CN105047926A - 一种混合储能器件及其制备方法 - Google Patents
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Abstract
本发明公开了一种混合储能器件,包括多孔炭正极、钛氧化物负极、含锂电解质溶液、由聚酰亚胺纤维膜及其单面附着的填料组成的隔膜。可以将超级电容器和电池的双电源外部组合,通过多孔碳、钛氧化物和耐高温隔膜等来实现内部融合,具有超级电容的双电层、锂离子电池的嵌脱锂混合储能特性。
Description
技术领域
本发明涉及一种混合储能器件及其制备方法,属于储能器件领域。
背景技术
目前所用的动力电池能量密度较低,重量体积大,使用寿命短,成本较高,工作温度范围窄,充电时间长。为了改善这些不利影响,人们从正极材料、负极材料、隔膜电解液等方面进行动力电池的研究开发。
能源危机和环境污染带来的一系列社会问题,促使了节能及新能源汽车的发展。这其中,动力电源成为制约瓶颈。动力电源除了要满足汽车的功率、能量、安全性能及安装方便等要求外,还要求充电快捷,使用寿命长,成本低;然而,目前所用的动力电源能量密度较低,汽车续驶里程短;功率密度较小,汽车启动、爬坡及加速性能差;重量体积大,安装不便;使用寿命短,不能与整车相同;成本较高,整车综合成本居高不下;工作温度范围窄,适应差;充电时间长,配套设施投入大。这些原因阻碍了动力电源在节能及新能源汽车上的大规模应用。因此,人们开始寻找满足功率和能量兼顾的方法。
双源外部组合模式,即电池和超级电容器组合成复合电源,在满足节能及新能源汽车的使用要求的同时,可以大大提高电池的效率,延长使用寿命。例如,将锂离子电池与超级电容器组成复合电源,作为汽车的动力电源,锂离子电池提供汽车的续驶里程所需动力,超级电容器可以在启动、加速、爬坡等大功率输出工况工作,二者的组合提高了汽车的动力性能,延长了电池的使用寿命。
双源内部融合模式,将某一种动力电池的特征元素与超级电容器的特征元素,通过体系的优化设计,在同一单体内融合,使其兼具两种动力电源的特征,可以在功率密度和能量密度之间寻找平衡点,满足特定汽车工况需要。例如,针对混合动力车,可以以满足功率要求为主,兼顾部分能量需求,进行一定距离的纯电动状态行驶。
日本的JMEnergy、旭化成、NEC-TOKIN、ACT、帝客、FDK、太阳诱电、日立化成等研究开发锂离子电容器,部分已经实现商品化,日本富士重工业株式会社(公开号US2009/0197171A1,US2010/0142121A1,US2010/0128415A1,US7,733,629B2,申请号200580004509.2,申请号200580001498.2,申请号200680032109.7,申请号200680038604.9,申请号200680042376.2,申请号200680046167.5,申请号200680049541.7,申请号200710145884.X)有计划将锂离子电容器应用于斯巴鲁汽车;申请号为200410093962.2的中国专利报道了一种高电压超级电容器,将负极材料制成糊状物涂覆在金属箔上,经干燥、辊压制成负极板后,嵌锂再部分脱锂化成,与活性炭正极组成超级电容器,具有约4V的最高工作电压。