超級電容器的工作原理和相關(guān)材料的研究進展綜述目錄TOC\o"1-3"\h\u16435超級電容器的工作原理和相關(guān)材料的研究進展綜述 1324721.1引言 1125261.2超級電容器的工作原理 220001.2.1雙電層電容器的工作原理 2220621.2.2贗電容器的工作原理 3252711.3超級電容器的電極材料研究進展 3174421.3.1碳材料 32501.3.2過渡金屬氧化物 511761.3.3導(dǎo)電聚合物 51.1引言隨著現(xiàn)代社會的高速發(fā)展以及化石能源的巨大消耗，人們對環(huán)境友好的可再生能源的需求量日益增加。如今，許多科研工作者致力于風(fēng)能、太陽能、潮汐能、地?zé)崮艿刃履茉吹难芯俊，F(xiàn)在正處于能源轉(zhuǎn)型的過渡期，我們應(yīng)當順應(yīng)潮流，采取以清潔、可再生的新能源代替?zhèn)鹘y(tǒng)化石能源的策略ADDINEN.CITE<EndNote><Cite><Author>Liu</Author><Year>2010</Year><RecNum>58</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>58</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618226493">58</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liu,Chang</author><author>Li,Feng</author><author>Ma,Lai-Peng</author><author>Cheng,Hui-Ming</author></authors></contributors><titles><title>AdvancedMaterialsforEnergyStorage</title><secondary-title>AdvancedMaterials</secondary-title></titles><periodical><full-title>AdvancedMaterials</full-title><abbr-1>Adv.Mater.</abbr-1><abbr-2>Adv.Mater.</abbr-2></periodical><pages>28-62</pages><volume>22</volume><number>8</number><dates><year>2010</year><pub-dates><date>Feb23</date></pub-dates></dates><isbn>0935-9648</isbn><accession-num>WOS:000275253400010</accession-num><urls><related-urls><url><GotoISI>://WOS:000275253400010</url></related-urls></urls><electronic-resource-num>10.1002/adma.200903328</electronic-resource-num></record></Cite></EndNote>[1]。不過由于新能源自身的不可持續(xù)性及其利用過程中存在的損耗，提高能源利用效率又成為我們需要越過的“障礙”。因此，在能源儲存裝置的選擇上也就變得尤為重要。目前，在生活中應(yīng)用最廣泛、最方便的能源是電能，因為電能的來源較為廣泛（如風(fēng)能、太陽能等），并且易與傳輸，可以說電能的儲存就是能源儲存的“關(guān)鍵點”ADDINEN.CITE<EndNote><Cite><Author>Yang</Author><Year>2011</Year><RecNum>59</RecNum><DisplayText><styleface="superscript">[2]</style></DisplayText><record><rec-number>59</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618230683">59</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yang,Zhenguo</author><author>Zhang,Jianlu</author><author>Kintner-Meyer,MichaelC.W.</author><author>Lu,Xiaochuan</author><author>Choi,Daiwon</author><author>Lemmon,JohnP.</author><author>Liu,Jun</author></authors></contributors><titles><title>ElectrochemicalEnergyStorageforGreenGrid</title><secondary-title>ChemicalReviews</secondary-title></titles><periodical><full-title>ChemicalReviews</full-title><abbr-1>Chem.Rev.</abbr-1><abbr-2>Chem.Rev.</abbr-2></periodical><pages>3577-3613</pages><volume>111</volume><number>5</number><dates><year>2011</year><pub-dates><date>May</date></pub-dates></dates><isbn>0009-2665</isbn><accession-num>WOS:000290373100014</accession-num><urls><related-urls><url><GotoISI>://WOS:000290373100014</url></related-urls></urls><electronic-resource-num>10.1021/cr100290v</electronic-resource-num></record></Cite></EndNote>[2]。超級電容器由于其自身快速的充-放電效率、高循環(huán)穩(wěn)定性、制備簡便易得等特性，成為備受科研工作者青睞的儲能器件ADDINEN.CITEADDINEN.CITE.DATA[3-5]。如今，超級電容器在運輸、軍事、電力備份及后備電源中的作用愈發(fā)重要ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2018</Year><RecNum>63</RecNum><DisplayText><styleface="superscript">[6]</style></DisplayText><record><rec-number>63</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618571680">63</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Lei</author><author>Hu,Xiaosong</author><author>Wang,Zhenpo</author><author>Sun,Fengchun</author><author>Dorrell,DavidG.