高比能超级电容器的研究进展
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摘要
与传统蓄电池相比,超级电容器具有高功率密度、长循环寿命和使用温度范围宽等优势,但其能量密度较低.本文对超级电容器的结构、分类以及发展状况进行了简要介绍,重点阐述了本实验室近年来在研制高性能超级电容器方面的相关工作.主要从两个方面来提高超级电容器的能量密度:(1)通过采用中性水系电解液、有机电解液和离子液体提高对称型碳基超级电容器的电压窗口;(2)应用非对称型超级电容器,即一个电极采用具有法拉第赝电容电极材料或电池电极材料,而另一个电极则采用具有双电层电容的电极材料.同时介绍了由锂离子电池电极材料/活性炭作为正极,石墨作为负极组成的锂离子混合型超级电容器.最后,对超级电容器的发展方向进行了展望.
Compared with traditional batteries, supercapacitors exhibit the high power density, long cycle life and wide operating temperature window. However, the relatively low energy density of supercapacitor still remains a challenge. In this paper, the structure, classification and development of supercapacitors are introduced, with an emphasis on recent work in high performance supercarpacitors of our group. The strategy for enhancement of energy density is to increase the voltage window of symmetric carbon-based supercapacitors using neutral, organic, and ionic liquid electrolytes, and adopt asymmetric supercapacitors in which one electrode is pseudocapacitive while the other utilizes double layer capacitance. Briefing is also presented on our recent investigation into hybrid supercapacitor with electrode material of lithium-ion battery/activated carbon as positive electrode, and graphite as negative electrode. This paper is ended by a perspective of future development of supercapacitors.
Compared with traditional batteries, supercapacitors exhibit the high power density, long cycle life and wide operating temperature window. However, the relatively low energy density of supercapacitor still remains a challenge. In this paper, the structure, classification and development of supercapacitors are introduced, with an emphasis on recent work in high performance supercarpacitors of our group. The strategy for enhancement of energy density is to increase the voltage window of symmetric carbon-based supercapacitors using neutral, organic, and ionic liquid electrolytes, and adopt asymmetric supercapacitors in which one electrode is pseudocapacitive while the other utilizes double layer capacitance. Briefing is also presented on our recent investigation into hybrid supercapacitor with electrode material of lithium-ion battery/activated carbon as positive electrode, and graphite as negative electrode. This paper is ended by a perspective of future development of supercapacitors.
引文
1 Simon P,Gogotsi Y.Materials for electrochemical capacitors.Nat Mater,2008,7:845–854
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3 Frackowiak E.Carbon materials for supercapacitor application.Phys Chem Chem Phys,2007,9:1774–1785
4 Inagaki M,Konno H,Tanaike O.Carbon materials for electrochemical capacitors.J Power Sources,2010,195:7880–7903
5 Zhang LL,Zhao XS.Carbon-based materials as supercapacitor electrodes.Chem Soc Rev,2009,38:2520–2531
6 Frackowiak E,Beguin F.Carbon materials for the electrochemical storage of energy in capacitors.Carbon,2001,39:937–950
7 Lu Q,Chen JGG,Xiao JQ.Nanostructured electrodes for high-performance pseudocapacitors.Angew Chem Int Ed,2013,52:1882–1889
8 张熊,马衍伟.电化学超级电容器电极材料的研究进展.物理,2011,40:656–663
9 张熊,马衍伟.纳米电极材料在高性能超级电容器中的应用进展.新材料产业,2011:16–21
