储能科学与技术 ›› 2018, Vol. 7 ›› Issue (6): 1233-1241.doi: 10.12028/j.issn.2095-4239.2018.0142

• 研究及进展 • 上一篇    下一篇

基于活性炭/镍钴锰酸锂(AC/LiNi0.5Co0.2Mn0.3O2)复合正极的锂离子超级电容电池的构建及其电化学性能

夏恒恒1, 安仲勋1,2, 黄廷立1, 方文英1, 杜连欢1, 吴明霞1,3, 索路路1, 徐甲强2,3, 华黎1   

  1. 1. 上海奥威科技开发有限公司国家车用超级电容器系统工程技术研究中心, 上海 201203;
    2. 上海大学材料科学与工程学院, 上海 200444;
    3. 上海大学理学院, 上海 200444
  • 收稿日期:2018-08-14 修回日期:2018-09-10 出版日期:2018-11-01 发布日期:2018-09-11
  • 通讯作者: 安仲勋,副总工程师,研究方向为高比能超级电容器的开发及应用,E-mail:an_zhongxun@aowei.com。
  • 作者简介:夏恒恒(1989-),男,硕士,工程师,研究方向为高性能锂离子电解液及高功率储能器件的开发,E-mail:xia_hheng@163.com
  • 基金资助:
    国家重点研发计划（2017YFB0102204），上海市科委第二代有机混合型高能量超级电容器关键技术及示范应用（16DZ1204300），上海市科委兆瓦级太阳能超级电容储能与调适"信息化"、超级电容车接驳与应急"零排放"示范项目（17DZ1201403）。

Construction of Li-ion supercapacitor-type battery using active carbon/LiNi0.5Co0.2Mn0.3O2 composite as cathode and its electrochemical performances

XIA Hengheng1, AN Zhongxun1,2, HUANG Tingli1, FANG Wenying1, DU Lianhuan1, WU Mingxia1,3, SUO Lulu1, XU Jiaqiang2,3, HUA Li1   

  1. 1. National Engineering Research Center for Supercapacitor for Vechicles, Shanghai AOWEI Technology Development Co. Ltd., Shanghai 201203, China;
    2. School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China;
    3. College of Science, Shanghai University, Shanghai 200444, China
  • Received:2018-08-14 Revised:2018-09-10 Online:2018-11-01 Published:2018-09-11
  • Contact: 10.12028/j.issn.2095-4239.2018.0142

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摘要： 采用有机体系（NMP+PVDF）混料及乙醇萃取的方法成功制得活性炭/LiNi0.5Co0.2Mn0.3O2（AC/NCM）复合电极片，通过设计不同AC/NCM配比能够调控能量和功率密度。选取AC/NCM为1/3配比的复合正极和硬碳（HC）负极组装的超级电容电池循环伏安（CV）曲线呈现近似矩形的容性特征，恒流充放电过程电压随时间的变化（V-t曲线）呈现出良好的线性行为。此外，采用导电炭黑（SP）/碳纳米管（CNT）/石墨烯（graphene）=3/1/1的质量比设计了复合导电剂，立体导电网络的构建有效降低了器件内阻。按照IEC 62660—1标准，在2.5～4.2 V电压窗口，83.4 W/kg功率密度下测得的能量密度高达66.6 W·h/kg，在最大功率密度6.5 kW/kg下测得的能量密度为21.5 W·h/kg。器件充满电后在65℃高温存储168 h能量保有率为97.4%，且无任何胀气现象，平均自放电率为27.5 mV/天，表现出优良的高温特性。采用14 C和50 C电流循环充放电1000次后能量保有率分别为99.06%和96.45%，体现出该超级电容电池的长寿命优势。在12 kW/kg平均放电功率密度下进行脉冲测试，连续放电100次后该器件仍表现出良好的稳定性，表明在车辆启动、脉冲器件等领域具有极大的应用潜力。

关键词: 超级电容电池, 锂离子, 活性炭, 镍钴锰酸锂, 复合正极

Abstract: The active carbon/LiNi0.5Co0.2Mn0.3O2 (AC/NCM) composite cathode slices are successfully prepared via physical blending using (NMP+PVDF) organic system and subsequent ethanol extraction method, and the energy-power characteristics can be regulated by tuning the AC/NCM ratio. Here in this paper, the AC/NCM 1/3 weight ratio is emphatically employed as cathode and hard carbon (HC) as anode to fabricate the soft-package supercapacitor-type battery. Subsequent electrochemical tests demonstrate that the as-prepared devices perform nearly rectangular shape for CV curves and good linear correlation between voltage and time (V-t curves) in constant current charging-discharging processes. Moreover, the construction strategy of Three-dimensional Conductive Network (the weight ratio of SP/CNT/Graphene is 3/1/1) is introduced to effectively reduce the internal resistance of device. According to IEC 62660-1 standard, the highest measured energy density under 2.5~4.2 V window reaches 66.6 W·h/kg with 83.4 W·kg of power density, and the maximum power density is up to 6.5 kW·kg-1 with 21.5 W·h·kg-1 of energy density. The fully charged devices exhibit excellent high-temperature storage performance with 97.4% of energy retention in the case of no flatulence, and 27.5 mV·day-1 of low average self-discharge rate after storing for 168 h at 65℃. The endurance evaluating at 14 C and 50 C show that the energy retention is up to 99.06% and 96.45%, respectively after 1000 cycles, revealing the long-life advantage of this kind of device. Furthermore, the pulse test even under the average discharge power density of 12 kW·kg-1 indicates that the device displays excellent stability after undergoing 100 times of pulse discharge, which demonstrates potential applications in vehicle start-up, pulse devices and other fields.

Key words: supercapacitor-type battery, Li-ion, active carbon, LiNi0.5Co0.2Mn0.3O2, composite cathode

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