申请号200810046091.7的中国专利报道了一种含有C、Fe和P元素的高电位超级电容器电极材料,申请号201010280801.X的中国专利报道了一种磷酸铁锂负载在活性炭作为正极活性物质,申请号200710035051.8的中国专利报道了一种采用锂离子电池正极材料与超级电容器电极材料的混合物作为正极活性物质,以锂离子电池负极材料与超级电容器电极材料的混合物作为负极活性物质,申请号200710035205.3的中国专利报道了一种超级电容电池,正极活性电极材料采用锂离子嵌入化合物和多孔炭材料的混合物,负极活性电极材料采用多孔炭材料和石墨类材料的混合物,申请号为200810031490.6的中国专利报道了一种兼具超级电容器与锂离子电池特征的新型储能器件及其制造方法,公开号为CN1866427A的中国专利报道了一种基于液相中的电化学活性物质的超级电容器,申请号201010592947.8的中国专利报道了一种新型水系/有机系混合型锂离子电池。
综合以上分析可以看出,为了发挥超级电容器的功率优势和锂离子电池的能量优势,可以将超级电容器和电池的双电源外部组合通过特征材料的内部组合来实现,从而获得兼具二者特征的混合储能器件。
发明内容
本发明的目的在于提供一种混合储能器件及其制备方法,可以将超级电容器和电池的双电源外部组合,通过多孔碳、钛氧化物和耐高温隔膜等来实现内部融合,具有超级电容的双电层、锂离子电池的嵌脱锂混合储能特性。
本发明技术方案是这样实现的:一种混合储能器件,包括多孔炭正极、钛氧化物负极、含锂电解质溶液、由聚酰亚胺纤维膜及其单面附着的填料组成的隔膜;其特征在于其制备方法如下:(1)多孔炭正极制备:多孔炭颗粒,比表面积为1500~2300m2/g的颗粒占多孔炭总质量的10~30%;按质量比称取活性炭、导电剂、羧甲基纤维素钠和丁苯橡胶乳液,加入去离子水混合3~6h,得到浆料,将浆料涂敷在铝箔上,真空干燥,裁片得到正极片;
(2)隔膜制备:称取填料,将粘结剂制成质量浓度为20%的溶液,首次将总体积的0.5~2%的粘结剂溶液与填料混合20~60min,然后将总体积的2%的粘结剂溶液与填料混合20~60min;将总体积的20%的粘结剂溶液与填料混合20~60min;将剩余的粘结剂溶液与填料混合20~60min,然后真空条件下,继续混合1h,加入溶剂,形成固含量为4~30%的分散液。得到的分散液涂敷在厚度为20~80um的聚酰亚胺纤维膜的单面,去除溶剂,得到隔膜;
(3)钛负极制备:按质量比称取钛氧化物、导电剂和聚偏氟乙烯,加入N-甲基吡咯烷酮搅拌,得到浆料,得到的浆料涂敷在铜箔上,真空干燥,裁片得到负极片。按照正极片、隔膜和负极片的顺序组合在一起,附着填料颗粒的隔膜面与钛氧化物电极接触;注入含锂电解质溶液,封装,老化,得到混合储能器件。
所述的正极活性炭、导电剂、羧甲基纤维素钠和丁苯橡胶乳液质量比为86~90:5~10:1~3:1~3;所述的钛酸锂、导电剂和聚偏氟乙烯质量比为80~85:10~15:5~8。
所述的填料包括三氧化二铝、蒙脱土、二氧化钛、氧化石墨烯、钛酸钡,质量为聚酰亚胺纤维膜质量的2~40%。
所述的粘结剂包括聚偏氟乙烯、六氟丙烯-聚偏氟乙烯共聚物、聚四氟乙烯、羧甲基纤维素钠、聚氧乙烯、聚乙烯醇,质量为填料质量的5~20%。
所述的多孔炭包括活性炭、活性石墨烯、炭气凝胶、泡沫炭、活性碳纤维、碳纳米管中的一种或几种。
所述的钛氧化物包括钛酸锂、二氧化钛及其改性材料。
本发明的积极效果可以将超级电容器和电池的双电源外部组合,通过多孔碳、钛氧化物和耐高温隔膜等来实现内部融合,具有超级电容的双电层、锂离子电池的嵌脱锂混合储能特性。本发明的混合储能器件制备工艺简单,安全性高,易于实现。