</author></authors></contributors><titles><title>Areviewofsupercapacitormodeling,estimation,andapplications:Acontrol/managementperspective</title><secondary-title>Renewable&SustainableEnergyReviews</secondary-title></titles><periodical><full-title>Renewable&SustainableEnergyReviews</full-title><abbr-1>Renew.Sust.Energ.Rev.</abbr-1><abbr-2>Renew.Sust.Energ.Rev.</abbr-2></periodical><pages>1868-1878</pages><volume>81</volume><dates><year>2018</year><pub-dates><date>Jan</date></pub-dates></dates><isbn>1364-0321</isbn><accession-num>WOS:000417078200019</accession-num><urls><related-urls><url><GotoISI>://WOS:000417078200019</url></related-urls></urls><electronic-resource-num>10.1016/j.rser.2017.05.283</electronic-resource-num></record></Cite></EndNote>[6]。在使用過程中，既能單獨使用，同時也可以與電池搭配使用，進而提高整體性能。超級電容器與電池進行搭配，利用其高速充放電以及循環(huán)壽命長等優(yōu)勢彌補電池的不足。超級電容器電極材料對于器件的性能有著舉足輕重的作用，是超級電容器的重點研究方向。當前文獻報的超級電容器的電極材料主要有碳材料、金屬氧化物、導(dǎo)電聚合物ADDINEN.CITE<EndNote><Cite><Author>Simon</Author><Year>2008</Year><RecNum>64</RecNum><DisplayText><styleface="superscript">[7]</style></DisplayText><record><rec-number>64</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618574864">64</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Simon,Patrice</author><author>Gogotsi,Yury</author></authors></contributors><titles><title>Materialsforelectrochemicalcapacitors</title><secondary-title>NatureMaterials</secondary-title></titles><periodical><full-title>NatureMaterials</full-title><abbr-1>Nat.Mater.</abbr-1><abbr-2>Nat.Mater.</abbr-2></periodical><pages>845-854</pages><volume>7</volume><number>11</number><dates><year>2008</year><pub-dates><date>Nov</date></pub-dates></dates><isbn>1476-1122</isbn><accession-num>WOS:000260472800016</accession-num><urls><related-urls><url><GotoISI>://WOS:000260472800016</url></related-urls></urls><electronic-resource-num>10.1038/nmat2297</electronic-resource-num></record></Cite></EndNote>[7]。遺憾的是，單一材料的超級電容器或多或少都有一些不足，故而在文獻報道和實際制作中經(jīng)常使用復(fù)合材料。石墨烯/聚苯胺復(fù)合材料因其顯著的協(xié)同作用更是引起了科研工作者強烈的關(guān)注ADDINEN.CITEADDINEN.CITE.DATA[8-10]。本文通過電化學(xué)聚合制備了石墨烯/聚苯胺復(fù)合水凝膠膜并制備相應(yīng)的超級電容器電極，隨后組裝成無需粘合劑的全固態(tài)超級電容器。1.2超級電容器的工作原理超級電容器的分類標準有很多，可以根據(jù)電極材料進行分類，也可以根據(jù)工作原理進行分類。按照電極材料進行分類，可以分為對稱超級電容器和非對稱超級電容器。對稱超級電容器中兩個電極的活性材料相同、反應(yīng)相同；而非對稱超級電容器中兩個電極的活性材料不同、反應(yīng)不同ADDINEN.CITE<EndNote><Cite><Author>Boota</Author><Year>2019</Year><RecNum>68</RecNum><DisplayText><styleface="superscript">[11]</style></DisplayText><record><rec-number>68</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618577744">68</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Boota,Muhammad</author><author>Gogotsi,Yury</author></authors></contributors><titles><title>MXene-ConductingPolymerAsymmetricPseudocapacitors</title><secondary-title>AdvancedEnergyMaterials</secondary-title></titles><periodical><full-title>AdvancedEnergyMaterials</full-title><abbr-1>Adv.EnergyMater.