胶体离子超级电容器的比容量评价

doi:10.11944/j.issn.1000-0518.2016.01.150308

摘要/Abstract

摘要：

胶体离子超级电容器作为一种新型的超级电容器,其同时具有能量密度和功率密度高的独特优势。目前已经发展了包括多种过渡金属阳离子和稀土阳离子,例如Mn²⁺、Fe²⁺、Co²⁺、Ni²⁺、Cu²⁺、Sn²⁺、Sn⁴⁺、La³⁺、Ce³⁺、Er³⁺和Yb³⁺的胶体离子超级电容器体系。在电化学反应中,识别出电活性物质的存在形式对研究电极反应机理和提高比容量具有重要价值。本文主要通过对电活性物质比容量的探讨,理解这种新型胶体离子超级电容器的电化学储能机理。评述了胶体离子超级电容器的比容量核算方式,提出了以阳离子为标准核算比容量的原因,并与传统超级电容器的核算方式进行了比较,表明胶体离子超级电容器在提高能量密度方面具有潜在优势,有望突破现有电化学储能设备的技术瓶颈,实现下一代高能量储能器件的开发。

关键词: 比电容评价, 胶体离子超级电容器, 赝电容, 法拉第反应

Abstract:

Although they show high power density, supercapacitors often suffer from low energy density. As a new kind of supercapacitors, colloidal ion supercapacitors that include various transition metal cations and rare earth cations, such as Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Sn²⁺, Sn⁴⁺, La³⁺, Ce³⁺, Er³⁺, Yb³⁺, etc, show both high energy density and high power density. Proper evaluation of specific capacitance of colloidal ion supercapacitors can deepen our understanding of the electrochemical mechanism of electroactive cations in pseudocapacitive electrode materials. This review firstly outlines the basic concept of colloidal ion supercapacitors and in situ coprecipitation synthesis methods. Then the specific capacitance based on active cations(named cationic capacitance) is used to evaluate the performance of colloidal ion supercapacitors. We then calculate the specific capacitances on the basis of hydroxides and oxides(named hydroxide capacitance and oxide capacitance), which are traditional evaluation methods for supercapacitors. Compared with three kinds of specific capacitances, cationic capacitance can really reflect the intrinsic reaction mechanism of pseudocapacitive materials. It is expected that colloidal ion supercapacitors can overcome the technical bottleneck of the existing electrochemical energy storage devices and be the next-generation high-energy storage devices.

Key words: capacitance evaluation, colloid ionic supercapacitor, pseudocapacitance, Faradic reaction

陈昆峰,薛冬峰. 胶体离子超级电容器的比容量评价[J]. 应用化学, 2016, 33(1): 18-24.

CHEN Kunfeng,XUE Dongfeng. Evaluation of Specific Capacitance of Colloidal Ionic Supercapacitor Systems[J]. Chinese Journal of Applied Chemistry, 2016, 33(1): 18-24.