附图说明
图1是本发明的混合储能器件的结构示意图。
图2是本发明实施例1的活性炭正极片的SEM照片。
图3是本发明实施例1的隔膜附着添加剂颗粒一面的SEM照片。
图4是本发明实施例1的隔膜未附着添加剂颗粒一面的SEM照片。
图5是本发明实施例1的钛酸锂负极片的SEM照片。
图6是本发明实施例1的充放电曲线图。
具体实施方式
所述的实施例只是对本发明的权利要求的具体描述,权利要求包括但不限于所述的实施例内容。
实施例1
(1)活性炭正极片制备:按质量比90:5:5称取活性炭(比表面积为1480m2/g的活性炭与比表面积为2300m2/g的活性炭按质量比9:1的混合物)、导电剂、1%羧甲基纤维素钠和50%丁苯橡胶乳液,加入去离子水混合3h,得到固含量为28%的浆料,将浆料涂敷在铝箔上,真空干燥,裁片得到正极片。
(2)隔膜制备:称取三氧化二铝(聚酰亚胺质量的10%),将六氟丙烯-偏氟乙烯共聚物制成质量浓度为20%的粘结剂溶液,首次将总体积的0.5%的粘结剂溶液与三氧化二铝混合20min,然后将总体积的2%的粘结剂溶液与三氧化二铝混合20min;将总体积的20%的粘结剂溶液与三氧化二铝混合1h;将剩余的粘结剂溶液与三氧化二铝混合1h,然后真空条件下,继续混合1h,加入丙酮,形成固含量为4%的分散液。得到的分散液涂敷在厚度为40um的聚酰亚胺纤维膜的单面,去除溶剂,得到隔膜。
(3)钛酸锂负极片制备:按质量比85:10:5称取钛酸锂、导电剂和聚偏氟乙烯,加入N-甲基吡咯烷酮搅拌,得到固含量为35%的浆料,得到的浆料涂敷在铜箔上,真空干燥,裁片得到负极片。
按照正极片1、隔膜2和负极片3的顺序组合在一起,附着填料颗粒的隔膜面与钛氧化物电极接触;注入含锂电解质溶液,封装,老化,得到混合储能器件。
实施例2
(1)活性炭正极片制备:按质量比88:7:5称取活性炭(比表面积为1420m2/g的活性炭与比表面积为1800m2/g的活性炭按质量比7:3的混合物)、导电剂、1%羧甲基纤维素钠和50%丁苯橡胶乳液,加入去离子水混合3h,得到固含量为29%的浆料,将浆料涂敷在铝箔上,真空干燥,裁片得到正极片。
(2)隔膜制备:称取蒙脱土(聚酰亚胺质量的2%),将聚氧乙烯制成质量浓度为40%的粘结剂溶液,首次将总体积的1%的粘结剂溶液与蒙脱土混合20min,然后将总体积的2%的粘结剂溶液与蒙脱土混合20min;将总体积的30%的粘结剂溶液与蒙脱土混合1h;将剩余的粘结剂溶液与蒙脱土混合1h,然后真空条件下,继续混合1h,加入去离子水,形成固含量为10%的分散液。得到的分散液涂敷在厚度为40um的聚酰亚胺纤维膜的单面,去除溶剂,得到隔膜。
(3)钛酸锂负极片制备:按质量比80:12:8称取钛酸锂、导电剂和聚偏氟乙烯,加入N-甲基吡咯烷酮搅拌,得到固含量为35%的浆料,得到的浆料涂敷在铜箔上,真空干燥,裁片得到负极片。
按照正极片1、隔膜2和负极片3的顺序组合在一起,附着填料颗粒的隔膜面与钛氧化物电极接触;注入含锂电解质溶液,封装,老化,得到混合储能器件。
实施例3
(1)活性炭正极片制备:按质量比86:6:8称取活性炭(比表面积为1480m2/g的活性炭与比表面积为1680m2/g的活性炭按质量比8:2的混合物)、导电剂、1%羧甲基纤维素钠和50%丁苯橡胶乳液,加入去离子水混合3h,得到固含量为27%的浆料,将浆料涂敷在铝箔上,真空干燥,裁片得到正极片。