</abbr-1><abbr-2>Adv.EnergyMater.</abbr-2></periodical><pages>1802917</pages><volume>9</volume><number>7</number><dates><year>2019</year><pub-dates><date>Feb14</date></pub-dates></dates><isbn>1614-6832</isbn><accession-num>WOS:000458912300002</accession-num><urls><related-urls><url><GotoISI>://WOS:000458912300002</url></related-urls></urls><custom7>1802917</custom7><electronic-resource-num>10.1002/aenm.201802917</electronic-resource-num></record></Cite></EndNote>[11]。然而在大多數(shù)文獻中，更多的是按照工作原理進行分類，即分為雙電層電容器（EDLC）和贗電容器ADDINEN.CITE<EndNote><Cite><Author>Allagui</Author><Year>2018</Year><RecNum>69</RecNum><DisplayText><styleface="superscript">[12]</style></DisplayText><record><rec-number>69</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618578071">69</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Allagui,Anis</author><author>Freeborn,ToddJ.</author><author>Elwakil,AhmedS.</author><author>Fouda,MohammedE.</author><author>Maundy,BrentJ.</author><author>Radwan,AhmadG.</author><author>Said,Zafar</author><author>Abdelkareem,MohammadAli</author></authors></contributors><titles><title>Reviewoffractional-orderelectricalcharacterizationofsupercapacitors</title><secondary-title>JournalofPowerSources</secondary-title></titles><periodical><full-title>JournalofPowerSources</full-title><abbr-1>J.PowerSources</abbr-1><abbr-2>J.PowerSources</abbr-2></periodical><pages>457-467</pages><volume>400</volume><dates><year>2018</year><pub-dates><date>Oct1</date></pub-dates></dates><isbn>0378-7753</isbn><accession-num>WOS:000447555400048</accession-num><urls><related-urls><url><GotoISI>://WOS:000447555400048</url></related-urls></urls><electronic-resource-num>10.1016/j.jpowsour.2018.08.047</electronic-resource-num></record></Cite></EndNote>[12]。1.2.1雙電層電容器的工作原理圖1-1EDLC工作原理示意圖?！半p電層”這一概念最早由Herlmholtz提出，Herlmholtz認為每個電極/溶液界面能夠視作一個平行板電容器，雙電層電容的產(chǎn)生來自于兩個電極/溶液界面上離子的定向排布ADDINEN.CITEADDINEN.CITE.DATA[13,14]。圖1-1為EDLC工作原理示意圖，在充電時，電解質(zhì)中的陰、陽離子能夠與電極材料中的異性電荷相互吸引，從而形成兩個電性相反的電荷層；在放電時，被吸引的陰、陽離子又重新返回電解質(zhì)中。因此，在EDLC中，儲存電荷僅僅依靠離子的物理吸附/解吸過程，并不涉及任何的化學(xué)反應(yīng)。EDLC電極的比電容值（C）計算公式為：C其中，εr：電解質(zhì)的相對介電常數(shù)；ε0：真空介電常數(shù)；d：雙電層之間的距離；1.2.2贗電容器的工作原理圖1-2贗電容器工作原理示意圖。贗電容也叫偽電容，贗電容器通過電極表面活性材料的氧化還原反應(yīng)儲能ADDINEN.CITE<EndNote><Cite><Author>Conway</Author><Year>1997</Year><RecNum>72</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>72</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618643990">72</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Conway,B.E.</author><author>Birss,V.</author><author>Wojtowicz,J.</author></authors></contributors><titles><title>Theroleandutilizationofpseudocapacitanceforenergystoragebysupercapacitors</title><secondary-title>JournalofPowerSources</secondary-title></titles><periodical><full-title>JournalofPowerSources</full-title><abbr-1>J.PowerSources</abbr-1><abbr-2>J.PowerSources</abbr-2></periodical><pages>1-14</pages><volume>66</volume><number>1-2</number><dates><year>1997</year><pub-dates><date>May-Jun</date></pub-dates></dates><isbn>0378-7753</isbn><accession-num>WOS:A1997XJ43700001</accession-num><urls><related-urls><url><GotoISI>://WOS:A1997XJ43700001</url></related-urls></urls><electronic-resource-num>10.1016/s0378-7753(96)02474-3</electronic-resource-num></record></Cite></EndNote>[15]。