固态超级电容器电解质的分类与研究进展
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摘要
电化学电容器(又称为超级电容器)作为一种功率密度大、循环寿命长、稳定性能优异的储能元件,近年来得到了越来越多的关注。固态/准固态超级电容器(以下简称固态超级电容器),由于其优异的可弯曲性能、挥发性与可燃性低、易于封装和成型等特点,在柔性电子、柔性储能器件、可穿戴设备等领域得到了越来越多的关注和研究。本文首先简述了固态超级电容器的优点及其构型,然后分别介绍了凝胶聚合物类电解质和无机固态电解质。凝胶聚合物电解质根据其溶剂的不同,可以分为水凝胶电解质、有机凝胶电解质和离子凝胶电解质;其中水凝胶聚合物电解质因为其优异的生物兼容性和良好的电化学性能,受到研究者的广泛关注。无机固态电解质虽然电化学性能相对较差,但是由于其完全干燥的特性,在卫星元件等特殊领域仍有重要作用。文中最后介绍了在固态电解质中氧化还原添加剂的种类和特点,并指出无机氧化还原添加剂在提高超级电容器的能量密度和功率密度方面是较好的选择。
Electrochemical capacitors(also known as supercapacitors), as a kind of energy storage device with high power density, long cyclic life and excellent stability, has attracted more and more attentions in recent years. Solid-state or quasi-solid-state supercapacitors can be widely applied in flexible electronics, flexible energy storage devices, wearable devices, and other areas due to their excellent mechanical flexibility, low volatility and flammability, easy assembly and molding. We thus introduce the advantages and configurations of solid-state supercapacitors. The solid-state electrolytes,which include the polymer gel electrolytes and the inorganic solid-state electrolytes, are introduced respectively. According to the different solvents, polymer gel electrolytes can be divided into hydrogel electrolytes, organogel electrolytes,and ionogel electrolytes. Among them, hydrogel electrolytes have been widely investigated due to their superior biocompatibility and good electrochemical performance. The inorganic solid-state electrolytes have relatively poorer electrochemical performance compared to the polymer gel electrolytes, they still play an important role in some specific areas such as satellite electronics because of the bone dry property. Lastly, different types and the characteristics of redox additives in solid-state electrolytes are introduced. It is noticed that the inorganic redox additive is a good option to increase the energy density as well as the power density of solid-state supercapacitors.
Electrochemical capacitors(also known as supercapacitors), as a kind of energy storage device with high power density, long cyclic life and excellent stability, has attracted more and more attentions in recent years. Solid-state or quasi-solid-state supercapacitors can be widely applied in flexible electronics, flexible energy storage devices, wearable devices, and other areas due to their excellent mechanical flexibility, low volatility and flammability, easy assembly and molding. We thus introduce the advantages and configurations of solid-state supercapacitors. The solid-state electrolytes,which include the polymer gel electrolytes and the inorganic solid-state electrolytes, are introduced respectively. According to the different solvents, polymer gel electrolytes can be divided into hydrogel electrolytes, organogel electrolytes,and ionogel electrolytes. Among them, hydrogel electrolytes have been widely investigated due to their superior biocompatibility and good electrochemical performance. The inorganic solid-state electrolytes have relatively poorer electrochemical performance compared to the polymer gel electrolytes, they still play an important role in some specific areas such as satellite electronics because of the bone dry property. Lastly, different types and the characteristics of redox additives in solid-state electrolytes are introduced. It is noticed that the inorganic redox additive is a good option to increase the energy density as well as the power density of solid-state supercapacitors.
引文
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[3]刘云鹏,李雪,韩颖慧,等.锂离子超级电容器电极材料研究进展[J].高电压技术,2018,44(4):1140-1148.LIU Yunpeng,LI Xue,HAN Yinghui,et al.Research progress in electrode materials for lithium-ion supercapacitor[J].High Voltage Engineering,2018,44(4):1140-1148.
