CN108054434A - 一种一次电纺柔性超薄锂离子电池的制备方法 - Google Patents

一种一次电纺柔性超薄锂离子电池的制备方法 Download PDF

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CN108054434A
CN108054434A CN201711286057.2A CN201711286057A CN108054434A CN 108054434 A CN108054434 A CN 108054434A CN 201711286057 A CN201711286057 A CN 201711286057A CN 108054434 A CN108054434 A CN 108054434A
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杨震宇
陈德良
李超锋
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Dongguan University of Technology
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Abstract

本发明公开了一种一次电纺柔性超薄锂离子电池的制备方法，按配比称取石墨烯、碳纳米管及溶剂，超声分散制成石墨烯/碳纳米管胶体溶液；利用高压静电喷雾装置在集流体上喷涂石墨烯/碳纳米管复合膜负极；按比例制备固体电解质材料，利用高压静电纺丝装置直接在形成的负极上电纺固体电解质薄膜；最后采用制备的正极材料纺丝液在形成的电解质薄膜上电纺一层正极；最后附上一层集流体；即得到锂离子电池。优点是：电纺的负极是一维碳管二维石墨烯复合的三维结构，具有良好的导电性；电纺的固体电解质与正负极接触性能良好，可以通过调控厚薄改善电解质膜的离子电导率；而且正负极薄膜厚度从10微米起可调，从而制备不同容量的电池(0.25Wh‑5Wh)。

Description

一种一次电纺柔性超薄锂离子电池的制备方法
技术领域
本发明涉及电化学技术领域，尤其涉及一种一次电纺柔性超薄锂离子电池的制备方法。
背景技术
随着科学技术的发展以及人们物质文化需求的提高，便携式及可穿戴电子产品与器件备受关注，包括可卷曲显示器，电子纸，柔性电池等。因此，柔性轻薄的锂离子电池将有很大的发展潜力和市场需求。
目前市场上的锂离子电池大都采用分离的部件如集流体、工作电极、电解质和隔膜，柔性较差，且重量、体积较大。在发生折叠或弯曲等形变时，锂离子电池各部件的相对移动会极大地损坏器件结构，导致超级电容器性能变差，循环稳定性降低。因此，减轻减薄锂离子电池及寻找一种集成化且低成本柔性超薄锂离子电池的制备方法对研究与开发新型储能装置及器件具有重要的价值和意义。
发明内容
为了解决现有的锂离子电池制备方法的不足，本发明目的在于提供一种一次电纺柔性超薄锂离子电池的制备方法。
本发明采取的技术方案是：
本发明的一次电纺柔性超薄锂离子电池的制备方法的具体步骤如下：
(1)按配比称取石墨烯、碳纳米管及溶剂，超声分散制成石墨烯/碳纳米管胶体溶液；
(2)利用高压静电喷雾装置在集流体上静电喷涂石墨烯/碳纳米管复合膜负极；
(3)按比例制备固体电解质材料，利用高压静电纺丝装置直接在形成的负极上电纺固体电解质薄膜；
(4)采用制备的正极材料纺丝液在形成的电解质薄膜上电纺一层正极；最后附上一层金属箔集流体；即得到本发明一次电纺柔性超薄锂离子电池。
步骤(1)中，石墨烯溶液的浓度5mg/ml；碳纳米管溶液浓度是0.5mg/ml，溶剂是水、乙醇、乙二醇、NMP或二元混合溶液，石墨烯溶液和碳纳米管溶液二者体积比是1:1或2:1。
步骤(2)中，静电喷涂电压12KV，恒温温度50摄氏度；石墨烯/碳纳米管复合膜负极膜厚度10-100微米。
步骤(3)中，固体电解质材料的组成是：10wt％PEO+(0.5mol/L)LiClO4(高氯酸锂)或5wt％PVDF+5wt％PEO+(0.5mol/L)LiClO4或10wt％PVDF+(0.5mol/L)LiClO4；溶剂是NMP，DMF及其混合物。
步骤(3)中，静电纺丝电压15-20KV，恒温温度50摄氏度；纺丝膜厚度10-100微米。
步骤(4)中，正极材料浆料的组成是：80％磷酸铁锂+10％导电剂+10％PVDF浆料或80％三元材料+10％导电剂+10％PVDF；溶剂是NMP。
步骤(4)中，静电喷涂电压15-20KV，恒温温度50摄氏度；纺丝膜厚度10-100微米。
本发明的积极效果如下：
本发明的优点是，电纺的负极是一维碳管二维石墨烯复合的三维结构，具有良好的导电性，薄膜电导率可达1000S/m；电纺的固体电解质与正负极接触性能良好，可以通过调控厚薄改善电解质膜的离子电导率；而且正负极薄膜厚度从10微米起可调，从而制备不同容量的电池(0.25Wh-5Wh)。静电纺丝技术先后电纺/电喷分步一次成型，容量可调，制作方便。电池质量比容量可达360Wh/kg。
附图说明
图1是柔性超薄锂离子电池结构示意图
具体实施方式
下面的实施例是对本发明的进一步详细描述。
实施例1
按体积配比1:1称取石墨烯(5mg/ml)和碳纳米管(0.5mg/ml)在水和乙醇混合溶剂中，超声分散制成石墨烯/碳纳米管胶体溶液；第一步，利用高压静电喷雾装置在集流体上喷涂石墨烯/碳纳米管复合膜负极(12KV)，负极膜厚度10微米。第二步，按比例10wt％PEO+(0.5mol/L)LiClO4(高氯酸锂)+DMF制备固体电解质材料，高压静电纺丝直接在上一步形成的负极上电纺一层10微米固体电解质薄膜(18KV)；第三步，采用制备正极浆料(80％磷酸铁锂+10％导电剂+10％PVDF)在第二步形成的电解质薄膜上静电喷涂一层10微米的正极(12KV)；最后附上一层集流体；即得到本发明连续电纺柔性超薄超级电容器(容量约0.25Wh，电池质量比容量约300Wh/kg)。
实施例2
按体积配比1:1称取石墨烯(5mg/ml)和碳纳米管(0.5mg/ml)在水和乙二醇混合溶剂中，超声分散制成石墨烯/碳纳米管胶体溶液；第一步，利用高压静电喷雾装置在集流体上喷涂石墨烯/碳纳米管复合膜负极(12KV)，负极膜厚度50微米。第二步，按比例5wt％PVDF+5wt％PEO(0.5mol/L)LiClO4+DMF制备固体电解质材料，高压静电纺丝直接在上一步形成的负极上电纺一层50微米固体电解质薄膜(18KV)；第三步，采用制备正极浆料(80％三元材料+10％导电剂+10％PVDF)在第二步形成的电解质薄膜上静电喷涂一层50微米的正极(12KV)；最后附上一层集流体；即得到本发明连续电纺柔性超薄超级电容器(容量约1.3Wh，电池质量比容量可达340Wh/kg)。
实施例3
按体积配比2:1称取石墨烯(5mg/ml)和碳纳米管(0.5mg/ml)在NMP和乙二醇混合溶剂中，超声分散制成石墨烯/碳纳米管胶体溶液；第一步，利用高压静电喷雾装置在集流体上喷涂石墨烯/碳纳米管复合膜负极(12KV)，负极膜厚度100微米。第二步，按比例5wt％PVDF+5wt％PEO(0.5mol/L)LiClO4+DMF制备固体电解质材料，高压静电纺丝直接在上一步形成的负极上电纺一层30微米固体电解质薄膜(18KV)；第三步，采用制备正极浆料(80％三元材料+10％导电剂+10％PVDF)在第二步形成的电解质薄膜上静电喷涂一层100微米的正极(12KV)；最后附上一层集流体；即得到本发明连续电纺柔性超薄超级电容器(容量约5Wh，电池质量比容量可达360
Wh/kg)。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (7)

