CN114530628A - 一种薄膜全固态电池 - Google Patents
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Abstract
本发明属于电化学技术领域,具体为一种全固态薄膜电池。本发明全固态薄膜电池包括:正极层,负极层,全固态隔膜层,柔性电池极板;其中,正极层和负极层位于同一平面中;并且正极层和负极层之间有间隙;正极层由正极活性材料、固态电解质、导电助剂和粘结剂按一定工艺混合而成;负极层由石墨与固态电解质复合而成,或由锂金属及Li‑Al,Li‑In,Li‑Sn合金组成;全固态隔膜层由具备超高离子电导率的固态电解质组成;柔性电池极板分别由超薄铝箔及铜箔组成;固态电解质层与正、负极接触侧采用网格状延伸结构。本发明从根本上避免了正、负极层堆叠结构带来的接触短路风险,并大大提高离子电导率。
Description
技术领域
本发明属于电化学技术领域,具体涉及一种全固态薄膜电池。
背景技术
全固态薄膜电池采用非液体电解质取代传统的液体电解质,有效避免了电池破损后的漏液问题,同时大大拓宽了电池有效工作温度区间 (通常采用传统液体电解质的薄膜电池工作区间为-10~60℃,全固态薄膜电池的工作区间拓展到-30~150℃)。但是目前的全固态薄膜电池结构仍存在比较明显的安全隐患。目前的传统固态薄膜电池的结构由正极层、隔膜、负极层堆叠封装而成,在高压力或周期性循环低压冲击服役环境中不可避免地存在电池短路失效及安全风险。
现行技术中一般采用如下技术措施来进行针对性改善:
1.适当增加固体电解质隔膜的厚度,降低短路风险。此方法有助于提高电池抗击外部压力的能力,使电池能承受的外部压力有所增加,但是无法从根本上解决受压短路尤其在承受冲击压力状态下的短路。
2.调节固体电解质隔膜的成分,使其具有一定的流变性和粘接能力,在被外界穿刺或者压力挤压的状态下能够隔断正负极的直接接触,从一定程度减小短路风险。此技术改进对规律性的、低频的压力挤压会有较好的效果,但仍然无法从根本上避免短路风险。
发明内容
针对目前固态薄膜电池的结构性短路风险,本发明的目的在于提供离子电导率高,且可避免短路风险的全新固态薄膜电池。
本发明提供的固态薄膜电池,其结构如图1所示,包括:正极层,负极层,全固态隔膜层,柔性电池极板;其中:
所述正极层和负极层位于同一平面中,并且,正极层和负极层间隔一定距离(间隙)(根据具体电池性能指标要求,该距离在纳米到毫米水平,例如为100纳米-2毫米),从根本上避免了正、负极层堆叠结构带来的接触短路风险;
所述正极层,由正极活性材料、固态电解质、导电助剂和粘结剂按一定工艺混合而成;进一步地:
所述正极活性材料选自钴酸锂(LCO),磷酸铁锂(LFP),锂镍钴话(NCM),锂镍钴铝(NCA)、锰酸锂(LMO),活性硫等;
所述固态电解质选自锂锗磷硫(LGPS)、锂磷硫(LPS)、锂镧锆氧(LLZ0)、锂磷氧氮(LPON)等;
所述导电助剂选自导电碳、铝,铜、金、银等金属粉末;
所述粘结剂选自聚偏氟乙烯(PVDF)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)、聚甲基丙烯酸甲酯(PMMA)等;
所述负极层,由石墨与固态电解质复合而成,或由锂金属及Li-Al,Li-In,Li-Sn等合金组成;进一步地,所述固态电解质选自锂锗磷硫(LGPS)、锂磷硫(LPS)、锂镧锆氧(LLZ0)、锂磷氧氮(LPON)等;
所述全固态隔膜层,由具备超高离子电导率的固态电解质组成,该固态电解质选自锂锗磷硫(LGPS)、锂磷硫(LPS)锂磷硫氯(LPSCl)、锂磷硫溴(LPSBr),可实现离子在正负极之间的快速穿梭。
进一步地,在正负极活性物质层中通过刻蚀方法形成沟槽,将固态电解质填充在此沟槽中,可进一步增大电极与电解质之间的界面接触面积,提高离子电导率。
所述柔性电池极板,分别由超薄铝箔及铜箔组成。
所述电池正、负极以及隔膜层材料分别由表面封装膜进行封装,实现与外界环境相隔离。
本发明还提供薄膜全固态电池的制备方法,具体步骤如下:
1、采用浆料涂覆法将正极复合材料涂覆于铝箔极板上,烘干成膜;正极复合材料及其浆料的成分、制作方法及设备沿用传统固体薄膜电池的材料和工艺;