[4]ZHONG C,DENG Y,HU W,et al.Electrolytes for electrochemical supercapacitors[M].Boca Raton,USA:CRC Press,2016.
[5]CONWAY B E.Electrochemical supercapacitors-scientific fundamentals and technological applications[M].New York,USA:Springer US,1999.
[6]ZHONG J,ZHANG Y,ZHONG Q,et al.Fiber-based generator for wearable electronics and mobile medication[J].ACS Nano,2014,8(6):6273-6280.
[7]GAO H,LIAN K.Proton-conducting polymer electrolytes and their applications in solid supercapacitors:a review[J].RSC Advances,2014,62(4):33091-33113.
[8]SHI X,ZENG Z,LIAO C,et al.Flexible,planar integratable and all-solid-state micro-supercapacitors based on nonporous gold/manganese oxide hybrid electrodes via template plasma etching method[J].Journal of Alloys and Compounds,2018,739:979-986.
[9]刘连梅,翁巍,彭慧胜,等.纤维状超级电容器的发展现状[J].中国材料进展,2016,35(2):81-90.LIU Lianmei,WENG Wei,PENG Huisheng,et al.The state of the art in fiber-shaped supercapacitors[J].Materials China,2016,35(2):81-90.
[10]WANG Z,CHENG J,ZHOU J,et al.All-climate aqueous fiber-shaped supercapacitors with record areal energy density and high safety[J].Nano Energy,2018,50:106-117.
[11]MA G,FENG E,SUN K,et al.A novel and high-effective redox-mediated gel polymer electrolyte for supercapacitor[J].Electrochimica Acta,2014,135:461-466.
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[13]郭渊,王晓焕,谢海燕,等.壳聚糖-聚乙烯醇-海藻酸钠聚电解质复合膜的制备及吸水性能研究[J].新疆农业大学学报,2017,40(3):198-203.GUO Yuan,WANG Xiaohuan,XIE Haiyan,et al.Preparation and water absorption properties of chitosan polyvinyl alcohol sodium alginate polyelectrolyte composite membrane[J].Journal of Xinjiang Agricultural University,2017,40(3):198-203.
[14]SOEDA K,YAMAGATA M,ISHIKAWA M.Outstanding features of alginate-based gel electrolyte with ionic liquid for electric double layer capacitors[J].Journal of Power Sources,2015,280:565-572.
[15]YANG I,KWON D,KIM M-S,et al.A comparative study of activated carbon aerogel and commercial activated carbons as electrode materials for organic electric double-layer capacitors[J].Carbon,2018,132:503-511.
[16]WU X L,WEN T,GUO H L,et al.Biomass-derived sponge-like carbonaceous hydrogels and aerogels for supercapacitors[J].ACSNano,2013,7(4):3589-3597.
[17]杨喜,孔令宇,刘杏娥,等.纤维素导电气凝胶及其复合材料在超级电容器中应用的研究进展[J].林产化学与工业,2018,38(1):1-8.YANG Xi,KONG Lingyu,LIU Xing’e,et al.Research progress of cellulose conductive aerogels and composites in supercapacitors[J].Chemistry and Industry of Forest Products,2018,38(1):1-8.
[18]YANG C,SUO Z.Hydrogelionotronics[J].Nature Reviews Materials,2018(3):125-142.
[19]LUO J,ZHONG W,ZOU Y,et al.Preparation of morphology-controllable polyaniline and polyaniline/graphene hydrogels for high performance binder-free supercapacitor electrodes[J].Journal of Power Sources,2016,319:73-81.
[20]BATISSE N,RAYMUNDOP E.A self-standing hydrogel neutral electrolyte for high voltage and safe flexible supercapacitors[J].Journal of Power Sources,2017,348:168-174.
[21]CHOUDHURY N A,SAMPATH S,SHUKLA A K.Hydrogel-polymer electrolytes for electrochemical capacitors:an overview[J].Energy&Environmental Science,2009,2(1):55-67.