如圖1-2所示，在充電時，電解質(zhì)中的離子進入到活性材料的表面以及內(nèi)部發(fā)生氧化還原反應(yīng)；在放電時，則通過逆向的化學(xué)反應(yīng)從電極材料體相中釋放回電解質(zhì)。這種可逆的氧化還原反應(yīng)以及對材料表面/內(nèi)部的充分利用能夠使贗電容器具有更大的比電容值和能量密度。雖然優(yōu)勢明顯，不足卻是不容忽視。在贗電容器的使用過程中，電極活性材料會產(chǎn)生不可避免的降解或者結(jié)構(gòu)坍塌，從而降低電容器的使用壽命。并且氧化還原反應(yīng)的發(fā)生比離子吸脫附所花費的時間更多，因此功率密度也較低。1.3超級電容器的電極材料研究進展1.3.1碳材料從上一節(jié)EDLC容量的計算公式可知，C的提升可選擇比表面積大的活性材料，而碳材料正是由于這種特性受到科研工作者的青睞。文獻報道中常見的碳基材料有活性炭ADDINEN.CITE<EndNote><Cite><Author>Dubey</Author><Year>2019</Year><RecNum>73</RecNum><DisplayText><styleface="superscript">[16]</style></DisplayText><record><rec-number>73</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618644768">73</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Dubey,Richa</author><author>Guruviah,Velmathi</author></authors></contributors><titles><title>Reviewofcarbon-basedelectrodematerialsforsupercapacitorenergystorage</title><secondary-title>Ionics</secondary-title></titles><periodical><full-title>Ionics</full-title></periodical><pages>1419-1445</pages><volume>25</volume><number>4</number><dates><year>2019</year><pub-dates><date>Apr</date></pub-dates></dates><isbn>0947-7047</isbn><accession-num>WOS:000468282200001</accession-num><urls><related-urls><url><GotoISI>://WOS:000468282200001</url></related-urls></urls><electronic-resource-num>10.1007/s11581-019-02874-0</electronic-resource-num></record></Cite></EndNote>[16]（AC）、石墨烯ADDINEN.CITE<EndNote><Cite><Author>Najib</Author><Year>2019</Year><RecNum>75</RecNum><DisplayText><styleface="superscript">[17]</style></DisplayText><record><rec-number>75</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618645010">75</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Najib,Sumaiyah</author><author>Erdem,Emre</author></authors></contributors><titles><title>Currentprogressachievedinnovelmaterialsforsupercapacitorelectrodes:minireview</title><secondary-title>NanoscaleAdvances</secondary-title></titles><periodical><full-title>NanoscaleAdvances</full-title><abbr-1>NanoscaleAdv.</abbr-1><abbr-2>NanoscaleAdv.</abbr-2></periodical><pages>2817-2827</pages><volume>1</volume><number>8</number><dates><year>2019</year><pub-dates><date>Aug1</date></pub-dates></dates><isbn>2516-0230</isbn><accession-num>WOS:000479061800002</accession-num><urls><related-urls><url><GotoISI>://WOS:000479061800002</url></related-urls></urls><electronic-resource-num>10.1039/c9na00345b</electronic-resource-num></record></Cite></EndNote>[17]（graphene）以及碳納米管ADDINEN.CITE<EndNote><Cite><Author>Ciszewski</Author><Year>2019</Year><RecNum>74</RecNum><DisplayText><styleface="superscript">[18]</style></DisplayText><record><rec-number>74</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618644843">74</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ciszewski,Mateusz</author><author>Koszorek,Andrzej</author><author>Radko,Tomasz</author><author>Szatkowski,Piotr</author><author>Janas,Dawid</author></authors></contributors><titles><title>ReviewoftheSelectedCarbon-BasedMaterialsforSymmetricSupercapacitorApplication</title><secondary-title>JournalofElectronicMaterials</secondary-title></titles><periodical><full-title>JournalofElectronicMaterials</full-title><abbr-1>J.Electron.Mater.