1.一种一次电纺柔性超薄锂离子电池的制备方法，其特征在于：所述方法的具体步骤如下：
(1)按配比称取石墨烯、碳纳米管及溶剂，超声分散制成石墨烯/碳纳米管胶体溶液；
(2)利用高压静电喷雾装置在集流体上喷涂石墨烯/碳纳米管复合膜负极；
(3)按比例制备固体电解质材料，利用高压静电纺丝装置直接在形成的负极上电纺固体电解质薄膜；
(4)采用制备的正极材料纺丝液在形成的电解质薄膜上电纺一层正极；最后附上一层金属箔集流体；即得到本发明一次电纺柔性超薄锂离子电池。
2.如权利要求1所述的制备方法，其特征在于：步骤(1)中，石墨烯溶液的浓度5mg/ml；碳纳米管溶液浓度是0.5mg/ml，溶剂是水、乙醇、乙二醇、NMP或二元混合溶液，石墨烯溶液和碳纳米管溶液二者体积比是1:1或2:1或1:2。
3.如权利要求1所述的制备方法，其特征在于：步骤(2)中，静电喷涂电压12KV，恒温温度50摄氏度；石墨烯/碳纳米管复合膜负极膜厚度10-100微米。
4.如权利要求1所述的制备方法，其特征在于：步骤(3)中，固体电解质材料的组成是：10wt％PEO+(0.5mol/L)LiClO4(高氯酸锂)或5wt％PVDF+5wt％PEO(0.5mol/L)LiClO4或10wt％PVDF+(0.5mol/L)LiClO4或其二元混合物；溶剂是NMP，DMF及其混合物。
5.如权利要求1所述的制备方法，其特征在于：步骤(3)中，静电纺丝电压15-20KV，恒温温度50摄氏度；纺丝膜厚度约10-100微米。
6.如权利要求1所述的制备方法，其特征在于：步骤(4)中，正极材料纺丝液的组成是：80％磷酸铁锂+10％导电剂+10％PVDF浆料或80％三元材料+10％导电剂+10％PVDF；溶剂是NMP。
7.如权利要求1所述的制备方法，其特征在于：步骤(4)中，静电喷涂电压15-20KV，恒温温度50摄氏度；纺丝膜厚度10-100微米。
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CN109860720A (zh) * 2019-01-30 2019-06-07 浙江锋锂新能源科技有限公司 一种复合电解质层的制备方法和固态电池
CN110137560A (zh) * 2019-04-26 2019-08-16 中国航发北京航空材料研究院 一种一体化复合电极材料及其制备方法与应用
CN110931845A (zh) * 2019-11-04 2020-03-27 浙江锋锂新能源科技有限公司 一种复合正极片、制备方法及固液混合锂蓄电池
CN111554882A (zh) * 2020-05-13 2020-08-18 中科(马鞍山)新材料科创园有限公司 一种三元正极极片及其涂布方法和应用
CN114079029A (zh) * 2020-08-14 2022-02-22 北京石墨烯研究院 柔性电池及其制备方法
CN115084448A (zh) * 2022-07-18 2022-09-20 洛阳理工学院 固态锂电池用固体电解质/电极一体化材料及其制备方法与应用

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