响锂离子电池性能的优化和提高。凝胶聚合物电解质是由聚合物、增塑剂和锂盐通过一定的方法形成的具有合适微结构的聚合物网络,利用固定在微结构中的液态电解质分子实现离子传导。目前研究较多的凝胶聚合物电解质体系主要有聚环氧乙烯、聚偏氟乙烯、聚丙烯腈和聚甲基丙烯酸甲酯。传统的凝胶聚合物电解质的制备方法主要采取溶剂浇铸,但是由于制备过程中加入较多量的增塑剂使得凝胶聚合物电解质存在离子导电率低、机械性能差等问题,且热稳定性差、凝固点高,在低温下电导率低,高温下电解液易分解变质。因此制备具有高电导率和优异的机械性能的凝胶聚合物电解质十分有必要。
发明内容
本发明所要解决的技术问题:针对传统凝胶聚合物电解质在制备过程中,需要加入增塑剂,导致离子导电率低、机械性能差的弊端,提供了一种将西瓜皮蒸煮后,与无水氯化钙等搅拌混合,再利用酵母菌协同沼气液中微生物共同进行发酵,取发酵液表面细菌纤维素膜,经冲洗、碱浸、水浴保温,抽滤得膜片,将膜片水浴处理、冷冻、二次解冻后,与聚乙二醇二甲醚和高氯酸锂混合,在真空条件下,浸渍得锂电池细菌纤维素凝胶聚合物电解质的方法。本发明制备步骤简单,充分利用细菌纤维素制备凝胶聚合物电解质,无须加入增塑剂,针对性强,有效解决了离子导电率低、机械性能差问题。
为解决上述技术问题,本发明采用如下所述的技术方案是:
(1)称取新鲜西瓜皮300~500g,加入盛有1~2L清水的蒸锅中,加热至沸腾,在沸腾状态下蒸煮20~30min,取出西瓜皮,待其自然冷却至室温后,加入盛有1~2L去离子水的密闭发酵罐中,再依次加入0.3~0.5g无水氯化钙,0.2~0.4g磷酸二氢钾,滴加质量浓度为6~8%柠檬酸溶液,调节pH至6.2~6.4,启动发酵罐搅拌器,以300~400r/min转速搅拌混合10~15min;
(2)待搅拌结束,依次加入2~4g酵母粉和10~15mL沼气液,用玻璃棒搅拌混合10~15min后,启动发酵罐加热器,加热升温至30~35℃,静置恒温密闭发酵5~7天,用镊子取出发酵液表层纤维素膜,并用去离子水冲洗3~5次后,将其浸入盛有100~150mL质量浓度为0.1~0.3mol/L氢氧化钠溶液的烧杯中;
(3)再将烧杯置于75~80℃恒温水浴锅中,保温处理45~60min,抽滤,除去滤液,得膜片,用去离子水洗涤膜片至洗涤液呈中性,随后将膜片转入盛有160~180mL去离子水的烧杯中,再将烧杯置于90~95℃振荡水浴锅中处理18~24h,取出膜片,再将膜片置于冰箱中于-20~-18℃冷冻6~8h,4~6℃解冻2~4h后,再于室温下解冻2~4h,得细菌纤维素凝胶;
(4)按重量份数计,在烧杯中,依次加入100~120份聚乙二醇二甲醚,15~20份高氯酸锂,20~25份上述所得细菌纤维素凝胶,用玻璃棒搅拌3~5min后,将烧杯转入真空烘箱内,在真空度为0.02~0.04MPa条件下,以3~5℃/min速率逐步升温至180~200℃,保温45~60min,待其自然冷却至室温后,即得锂电池细菌纤维素凝胶聚合物电解质。
本发明制得的锂电池细菌纤维素凝胶聚合物电解质拉伸强度达38.6~39.8MPa,断裂伸长率为48~50%,分解温度为248~250℃,室温下电导率达1.60×10-2~1.63×10- 2S·cm-1。
本发明与其他方法相比,有益技术效果是:
(1)本发明制备步骤简单,充分利用细菌纤维素制备凝胶聚合物电解质,无须加入增塑剂,针对性强;
(2)所得电解质电导率高,机械性能好。
(3)本发明以廉价易得的西瓜皮为细菌发酵的营养来源,提高了西瓜皮的经济利用价值,减少了淀粉等粮食作物的消耗,为果农增加了新的经济来源。
具体实施方式