</abbr-1><abbr-2>J.Electron.Mater.</abbr-2></periodical><pages>717-744</pages><volume>48</volume><number>2</number><dates><year>2019</year><pub-dates><date>Feb</date></pub-dates></dates><isbn>0361-5235</isbn><accession-num>WOS:000455263100001</accession-num><urls><related-urls><url><GotoISI>://WOS:000455263100001</url></related-urls></urls><electronic-resource-num>10.1007/s11664-018-6811-7</electronic-resource-num></record></Cite></EndNote>[18]（CNTs）等。石墨烯是本篇工作的重點內(nèi)容，將在1.4節(jié)進行詳細闡述。AC具有化學(xué)性質(zhì)穩(wěn)定、來源廣泛、經(jīng)濟易得的優(yōu)勢，加之其較大的比表面積，常常應(yīng)用于EDLC中。AC主要來源于含碳量高的有機前驅(qū)體，比如蔗糖、植物纖維、瀝青和淀粉ADDINEN.CITEADDINEN.CITE.DATA[19-22]。通常利用物理、化學(xué)活化增加AC的孔隙率，進而達到提高其電化學(xué)性能的目的。Zhu等人ADDINEN.CITE<EndNote><Cite><Author>Zhu</Author><Year>2018</Year><RecNum>81</RecNum><DisplayText><styleface="superscript">[23]</style></DisplayText><record><rec-number>81</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618649621">81</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhu,Xinqiang</author><author>Yu,Shuai</author><author>Xu,Keting</author><author>Zhang,Yan</author><author>Zhang,Lumin</author><author>Lou,Gaobo</author><author>Wu,Yatao</author><author>Zhu,Enhui</author><author>Chen,Hao</author><author>Shen,Zhehong</author><author>Bao,Binfu</author><author>Fu,Shenyuan</author></authors></contributors><titles><title>Sustainableactivatedcarbonsfromdeadginkgoleavesforsupercapacitorelectrodeactivematerials</title><secondary-title>ChemicalEngineeringScience</secondary-title></titles><periodical><full-title>ChemicalEngineeringScience</full-title><abbr-1>Chem.Eng.Sci.</abbr-1><abbr-2>Chem.Eng.Sci.</abbr-2></periodical><pages>36-45</pages><volume>181</volume><dates><year>2018</year><pub-dates><date>May18</date></pub-dates></dates><isbn>0009-2509</isbn><accession-num>WOS:000431193400003</accession-num><urls><related-urls><url><GotoISI>://WOS:000431193400003</url></related-urls></urls><electronic-resource-num>10.1016/j.ces.2018.02.004</electronic-resource-num></record></Cite></EndNote>[23]以銀杏葉為原料制備了活性炭材料，在經(jīng)過KOH、ZnCl2和H3BO3活化后的材料比表面積最高為835.4m2g-1（相應(yīng)的SEM圖像如圖1-3所示），所制備的電極比電容可達374Fg-1（電流密度0.2Ag-1）。不過，活性炭材料的孔徑分布比較廣泛，微孔（<2nm）、介孔（2–50nm）以及大孔（>50nm）都有，并且有些微孔孔徑小于0.5nm，這樣電解質(zhì)中的例子很難進入材料內(nèi)部，因此離子的傳輸性能較差，能量密度也相對降低，這些都限制了活性炭超級電容器的發(fā)展。圖1-3經(jīng)過KOH活化的活性炭材料的SEM圖像ADDINEN.CITE<EndNote><Cite><Author>Zhu</Author><Year>2018</Year><RecNum>81</RecNum><DisplayText><styleface="superscript">[23]</style></DisplayText><record><rec-number>81</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618649621">81</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhu,Xinqiang</author><author>Yu,Shuai</author><author>Xu,Keting</author><author>Zhang,Yan</author><author>Zhang,Lumin</author><author>Lou,Gaobo</author><author>Wu,Yatao</author><author>Zhu,Enhui</author><author>Chen,Hao</author><author>Shen,Zhehong</author><author>Bao,Binfu</author><author>Fu,Shenyuan</author></authors></contributors><titles><title>Sustainableactivatedcarbonsfromdeadginkgoleavesforsupercapacitorelectrodeactivematerials</title><secondary-title>ChemicalEngineeringScience</secondary-title></titles><periodical><full-title>ChemicalEngineeringScience</full-title><abbr-1>Chem.Eng.Sci.