10 Long JW,Belanger D,Brousse T,Sugimoto W,Sassin MB,Crosnier O.Asymmetric electrochemical capacitors-stretching the limits of aqueous electrolytes.MRS Bull,2011,36:513–522
11 刘海晶,夏永姚.混合型超级电容器的研究进展.化学进展,2011,23:595–604
12 温祖标,田舒,曲群婷,吴宇平.以嵌入化合物为正极的混合超级电容器.化学进展,2011,23:589–594
13 Brandt A,Pohlmann S,Varzi A,Balducci A,Passerini S.Ionic liquids in supercapacitors.MRS Bull,2013,38:554–559
14 Chen Y,Zhang X,Zhang D,Ma Y.High power density of graphene-based supercapacitors in ionic liquid electrolytes.Mater Lett,2012,68:475 –477
15 孙现众,张熊,张大成,马衍伟.活性炭基Li2SO4水系电解液超级电容器.物理化学学报,2012,28:367–372
16 Sun XZ,Zhang X,Zhang HT,Zhang DC,Ma YW.A comparative study of activated carbon-based symmetric supercapacitors in Li2SO4 and KOH aqueous electrolytes.J Solid State Electrochem,2012,16:2597–2603
17 Demarconnay L,Raymundo-Pinero E,Beguin F.A symmetric carbon/carbon supercapacitor operating at 1.6 V by using a neutral aqueous solution.Electrochem Commun,2010,12:1275–1278
18 Bichat MP,Raymundo-Pinero E,Beguin F.High voltage supercapacitor built with seaweed carbons in neutral aqueous electrolyte.Carbon,2010,48:4351–4361
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20 Yang X,He YS,Jiang G,Liao XZ,Ma ZF.High voltage supercapacitors using hydrated graphene film in a neutral aqueous electrolyte.Electrochem Commun,2011,13:1166–1169
21 Cao J,Wang Y,Zhou Y,Jia D,Ouyang JH,Guo L.Performances of high voltage electrochemical capacitor using ball-milled graphite/Mn3O4 composite electrodes.J Electroanal Chem,2012,682:23–28
22 Karthikeyan K,Kalpana D,Amaresh S,Lee YS.Microwave synthesis of graphene/magnetite composite electrode material for symmetric supercapacitor with superior rate performance.RSC Advances,2012,2:12322–12328
23 Xia H,Meng YS,Yuan GL,Cui C,Luc L.A symmetric RuO2/RuO2 supercapacitor operating at 1.6 V by using a neutral aqueous electrolyte.Electrochem Solid State Lett,2012,15:A60–A63
24 Yuan CZ,Hou LR,Li DK,Zhang YW,Xiong SL,Zhang XG.Unusual electrochemical behavior of Ru-Cr binary oxide-based aqueous symmetric supercapacitors in KOH solution.Electrochim Acta,2013,88:654–658
25 Yuan CZ,Dou H,Gao B,Su LH,Zhang XG.High-voltage aqueous symmetric electrochemical capacitor based on Ru0.7Sn0.3O2?nH2O electrodes in 1 mol/L KOH.J Solid State Electrochem,2008,12:1645–1652
26 Jagadale AD,Kumbhar VS,Dhawale DS,Lokhande CD.Performance evaluation of symmetric supercapacitor based on cobalt hydroxide[Co(OH)2]thin film electrodes.Electrochim Acta,2013,98:32–38
27 Sun X,Zhang X,Zhang H,Huang B,Ma Y.Application of a novel binder for activated carbon-based electrical double layer capacitors with nonaqueous electrolytes.J Solid State Electrochem,2013,17:2035–2042
28 Borenstien A,Noked M,Okashy S,Aurbach D.Composite carbon nano-tubes(CNT)/activated carbon electrodes for non-aqueous super capacitors using organic electrolyte solutions.J Electrochem Soc,2013,160:A1282–A1285
29 黄博,孙现众,张熊,张大成,马衍伟.活性炭基软包装超级电容器用有机电解液.物理化学学报,2013,29:1998–2004
30 Novoselov KS,Geim AK,Morozov SV,Jiang D,Zhang Y,Dubonos SV,Grigorieva IV,Firsov AA.Electric field effect in atomically thin carbon films.Science,2004,306:666–669
31 陈冠雄,谈紫琪,赵元,倪彬彬,朱彦武,陆亚林.面向能源领域的石墨烯研究.中国科学:化学,2013,43:704–715