(2)隔膜制备:称取钛酸钡(聚酰亚胺质量的40%),将聚乙烯醇制成质量浓度为40%的粘结剂溶液,首次将总体积的5%的粘结剂溶液与钛酸钡混合20min,然后将总体积的5%的粘结剂溶液与钛酸钡混合20min;将总体积的20%的粘结剂溶液与钛酸钡混合1h;将剩余的粘结剂溶液与三氧化二铝混合1h,然后真空条件下,继续混合1h,加入去离子水,形成固含量为30%的分散液。得到的分散液涂敷在厚度为40um的聚酰亚胺纤维膜的单面,去除溶剂,得到隔膜。
(3)钛酸锂负极片制备:按质量比85:10:5称取钛酸锂、导电剂和聚偏氟乙烯,加入N-甲基吡咯烷酮搅拌,得到固含量为37%的浆料,得到的浆料涂敷在铜箔上,真空干燥,裁片得到负极片。
按照正极片1、隔膜2和负极片3的顺序组合在一起,附着填料颗粒的隔膜面与钛氧化物电极接触;注入含锂电解质溶液,封装,老化,得到混合储能器件。
Claims (5)
1.一种混合储能器件,包括多孔炭正极、钛氧化物负极、含锂电解质溶液、由聚酰亚胺纤维膜及其单面附着的填料组成的隔膜,其特征在于,制备方法包括如下步骤:
(1)多孔炭正极制备:多孔炭颗粒,比表面积为1500~2300m2/g的颗粒占多孔炭总质量的10~30%;按质量比称取活性炭、导电剂、羧甲基纤维素钠和丁苯橡胶乳液,加入去离子水混合3~6h,得到浆料,将浆料涂敷在铝箔上,真空干燥,裁片得到正极片;
(2)隔膜制备:称取填料,将粘结剂制成质量浓度为20%的溶液,首次将总体积的0.5~2%的粘结剂溶液与填料混合20~60min,然后将总体积的2%的粘结剂溶液与填料混合20~60min;将总体积的20%的粘结剂溶液与填料混合20~60min;将剩余的粘结剂溶液与填料混合20~60min,然后真空条件下,继续混合1h,加入溶剂,形成固含量为4~30%的分散液;得到的分散液涂敷在厚度为20~80um的聚酰亚胺纤维膜的单面,去除溶剂,得到隔膜;
(3)钛负极制备:按质量比称取钛氧化物、导电剂和聚偏氟乙烯,加入N-甲基吡咯烷酮搅拌,得到浆料,得到的浆料涂敷在铜箔上,真空干燥,裁片得到负极片;按照正极片、隔膜和负极片的顺序组合在一起,附着填料颗粒的隔膜面与钛氧化物电极接触;注入含锂电解质溶液,封装,老化,得到混合储能器件。
2.根据权利要求1所述的一种混合储能器件及其制备方法,其特征在于,所述的正极活性炭、导电剂、羧甲基纤维素钠和丁苯橡胶乳液质量比为86~90:5~10:1~3:1~3。
3.根据权利要求1所述的一种混合储能器件及其制备方法,其特征在于,所述的钛酸锂、导电剂和聚偏氟乙烯质量比为80~85:10~15:5~8。
4.根据权利要求1所述的一种混合储能器件及其制备方法,其特征在于,所述的填料包括三氧化二铝、蒙脱土、二氧化钛、氧化石墨烯、钛酸钡,质量为聚酰亚胺纤维膜质量的2~40%。
5.根据权利要求1所述的一种混合储能器件及其制备方法,其特征在于,所述的粘结剂包括聚偏氟乙烯、六氟丙烯-聚偏氟乙烯共聚物、聚四氟乙烯、羧甲基纤维素钠、聚氧乙烯、聚乙烯醇,质量为填料质量的5~20%。
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WO2020207362A1 (zh) * | 2019-04-08 | 2020-10-15 | 青岛九环新越新能源科技股份有限公司 | 双极导电薄膜连接结构的储能设备 |
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