</abbr-1><abbr-2>Chem.Eng.Sci.</abbr-2></periodical><pages>36-45</pages><volume>181</volume><dates><year>2018</year><pub-dates><date>May18</date></pub-dates></dates><isbn>0009-2509</isbn><accession-num>WOS:000431193400003</accession-num><urls><related-urls><url><GotoISI>://WOS:000431193400003</url></related-urls></urls><electronic-resource-num>10.1016/j.ces.2018.02.004</electronic-resource-num></record></Cite></EndNote>[23]。CNTs是具有柱狀一維結(jié)構(gòu)的碳同素異形體，由日本的飯島博士于1991年發(fā)現(xiàn)。CNTs可經(jīng)由碳氫化合物的催化分解獲得，分為單壁碳納米管（單個石墨薄片形成，SWCNTs）和多壁碳納米管（多個石墨薄片組成，MWCNTs）。CNTs有著較高的機械強度以及出色的熱穩(wěn)定性，但是其微孔體積相對較小，離子傳輸困難，電化學(xué)性能較差。因此，科研工作者們設(shè)計一些方法提高其超級電容性能。Lee等人ADDINEN.CITE<EndNote><Cite><Author>Lee</Author><Year>2011</Year><RecNum>82</RecNum><DisplayText><styleface="superscript">[24]</style></DisplayText><record><rec-number>82</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618656998">82</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lee,Hyuck</author><author>Kim,Hyeongkeun</author><author>Cho,MiSuk</author><author>Choi,Jaeboong</author><author>Lee,Youngkwan</author></authors></contributors><titles><title>Fabricationofpolypyrrole(PPy)/carbonnanotube(CNT)compositeelectrodeonceramicfabricforsupercapacitorapplications</title><secondary-title>ElectrochimicaActa</secondary-title></titles><periodical><full-title>ElectrochimicaActa</full-title><abbr-1>Electrochim.Acta</abbr-1><abbr-2>Electrochim.Acta</abbr-2></periodical><pages>7460-7466</pages><volume>56</volume><number>22</number><dates><year>2011</year><pub-dates><date>Sep1</date></pub-dates></dates><isbn>0013-4686</isbn><accession-num>WOS:000295303700006</accession-num><urls><related-urls><url><GotoISI>://WOS:000295303700006</url></related-urls></urls><electronic-resource-num>10.1016/j.electacta.2011.06.113</electronic-resource-num></record></Cite></EndNote>[24]以化學(xué)氣相沉積(CVD)法，使得碳納米管長在陶瓷纖維上，有利于比表面積的增加，增強了其電荷儲存能力。另一方面，通過引入金屬有機骨架材料（MOFs），利用MOFs和CNTs的協(xié)同作用促進電解質(zhì)離子的傳輸，進而提高其電化學(xué)性能。Wen等人ADDINEN.CITE<EndNote><Cite><Author>Wen</Author><Year>2015</Year><RecNum>83</RecNum><DisplayText><styleface="superscript">[25]</style></DisplayText><record><rec-number>83</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618657545">83</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wen,Ping</author><author>Gong,Peiwei</author><author>Sun,Jinfeng</author><author>Wang,Jinqing</author><author>Yang,Shengrong</author></authors></contributors><titles><title>DesignandsynthesisofNi-MOF/CNTcompositesandrGO/carbonnitridecompositesforanasymmetricsupercapacitorwithhighenergyandpowerdensity</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