参考文献

[1]	Chen K,Song S,Liu F,et al.Structural Design of Graphene for Electrochemical Energy Storage[J]. Chem Soc Rev,2015,44(17):6230-6257.
[2]	XU Guorong,LI Yubing,DONG Wenhao,et al.Preparation of Mn3O4 Nanoparticles in Alkaline Solution and Their Application in Supercapacitor[J]. Chinese J Appl Chem,2015,32(6):701-707(in Chinese). 徐国荣,李钰冰,董文豪,等. 碱性介质中制备纳米四氧化三锰及其超级电容特性[J]. 应用化学,2015,32(6):701-707.
[3]	Augustyn V,Simon P,Dunn B. Pseudocapacitive Oxide Materials for High-Rate Electrochemical Energy Storage[J]. Energy Environ Sci,2014,7(5):1597-1614.
[4]	CHEN Kunfeng,XUE Dongfeng. Chemical Reaction and Crystallization Control on Electrode Materials for Electrochemical Energy Storage[J]. Sci China:Technol Sci,2015,45(1):36-49(in Chinese). 陈昆峰,薛冬峰. 化学反应和结晶控制的电化学储能电极材料[J]. 中国科学:技术科学,2015,45(1):36-49.
[5]	HU Xiaozhou,WANG Jing,TANG Jing. Synthesis of Mixture Salt Activated Porous Carbon from Scaphium Scaphigerum and Its Performance as Super Capacitor Electrode Material[J]. Chinese J Appl Chem,2015,32(5):591-596(in Chinese). 呼小洲,王静,唐靖. 混合盐活化胖大海基多孔炭的制备及超级电容器电极材料性能[J]. 应用化学,2015,32(5):591-596.
[6]	CHEN Kunfeng,YANG Yangyang,CHEN Xu,et al.Study of Transition Metal-Based Material for Electrochemical Energy Storage[J]. J He'nan Univ(Nat Sci),2014,44(4):398-415(in Chinese). 陈昆峰,杨阳阳,陈旭,等. 过渡金属材料的电化学储能性能研究[J]. 河南大学学报(自然科学版),2014,44(4):398-415.
[7]	LIU Yaliu,YUAN Zhongzhi,LIU Liling. Preparation and Electrochemical Characteristics of Manganese Dioxide/graphene Composite Paper Electrode[J]. Chinese J Appl Chem,2015,32(7):843-848(in Chinese). 刘亚柳,袁中直,刘俐伶. 二氧化锰/石墨烯纸电极的制备及其电化学性能[J]. 应用化学,2015,32(7):843-848.
[8]	Chen K F,Xue D F. Rare Earth and Transitional Metal Colloidal Supercapacitors[J]. Sci China Technol Sci,2015,58:1768-1778.
[9]	Chen K F,Xue D F. Searching for Electrode Materials with High Electrochemical Reactivity[J]. J Materiomics,2015,1(3):170-1787.
[10]	Lu Q,Chen J,Xiao J. Nanostructured Electrodes for High-Performance Pseudocapacitors[J]. Angew Chem Int Ed,2013,52(7):1882-1889.
[11]	Chen K F,Xue D F. Ionic Supercapacitor Electrode Materials:A System-Level Design of Electrode and Electrolyte for Transforming Ions into Colloids[J]. Colloid Interface Sci Commun,2014,1(1):39-42.
[12]	Chen X,Chen K F,Wang H,et al.Crystallization of Fe3+ in an Alkaline Aqueous Pseudocapacitor System[J]. Cryst Eng Comm,2014,16(29):6707-6715.
[13]	Chen K F,Xue D F. Crystallization of Tin Chloride for Promising Pseudocapacitor Electrode[J]. CrystEngComm,2014,16(21):4610-4618.
[14]	Chen K F,Xue D F. YbCl3 Electrode in Alkaline Aqueous Electrolyte with High Pseudocapacitance[J]. J Colloid Interface Sci,2014,424(1):84-89.
[15]	Chen K F,Xue D F. Formation of Electroactive Colloids via In-Situ Coprecipitation under Electric Field:Erbium Chloride Alkaline Aqueous Pseudocapacitor[J]. J Colloid Interface Sci,2014,430(1):265-271.
[16]	Chen K F,Xue D F. Water-Soluble Inorganic Salt with Ultrahigh Specific Capacitance:Ce(NO3)3 Can be Designed as Excellent Pseudocapacitor Electrode[J]. J Colloid Interface Sci,2014,416(1):172-176.
[17]	Chen K F,Xue D F,Komarneni S. Colloidal Pseudocapacitor:Nanoscale Aggregation of Mn Colloids from MnCl2 under Alkaline Condition[J]. J Power Sources,2015,279(1):365-371.
[18]	Chen K F,Yang Y,Li K,et al.CoCl2 Designed as Excellent Pseudocapacitor Electrode Materials[J]. ACS Sustain Chem Eng,2014,2(3):440-444.
[19]	Chen X,Chen K F,Wang H,et al.Functionality of Fe(NO3)3 Salts as Both Positive and Negative Pseudocapacitor Electrodes in Alkaline Aqueous Electrolyte[J]. Electrochim Acta,2014,147(1):216-224.
[20]	Chen X,Chen K F,Wang H,et al.A Colloidal Pseudocapacitor:Direct Use of Fe(NO3)3 in Electrode can Lead to a High Performance Alkaline Supercapacitor System[J]. J Colloid Interface Sci,2015,444(1):49-57.
[21]	Chen K F,Yin S,Xue D F. Binary AxB1-x Ionic Alkaline Pseudocapacitor System Involving Manganese, Iron, Cobalt, and Nickel: Formation of Electroactive Colloids via In-Situ Electric Field Assisted Coprecipitation[J]. Nanoscale,2015,7(3):1161-1166.
[22]	Chen K F,Song S,Li K,et al.Water-Soluble Inorganic Salts with Ultrahigh Specific Capacitance:Crystallization Transformation Investigation of CuCl2 Electrodes[J]. CrystEngComm,2013,15(47):10367-10373.
[23]	Lu Z,Chang Z,Zhu W,et al.Beta-phased Ni(OH)2 Nanowall Film with Reversible Capacitance Higher than Theoretical Faradic Capacitance[J]. Chem Commun,2011,47(34):9651-9653.
[24]	Sathiya M,Rousse G,Ramesha K,et al.Reversible Anionic Redox Chemistry in High-Capacity Layered-Oxide Electrodes[J]. Nat Mater,2013,12(9):827-835.
[25]	Simon P,Gogotsi Y. Materials for Electrochemical Capacitors[J]. Nat Mater,2008,7(11):845-854.
[26]	Beidaghi M,Gogotsi Y. Capacitive Energy Storage in Micro-Scale Devices: Recent Advances in Design and Fabrication of Microsupercapacitors[J]. Energy Environ Sci,2014,7(3):867-884.
[27]	Aravindan V,Gnanaraj J,Lee Y,et al.Insertion-Type Electrodes for Nonaqueous Li-Ion Capacitors[J]. Chem Rev,2014,114(23):11619-11635.