[22]GUO Y,ZHOU X,TANG Q,et al.A self-healable and easily recyclable supramolecular hydrogel electrolyte for flexible supercapacitors[J].Journal of Materials Chemistry A,2016,4(22):8769-8776.
[23]KIM K M,NAM J H,LEE Y-G,et al.Supercapacitive properties of electrodeposited RuO2 electrode in acrylic gel polymer electrolytes[J].Current Applied Physics,2013,13(8):1702-1706.
[24]TANG Q,CHEN M,YANG C,et al.Enhancing the energy density of asymmetric stretchable supercapacitor based on wrinkled CNT@MnO2 cathode and CNT@polypyrroleanode[J].ACS Applied Materials&Interfaces,2015,7(28):15303-15313.
[25]TANG Q,CHEN M,WANG G,et al.A facile prestrain-stick-release assembly of stretchable supercapacitors based on highly stretchable and sticky hydrogel electrolyte[J].Journal of Power Sources,2015,284:400-408.
[26]ZHANG G,CHEN Y,DENG Y,et al.A Triblock copolymer design leads to robust hybrid hydrogels for high-performance flexible supercapacitors[J].ACS Applied Materials&Interfaces,2017,9(41):36301-36310.
[27]KIM K M,LEE Y G,SHIN D O,et al.Supercapacitive properties of activated carbon electrode in potassium-polyacrylate hydrogel electrolytes[J].Journal of Applied Electrochemistry,2016,46(5):567-573.
[28]KIM K M,LATIFATU M,LEE Y G,et al.Effect of ceramic filler-containing polymer hydrogel electrolytes coated on the polyolefin separator on the electrochemical properties of activated carbon supercapacitor[J].Journal of Electroceramics,2013,32(2-3):146-153.
[29]AIHARA Y,APPETECCHI G B,SCROSATI B A.New concept for the formation of homogeneous,poly(ethylene oxide)based,gel-type polymer electrolyte[J].Journal of the Electrochemical Society,2002,149(7):A849.
[30]IBRAHIM S,YASSIN M M,AHMAD R,et al.Effects of various Li PF6 salt concentrations on PEO-based solid polymer electrolytes[J].Ionics,2011,17(5):399-405.
[31]YIN Y,ZHOU J,MANSOUR A N,et al.Effect of NaI/I2 mediators on properties of PEO/LiAlO2 based all-solid-state supercapacitors[J].Journal of Power Sources,2011,196(14):5997-6002.
[32]CHEN Q,LI X,ZANG X,et al.Effect of different gel electrolytes on graphene-based solid-state supercapacitors[J].RSC Advances,2014,4(68):36253-36256.
[33]KIM M,KIM J.Redox active KI solid-state electrolyte for battery-like electrochemical capacitive energy storage based on MgCo2O4 nanoneedles on porousβ-polytype silicon carbide[J].Electrochimica Acta,2018,260:921-931.
[34]WANG Z,TAO F,PAN Q.A self-healable polyvinyl alcohol-based hydrogel electrolyte for smart electrochemical capacitors[J].Journal of Materials Chemistry A,2016,4(45):17732-17739.
[35]HEY M J,JACKSON D P,YAN H.The salting-out effect and phase separation in aqueous solutions of electrolytes and poly(ethylene glycol)[J].Polymer,2005,46(8):2567-2572.
[36]HUANG Y F,WU P F,ZHANG M Q,et al.Boron cross-linked graphene oxide/polyvinyl alcohol nanocomposite gel electrolyte for flexible solid-state electric double layer capacitor with high performance[J].Electrochimica Acta,2014,132:103-111.
[37]LIM C S,TEOH K H,LIEW C W,et al.Capacitive behavior studies on electrical double layer capacitor using poly(vinyl alcohol)-lithium perchlorate based polymer electrolyte incorporated with TiO2[J].Materials Chemistry and Physics,2014,143(2):661-667.
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