title><abbr-1>J.Mater.Chem.A</abbr-1><abbr-2>J.Mater.Chem.A</abbr-2></periodical><pages>13874-13883</pages><volume>3</volume><number>26</number><dates><year>2015</year><pub-dates><date>2015</date></pub-dates></dates><isbn>2050-7488</isbn><accession-num>WOS:000356865300032</accession-num><urls><related-urls><url><GotoISI>://WOS:000356865300032</url></related-urls></urls><electronic-resource-num>10.1039/c5ta02461g</electronic-resource-num></record></Cite></EndNote>[25]制備了Ni-MOF/CNT復(fù)合材料（相應(yīng)的SEM和TEM圖像如圖1-4所示），具有極大的比電容值（1765Fg-1，電流密度為0.5Ag-1）；基于該復(fù)合材料的超級電容器在經(jīng)過5000次循環(huán)測試之后電容僅損失5%。圖1-4碳納米管沉積在陶瓷纖維上的(a)SEM圖像和(b)TEM圖像ADDINEN.CITE<EndNote><Cite><Author>Wen</Author><Year>2015</Year><RecNum>83</RecNum><DisplayText><styleface="superscript">[25]</style></DisplayText><record><rec-number>83</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618657545">83</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wen,Ping</author><author>Gong,Peiwei</author><author>Sun,Jinfeng</author><author>Wang,Jinqing</author><author>Yang,Shengrong</author></authors></contributors><titles><title>DesignandsynthesisofNi-MOF/CNTcompositesandrGO/carbonnitridecompositesforanasymmetricsupercapacitorwithhighenergyandpowerdensity</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title><abbr-1>J.Mater.Chem.A</abbr-1><abbr-2>J.Mater.Chem.A</abbr-2></periodical><pages>13874-13883</pages><volume>3</volume><number>26</number><dates><year>2015</year><pub-dates><date>2015</date></pub-dates></dates><isbn>2050-7488</isbn><accession-num>WOS:000356865300032</accession-num><urls><related-urls><url><GotoISI>://WOS:000356865300032</url></related-urls></urls><electronic-resource-num>10.1039/c5ta02461g</electronic-resource-num></record></Cite></EndNote>[25]。1.3.2過渡金屬氧化物過渡金屬氧化物不僅能夠通過離子吸脫附儲存電荷，還可以通過發(fā)生氧化還原反應(yīng)儲能。1975年，Convey等首次提出法拉第準電容模型，隨后又發(fā)現(xiàn)RuO2能夠儲存電荷，并且理論比電容值最高（可達1580Fg-1）ADDINEN.CITE<EndNote><Cite><Author>Hu</Author><Year>2006</Year><RecNum>84</RecNum><DisplayText><styleface="superscript">[26]</style></DisplayText><record><rec-number>84</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618664953">84</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hu,Chi-Chang</author><author>Chang,Kuo-Hsin</author><author>Lin,Ming-Champ</author><author>Wu,Yung-Tai</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">DesignandtailoringofthenanotubulararrayedarchitectureofhydrousRuO</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">fornextgenerationsupercapacitors</style></title><secondary-title>NanoLetters</secondary-title></titles><periodical><full-title>NanoLetters</full-title><abbr-1>NanoLett.</abbr-1><abbr-2>NanoLett.</abbr-2></periodical><pages>2690-2695</pages><volume>6</volume><number>12</number><dates><year>2006</year><pub-dates><date>Dec13</date></pub-dates></dates><isbn>1530-6984</isbn><accession-num>WOS:000242786500010</accession-num><urls><related-urls><url><GotoISI>://WOS:000242786500010</url></related-urls></urls><electronic-resource-num>10.1021/nl061576a</electronic-resource-num></record></Cite></EndNote>[26]。