32 Huang Y,Liang JJ,Chen YS.An overview of the applications of graphene-based materials in supercapacitors.Small,2012,8:1805–1834
33 Zhang LL,Zhou R,Zhao XS.Graphene-based materials as supercapacitor electrodes.J Mater Chem,2010,20:5983–5992
34 Chen J,Li C,Shi GQ.Graphene materials for electrochemical capacitors.J Phys Chem Lett,2013,4:1244–1253
35 Chen Y,Zhang X,Zhang D,Yu P,Ma Y.High performance supercapacitors based on reduced graphene oxide in aqueous and ionic liquid electrolytes.Carbon,2011,49:573–580
36 Zhang D,Zhang X,Chen Y,Wang C,Ma Y.An environment-friendly route to synthesize reduced graphene oxide as a supercapacitor electrode material.Electrochim Acta,2012,69:364–370
37 Zhang D,Zhang X,Chen Y,Wang C,Ma Y,Dong H,Jiang L,Meng Q,Hu W.Supercapacitor electrodes with especially high rate capability and cyclability based on a novel Pt nanosphere and cysteine-generated graphene.Phys Chem Chem Phys,2012,14:10899–10903
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39 Zhu YW,Murali S,Stoller MD,Ganesh KJ,Cai WW,Ferreira PJ,Pirkle A,Wallace RM,Cychosz KA,Thommes M,Su D,Stach EA,Ruoff RS.Carbon-based supercapacitors produced by activation of graphene.Science,2011,332:1537–1541
40 Zhang HT,Zhang X,Sun XZ,Zhang DC,Lin H,Wang CH,Wang HJ,Ma YW.Large-scale production of nanographene sheets with a controlled mesoporous architecture as high-performance electrochemical electrode materials.ChemSusChem,2013,6:1084–1090
41 Zhang H,Zhang X,Sun X,Ma Y.Shape-controlled synthesis of nanocarbons through direct conversion of carbon dioxide.Sci Rep,2013,3:3534
42 Chen Y,Zhang X,Zhang H,Sun X,Zhang D,Ma Y.High-performance supercapacitors based on graphene/activated carbon composite by chemical activation.RSC Adv,2012,2:7747–7753
43 Pell WG,Conway BE.Peculiarities and requirements of asymmetric capacitor devices based on combination of capacitor and battery-type electrodes.J Power Sources,2004,136:334–345
44 Wei W,Cui X,Chen W,Ivey DG.Manganese oxide-based materials as electrochemical supercapacitor electrodes.Chem Soc Rev,2011,40:1697–1721
45 Zhang Y,Xue D.MnO2 for the electrode materials of supercapacitors.Energy Environ Focus,2012,1:4–18
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47 Yu P,Zhang X,Chen Y,Ma YW,Qi ZP.Preparation and pseudo-capacitance of birnessite-type MnO2 nanostructures via microwaveassisted emulsion method.Mater Chem Phys,2009,118:303–307
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2 Winter M,Brodd RJ.What are batteries,fuel cells,and supercapacitors?Chem Rev,2004,104:4245–4269
3 Frackowiak E.Carbon materials for supercapacitor application.Phys Chem Chem Phys,2007,9:1774–1785
4 Inagaki M,Konno H,Tanaike O.Carbon materials for electrochemical capacitors.J Power Sources,2010,195:7880–7903
5 Zhang LL,Zhao XS.Carbon-based materials as supercapacitor electrodes.Chem Soc Rev,2009,38:2520–2531
6 Frackowiak E,Beguin F.Carbon materials for the electrochemical storage of energy in capacitors.Carbon,2001,39:937–950
7 Lu Q,Chen JGG,Xiao JQ.Nanostructured electrodes for high-performance pseudocapacitors.Angew Chem Int Ed,2013,52:1882–1889
8 张熊,马衍伟.电化学超级电容器电极材料的研究进展.物理,2011,40:656–663
9 张熊,马衍伟.纳米电极材料在高性能超级电容器中的应用进展.新材料产业,2011:16–21