首先称取新鲜西瓜皮300~500g,加入盛有1~2L清水的蒸锅中,加热至沸腾,在沸腾状态下蒸煮20~30min,取出西瓜皮,待其自然冷却至室温后,加入盛有1~2L去离子水的密闭发酵罐中,再依次加入0.3~0.5g无水氯化钙,0.2~0.4g磷酸二氢钾,滴加质量浓度为6~8%柠檬酸溶液,调节pH至6.2~6.4,启动发酵罐搅拌器,以300~400r/min转速搅拌混合10~15min;待搅拌结束,依次加入2~4g酵母粉和10~15mL沼气液,用玻璃棒搅拌混合10~15min后,启动发酵罐加热器,加热升温至30~35℃,静置恒温密闭发酵5~7天,用镊子取出发酵液表层纤维素膜,并用去离子水冲洗3~5次后,将其浸入盛有100~150mL质量浓度为0.1~0.3mol/L氢氧化钠溶液的烧杯中;然后再将烧杯置于75~80℃恒温水浴锅中,保温处理45~60min,抽滤,除去滤液,得膜片,用去离子水洗涤膜片至洗涤液呈中性,随后将膜片转入盛有160~180mL去离子水的烧杯中,再将烧杯置于90~95℃振荡水浴锅中处理18~24h,取出膜片,再将膜片置于冰箱中于-20~-18℃冷冻6~8h,4~6℃解冻2~4h后,再于室温下解冻2~4h,得细菌纤维素凝胶;最后按重量份数计,在烧杯中,依次加入100~120份聚乙二醇二甲醚,15~20份高氯酸锂,20~25份上述所得细菌纤维素凝胶,用玻璃棒搅拌3~5min后,将烧杯转入真空烘箱内,在真空度为0.02~0.04MPa条件下,以3~5℃/min速率逐步升温至180~200℃,保温45~60min,待其自然冷却至室温后,即得锂电池细菌纤维素凝胶聚合物电解质。
实例1
首先称取新鲜西瓜皮300g,加入盛有1L清水的蒸锅中,加热至沸腾,在沸腾状态下蒸煮20min,取出西瓜皮,待其自然冷却至室温后,加入盛有1L去离子水的密闭发酵罐中,再依次加入0.3g无水氯化钙,0.2g磷酸二氢钾,滴加质量浓度为6%柠檬酸溶液,调节pH至6.2,启动发酵罐搅拌器,以300r/min转速搅拌混合10min;待搅拌结束,依次加入2g酵母粉和10mL沼气液,用玻璃棒搅拌混合10min后,启动发酵罐加热器,加热升温至30℃,静置恒温密闭发酵5天,用镊子取出发酵液表层纤维素膜,并用去离子水冲洗3次后,将其浸入盛有100mL质量浓度为0.1mol/L氢氧化钠溶液的烧杯中;然后再将烧杯置于75℃恒温水浴锅中,保温处理45min,抽滤,除去滤液,得膜片,用去离子水洗涤膜片至洗涤液呈中性,随后将膜片转入盛有160mL去离子水的烧杯中,再将烧杯置于90℃振荡水浴锅中处理18h,取出膜片,再将膜片置于-20℃冰箱中冷冻6h,4℃解冻2h后,再于室温下解冻2h,得细菌纤维素凝胶;最后按重量份数计,在烧杯中,依次加入100份聚乙二醇二甲醚,15份高氯酸锂,20份上述所得细菌纤维素凝胶,用玻璃棒搅拌3min后,将烧杯转入真空烘箱内,在真空度为0.02MPa条件下,以3℃/min速率逐步升温至180℃,保温45min,待其自然冷却至室温后,即得锂电池细菌纤维素凝胶聚合物电解质。
本发明制备步骤简单,充分利用细菌纤维素制备凝胶聚合物电解质,针对性强;所得电解质电导率高,机械性能好;制得的锂电池细菌纤维素凝胶聚合物电解质拉伸强度达38.6MPa,断裂伸长率为48%,分解温度为248℃,室温下电导率达1.60×10-2S·cm-1。
实例2
首先称取新鲜西瓜皮400g,加入盛有2L清水的蒸锅中,加热至沸腾,在沸腾状态下蒸煮25min,取出西瓜皮,待其自然冷却至室温后,加入盛有2L去离子水的密闭发酵罐中,再依次加入0.4g无水氯化钙,0.3g磷酸二氢钾,滴加质量浓度为7%柠檬酸溶液,调节pH至6.3,启动发酵罐搅拌器,以350r/min转速搅拌混合13min;待搅拌结束,依次加入3g酵母粉和13mL沼气液,用玻璃棒搅拌混合13min后,启动发酵罐加热器,加热升温至33℃,静置恒温密闭发酵6天,用镊子取出发酵液表层纤维素膜,并用去离子水冲洗4次后,将其浸入盛有125mL质量浓度为0.2mol/L氢氧化钠溶液的烧杯中;然后再将烧杯置于78℃恒温水浴锅中,保温处理52min,抽滤,除去滤液,得膜片,用去离子水洗涤膜片至洗涤液呈中性,随后将膜片转入盛有170mL去离子水的烧杯中,再将烧杯置于93℃振荡水浴锅中处理21h,取出膜片,再将膜片置于-19℃冰箱中冷冻7h,5℃解冻3h后,再于室温下解冻3h,得细菌纤维素凝胶;最后按重量份数计,在烧杯中,依次加入110份聚乙二醇二甲醚,18份高氯酸锂,23份上述所得细菌纤维素凝胶,用玻璃棒搅拌4min后,将烧杯转入真空烘箱内,在真空度为0.03MPa条件下,以4℃/min速率逐步升温至190℃,保温52min,待其自然冷却至室温后,即得锂电池细菌纤维素凝胶聚合物电解质。