在隨后的科研工作中，NiOADDINEN.CITE<EndNote><Cite><Author>Kim</Author><Year>2013</Year><RecNum>8</RecNum><DisplayText><styleface="superscript">[27]</style></DisplayText><record><rec-number>8</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092257">8</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kim,Sun-I.</author><author>Lee,Jung-Soo</author><author>Ahn,Hyo-Jin</author><author>Song,Hyun-Kon</author><author>Jang,Ji-Hyun</author></authors></contributors><titles><title>FacileRoutetoanEfficientNiOSupercapacitorwithaThree-DimensionalNanonetworkMorphology</title><secondary-title>ACSAppliedMaterials&Interfaces</secondary-title></titles><periodical><full-title>ACSAppliedMaterials&Interfaces</full-title><abbr-1>ACSAppl.Mater.Interfaces</abbr-1><abbr-2>ACSAppl.Mater.Interfaces</abbr-2></periodical><pages>1596-1603</pages><volume>5</volume><number>5</number><dates><year>2013</year><pub-dates><date>Mar13</date></pub-dates></dates><isbn>1944-8244</isbn><accession-num>WOS:000316308100011</accession-num><urls><related-urls><url><GotoISI>://WOS:000316308100011</url></related-urls></urls><electronic-resource-num>10.1021/am3021894</electronic-resource-num></record></Cite></EndNote>[27]、MnOxADDINEN.CITE<EndNote><Cite><Author>He</Author><Year>2013</Year><RecNum>9</RecNum><DisplayText><styleface="superscript">[28]</style></DisplayText><record><rec-number>9</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092257">9</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>He,Yongmin</author><author>Chen,Wanjun</author><author>Li,Xiaodong</author><author>Zhang,Zhenxing</author><author>Fu,Jiecai</author><author>Zhao,Changhui</author><author>Xie,Erqing</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">FreestandingThree-DimensionalGraphene/MnO</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">CompositeNetworksAsUltralightandFlexibleSupercapacitorElectrodes</style></title><secondary-title>ACSNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>174-182</pages><volume>7</volume><number>1</number><dates><year>2013</year><pub-dates><date>Jan</date></pub-dates></dates><isbn>1936-0851</isbn><accession-num>WOS:000314082800021</accession-num><urls><related-urls><url><GotoISI>://WOS:000314082800021</url></related-urls></urls><electronic-resource-num>10.1021/nn304833s</electronic-resource-num></record></Cite></EndNote>[28]、ZnOADDINEN.CITE<EndNote><Cite><Author>Cai</Author><Year>2014</Year><RecNum>10</RecNum><DisplayText><styleface="superscript">[29]</style></DisplayText><record><rec-number>10</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092257">10</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cai,Daoping</author><author>Huang,Hui</author><author>Wang,Dandan</author><author>Liu,Bin</author><author>Wang,Lingling</author><author>Liu,Yuan</author><author>Li,Qiuhong</author><author>Wang,Taihong</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">High-PerformanceSupercapacitorElectrodeBasedontheUniqueZnO@Co</style><styleface="subscript"font="default"size="100%">3</style><styleface="normal"font="default"size="10