10 Long JW,Belanger D,Brousse T,Sugimoto W,Sassin MB,Crosnier O.Asymmetric electrochemical capacitors-stretching the limits of aqueous electrolytes.MRS Bull,2011,36:513–522
11 刘海晶,夏永姚.混合型超级电容器的研究进展.化学进展,2011,23:595–604
12 温祖标,田舒,曲群婷,吴宇平.以嵌入化合物为正极的混合超级电容器.化学进展,2011,23:589–594
13 Brandt A,Pohlmann S,Varzi A,Balducci A,Passerini S.Ionic liquids in supercapacitors.MRS Bull,2013,38:554–559
14 Chen Y,Zhang X,Zhang D,Ma Y.High power density of graphene-based supercapacitors in ionic liquid electrolytes.Mater Lett,2012,68:475 –477
15 孙现众,张熊,张大成,马衍伟.活性炭基Li2SO4水系电解液超级电容器.物理化学学报,2012,28:367–372
16 Sun XZ,Zhang X,Zhang HT,Zhang DC,Ma YW.A comparative study of activated carbon-based symmetric supercapacitors in Li2SO4 and KOH aqueous electrolytes.J Solid State Electrochem,2012,16:2597–2603
17 Demarconnay L,Raymundo-Pinero E,Beguin F.A symmetric carbon/carbon supercapacitor operating at 1.6 V by using a neutral aqueous solution.Electrochem Commun,2010,12:1275–1278
18 Bichat MP,Raymundo-Pinero E,Beguin F.High voltage supercapacitor built with seaweed carbons in neutral aqueous electrolyte.Carbon,2010,48:4351–4361
19 Wang YM,Cao JY,Zhou Y,Ouyang JH,Jia DC,Guo LX.Ball-milled graphite as an electrode material for high voltage supercapacitor in neutral aqueous electrolyte.J Electrochem Soc,2012,159:A579–A583
20 Yang X,He YS,Jiang G,Liao XZ,Ma ZF.High voltage supercapacitors using hydrated graphene film in a neutral aqueous electrolyte.Electrochem Commun,2011,13:1166–1169
21 Cao J,Wang Y,Zhou Y,Jia D,Ouyang JH,Guo L.Performances of high voltage electrochemical capacitor using ball-milled graphite/Mn3O4 composite electrodes.J Electroanal Chem,2012,682:23–28
22 Karthikeyan K,Kalpana D,Amaresh S,Lee YS.Microwave synthesis of graphene/magnetite composite electrode material for symmetric supercapacitor with superior rate performance.RSC Advances,2012,2:12322–12328
23 Xia H,Meng YS,Yuan GL,Cui C,Luc L.A symmetric RuO2/RuO2 supercapacitor operating at 1.6 V by using a neutral aqueous electrolyte.Electrochem Solid State Lett,2012,15:A60–A63
24 Yuan CZ,Hou LR,Li DK,Zhang YW,Xiong SL,Zhang XG.Unusual electrochemical behavior of Ru-Cr binary oxide-based aqueous symmetric supercapacitors in KOH solution.Electrochim Acta,2013,88:654–658
25 Yuan CZ,Dou H,Gao B,Su LH,Zhang XG.High-voltage aqueous symmetric electrochemical capacitor based on Ru0.7Sn0.3O2?nH2O electrodes in 1 mol/L KOH.J Solid State Electrochem,2008,12:1645–1652
26 Jagadale AD,Kumbhar VS,Dhawale DS,Lokhande CD.Performance evaluation of symmetric supercapacitor based on cobalt hydroxide[Co(OH)2]thin film electrodes.Electrochim Acta,2013,98:32–38
27 Sun X,Zhang X,Zhang H,Huang B,Ma Y.Application of a novel binder for activated carbon-based electrical double layer capacitors with nonaqueous electrolytes.J Solid State Electrochem,2013,17:2035–2042
28 Borenstien A,Noked M,Okashy S,Aurbach D.Composite carbon nano-tubes(CNT)/activated carbon electrodes for non-aqueous super capacitors using organic electrolyte solutions.J Electrochem Soc,2013,160:A1282–A1285
29 黄博,孙现众,张熊,张大成,马衍伟.活性炭基软包装超级电容器用有机电解液.物理化学学报,2013,29:1998–2004
30 Novoselov KS,Geim AK,Morozov SV,Jiang D,Zhang Y,Dubonos SV,Grigorieva IV,Firsov AA.Electric field effect in atomically thin carbon films.Science,2004,306:666–669