2、负极材料为石墨与电解质复合材料的情况,其制作工艺与正极相似;负极材料为金属或合金的情况,采用辊压法将负极材料与铜箔极板叠轧在一体;
3、采用刻线法在正极和负极侧分别除去部分电极材料,形成密集网格网络;
4、将上述正极和负极压装于同一片封装膜上;
5、将固态电解质分散于有机溶剂(如四氢呋喃,丙酮,乙酸乙酯,丁酸乙酯,三甲醇二甲醚等)中,添加适量粘结剂后制作成隔膜浆料,采用涂覆法将上述隔膜浆料涂覆于封装膜(如铝塑膜)上,真空烘干成型;
6、将上述薄膜电池辊压成型,增加颗粒间界面接触面积和薄膜强度;采用封装膜真空封装。
附图说明
图1为本发明薄膜全固态电池结构图示。
图2为实施例1的电池样品的充放电循环性能。
图3为实施例2的电池样品的充放电倍率性能。
图中标号:1为正极层,2为负极层,3为全固态隔膜层,4为柔性电池极板,5为表面封装膜;6为正极集电体,7为负极集电体,8为正极活性物质层,9为负极活性物质层,10为刻线槽。
具体实施方式
下面结合附图和实施例进一步介绍本发明。
实施例1,循环型
将由磷酸铁锂(LiFeP04)、锂锗磷硫固态电解质(Li10GeP2S12)、碳黑导电助剂、粘结剂组成的正极浆料涂布在电极铝箔上,烘干并切割成一定尺寸的正极膜片。将由石墨、锂锗磷硫固态电解质(Li10GeP2S12)组成的负极浆料涂布在电极铜箔上,烘干并切割成一定尺寸的负极膜片。将正、负极膜片采用辊压法平行压装于封装膜A的同一面。采用刻线法在正极和负极膜片上分别除去部分电极材料,形成密集网格。刻线的宽度为10~100μm。将锂锗磷硫固态电解质和粘结剂用有机溶剂分散并揽拌均匀形成电解质浆料,采用涂覆法将上述隔膜浆料涂覆于正、负极膜片以及正、负极膜片二者间隙中,与正、负极膜片位于同一面并连接正、负极膜片。将上述薄膜电池辊压成型,烘干后采用封装膜B真空封装成最终电池产品。封装完成的电池样品在室温下2mA电流下的充放电性能如图2所示。
实施例2,倍率型
将由钴酸锂(LCO)、锂磷氧氯固态电解质(LPON)在高温高压下烧结压片成膜并压装在电极铝箔上,切割成一定尺寸的正极膜片。将LiIn合金压装在电极铜箔上,切割成一定尺寸的负极膜片。采用刻线法在正极和负极膜片上分别除去部分电极材料,形成密集网格。刻线的宽度为10-100μm。将锂磷硫氯固态电解质(Li5.5PS4.5C11.5)和粘结剂用有机溶剂分散并揽拌均匀形成电解质浆料,采用涂布法将上述隔膜奖料涂覆于正负极膜片以及二者间隙中,与正、负极膜片位于同一面并连接正、负极膜片。将上述薄膜电池辊压成型,烘干后采用封装膜B直空封装成最终电池产品。封装完成的电池样品在室温下的倍率性能如图3所示。
Claims (5)
1.一种固态薄膜电池,其特征在于,包括:正极层,负极层,全固态隔膜层,柔性电池极板;其中:
所述正极层和负极层位于同一平面中;并且,正极层和负极层之间有间隙;
所述正极层,由正极活性材料、固态电解质、导电助剂和粘结剂混合而成;
所述负极层,由石墨与固态电解质复合而成,或由锂金属及Li-Al,Li-In,Li-Sn合金组成;
所述全固态隔膜层,由具备超高离子电导率的固态电解质组成;
所述柔性电池极板,分别由超薄铝箔及铜箔组成;
所述电池正、负极以及隔膜层材料分别由表面封装膜进行封装。
2.根据权利要求1所述的固态薄膜电池,其特征在于, 所述正极层中,正极活性材料选自钴酸锂,磷酸铁锂,锂镍钴话,锂镍钴铝、锰酸锂、活性硫;
所述固态电解质选自锂锗磷硫、锂磷硫、锂镧锆氧、锂磷氧氮;
所述导电助剂选自导电碳、铝,铜、金、银粉末;
所述粘结剂选自聚偏氟乙烯、聚氯乙烯、聚四氟乙烯、聚甲基丙烯酸甲酯。
3.根据权利要求1所述的固态薄膜电池,其特征在于,所述负极层中的固态电解质选自锂锗磷硫、锂磷硫、锂镧锆氧、锂磷氧氮。
4.根据权利要求1所述的固态薄膜电池,其特征在于,所述全固态隔膜层中的固态电解质选自锂锗磷硫、锂磷硫锂磷硫氯、锂磷硫溴。
5.根据权利要求1所述的固态薄膜电池,其特征在于,所述固态电解质层与正、负极接触侧采用网格状延伸结构。
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