本发明制备步骤简单,充分利用细菌纤维素制备凝胶聚合物电解质,针对性强;所得电解质电导率高,机械性能好;制得的锂电池细菌纤维素凝胶聚合物电解质拉伸强度达39.2MPa,断裂伸长率为49%,分解温度为249℃,室温下电导率达1.62×10-2S·cm-1。
实例3
首先称取新鲜西瓜皮500g,加入盛有2L清水的蒸锅中,加热至沸腾,在沸腾状态下蒸煮30min,取出西瓜皮,待其自然冷却至室温后,加入盛有2L去离子水的密闭发酵罐中,再依次加入0.5g无水氯化钙,0.4g磷酸二氢钾,滴加质量浓度为8%柠檬酸溶液,调节pH至6.4,启动发酵罐搅拌器,以400r/min转速搅拌混合15min;待搅拌结束,依次加入4g酵母粉和15mL沼气液,用玻璃棒搅拌混合15min后,启动发酵罐加热器,加热升温至35℃,静置恒温密闭发酵7天,用镊子取出发酵液表层纤维素膜,并用去离子水冲洗5次后,将其浸入盛有150mL质量浓度为0.3mol/L氢氧化钠溶液的烧杯中;然后再将烧杯置于80℃恒温水浴锅中,保温处理60min,抽滤,除去滤液,得膜片,用去离子水洗涤膜片至洗涤液呈中性,随后将膜片转入盛有180mL去离子水的烧杯中,再将烧杯置于95℃振荡水浴锅中处理24h,取出膜片,再将膜片置于-18℃冰箱中冷冻8h,6℃解冻4h后,再于室温下解冻4h,得细菌纤维素凝胶;最后按重量份数计,在烧杯中,依次加入120份聚乙二醇二甲醚,20份高氯酸锂,25份上述所得细菌纤维素凝胶,用玻璃棒搅拌5min后,将烧杯转入真空烘箱内,在真空度为0.04MPa条件下,以5℃/min速率逐步升温至200℃,保温60min,待其自然冷却至室温后,即得锂电池细菌纤维素凝胶聚合物电解质。
本发明制备步骤简单,充分利用细菌纤维素制备凝胶聚合物电解质,针对性强;所得电解质电导率高,机械性能好;制得的锂电池细菌纤维素凝胶聚合物电解质拉伸强度达39.8MPa,断裂伸长率为50%,分解温度为250℃,室温下电导率达1.63×10-2S·cm-1。
Claims (1)
1.一种锂电池细菌纤维素凝胶聚合物电解质的制备方法,其特征在于具体制备步骤为:
(1)称取新鲜西瓜皮300~500g,加入盛有1~2L清水的蒸锅中,加热至沸腾,在沸腾状态下蒸煮20~30min,取出西瓜皮,待其自然冷却至室温后,加入盛有1~2L去离子水的密闭发酵罐中,再依次加入0.3~0.5g无水氯化钙,0.2~0.4g磷酸二氢钾,滴加质量浓度为6~8%柠檬酸溶液,调节pH至6.2~6.4,启动发酵罐搅拌器,以300~400r/min转速搅拌混合10~15min;
(2)待搅拌结束,依次加入2~4g酵母粉和10~15mL沼气液,用玻璃棒搅拌混合10~15min后,启动发酵罐加热器,加热升温至30~35℃,静置恒温密闭发酵5~7天,用镊子取出发酵液表层纤维素膜,并用去离子水冲洗3~5次后,将其浸入盛有100~150mL质量浓度为0.1~0.3mol/L氢氧化钠溶液的烧杯中;
(3)再将烧杯置于75~80℃恒温水浴锅中,保温处理45~60min,抽滤,除去滤液,得膜片,用去离子水洗涤膜片至洗涤液呈中性,随后将膜片转入盛有160~180mL去离子水的烧杯中,再将烧杯置于90~95℃振荡水浴锅中处理18~24h,取出膜片,再将膜片置于冰箱中于-20~-18℃冷冻6~8h,4~6℃解冻2~4h后,再于室温下解冻2~4h,得细菌纤维素凝胶;
(4)按重量份数计,在烧杯中,依次加入100~120份聚乙二醇二甲醚,15~20份高氯酸锂,20~25份上述所得细菌纤维素凝胶,用玻璃棒搅拌3~5min后,将烧杯转入真空烘箱内,在真空度为0.02~0.04MPa条件下,以3~5℃/min速率逐步升温至180~200℃,保温45~60min,待其自然冷却至室温后,即得锂电池细菌纤维素凝胶聚合物电解质。
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