31 陈冠雄,谈紫琪,赵元,倪彬彬,朱彦武,陆亚林.面向能源领域的石墨烯研究.中国科学:化学,2013,43:704–715
32 Huang Y,Liang JJ,Chen YS.An overview of the applications of graphene-based materials in supercapacitors.Small,2012,8:1805–1834
33 Zhang LL,Zhou R,Zhao XS.Graphene-based materials as supercapacitor electrodes.J Mater Chem,2010,20:5983–5992
34 Chen J,Li C,Shi GQ.Graphene materials for electrochemical capacitors.J Phys Chem Lett,2013,4:1244–1253
35 Chen Y,Zhang X,Zhang D,Yu P,Ma Y.High performance supercapacitors based on reduced graphene oxide in aqueous and ionic liquid electrolytes.Carbon,2011,49:573–580
36 Zhang D,Zhang X,Chen Y,Wang C,Ma Y.An environment-friendly route to synthesize reduced graphene oxide as a supercapacitor electrode material.Electrochim Acta,2012,69:364–370
37 Zhang D,Zhang X,Chen Y,Wang C,Ma Y,Dong H,Jiang L,Meng Q,Hu W.Supercapacitor electrodes with especially high rate capability and cyclability based on a novel Pt nanosphere and cysteine-generated graphene.Phys Chem Chem Phys,2012,14:10899–10903
38 Zhang D,Zhang X,Chen Y,Yu P,Wang C,Ma Y.Enhanced capacitance and rate capability of graphene/polypyrrole composite as electrode material for supercapacitors.J Power Sources,2011,196:5990–5996
39 Zhu YW,Murali S,Stoller MD,Ganesh KJ,Cai WW,Ferreira PJ,Pirkle A,Wallace RM,Cychosz KA,Thommes M,Su D,Stach EA,Ruoff RS.Carbon-based supercapacitors produced by activation of graphene.Science,2011,332:1537–1541
40 Zhang HT,Zhang X,Sun XZ,Zhang DC,Lin H,Wang CH,Wang HJ,Ma YW.Large-scale production of nanographene sheets with a controlled mesoporous architecture as high-performance electrochemical electrode materials.ChemSusChem,2013,6:1084–1090
41 Zhang H,Zhang X,Sun X,Ma Y.Shape-controlled synthesis of nanocarbons through direct conversion of carbon dioxide.Sci Rep,2013,3:3534
42 Chen Y,Zhang X,Zhang H,Sun X,Zhang D,Ma Y.High-performance supercapacitors based on graphene/activated carbon composite by chemical activation.RSC Adv,2012,2:7747–7753
43 Pell WG,Conway BE.Peculiarities and requirements of asymmetric capacitor devices based on combination of capacitor and battery-type electrodes.J Power Sources,2004,136:334–345
44 Wei W,Cui X,Chen W,Ivey DG.Manganese oxide-based materials as electrochemical supercapacitor electrodes.Chem Soc Rev,2011,40:1697–1721
45 Zhang Y,Xue D.MnO2 for the electrode materials of supercapacitors.Energy Environ Focus,2012,1:4–18
46 Yu P,Zhang X,Wang DL,Wang L,Ma YW.Shape-controlled synthesis of 3D hierarchical MnO2 nanostructures for electrochemical supercapacitors.Cryst Growth Des,2009,9:528–533
47 Yu P,Zhang X,Chen Y,Ma YW,Qi ZP.Preparation and pseudo-capacitance of birnessite-type MnO2 nanostructures via microwaveassisted emulsion method.Mater Chem Phys,2009,118:303–307
48 Zhang X,Yang W,Ma Y.Synthesis of polypyrrole-intercalated layered manganese oxide nanocomposite by a delamination/reassembling method and its electrochemical capacitance performance.Electrochem Solid State Lett,2009,12:A95–A98
49 Zhang X,Chen Y,Yu P,Ma Y.Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.J Nanosci Nanotechnol,2010,10:7711–7714
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