石墨烯基超級電容器電極材料研究進展

**大學研究生課程考試（查）論文2014——2015學年第二學期《石墨烯基超級電容器電極材料研究進展》課程名稱：材料化學任課教師：學院：專業(yè)：學號：姓名：成績：石墨烯基超級電容器電極材料研究進展摘要：超級電容器是目前研究較多的新型儲能元件，其大的比電容、高的循環(huán)穩(wěn)定性以及快速的充放電過程等優(yōu)良特性，使其在電能儲存及轉化方面得到廣泛應用。超級電容器的電極材料是它的技術核心。石墨烯作為一種新型的納米材料，具有良好的導電性和較大的比表面積，可作為超級電容器的電極材料。利用其他導電物質(zhì)對石墨烯進行改性和復合，可以在保持其本身獨特優(yōu)點的同時提高作為電極材料的導電率、循環(huán)穩(wěn)定性等其他性能。本文對近年來石墨烯基電極材料在兩種不同類型超級電容器中的應用研究進行了綜述。關鍵詞：超級電容器；石墨烯；導電聚合物；金屬氧化物隨著人類社會賴以生存的環(huán)境狀況的日益惡化，過多的CO2排放造成氣候變化不穩(wěn)定，人們對能源的開發(fā)和研究重點已經(jīng)轉移到綠色能源（如太陽能、風能等）上面ADDINEN.CITEADDINEN.CITE.DATA[\o"Arico,2005#553"1,\o"Wang,2012#666"2]，但是它們是靠大自然的資源來儲能和轉化能量的，其發(fā)電能力極大程度要受到自然環(huán)境以及季節(jié)變化的影響，如果被廣泛應用于日常生活，有很多不穩(wěn)定性，這也是目前太陽能、風能領域的瓶頸。超級電容器，又稱作電化學電容器，是一種既穩(wěn)定又環(huán)保的新型儲能元件。它具有充電時間短、使用壽命長、功率密度高、安全系數(shù)高、節(jié)能環(huán)保、低溫特性好等優(yōu)點。超級電容器在現(xiàn)代科技、工業(yè)、航天事業(yè)方面的應用都十分廣泛，它代表了高儲能技術的一次突破。目前，國內(nèi)在相關方面做了許多研究，并實現(xiàn)了商業(yè)化生產(chǎn)。但是，它們的廣泛應用還存在，例如，能量密低、成本過高等問題。從原理出發(fā)，超級電容器可分為雙電層電容器和法拉第贗電容器兩類。兩者均是由多孔雙電極、電解質(zhì)、集流體、隔離物4部分所構成（超級電容器結構如圖1所示）。為了減小接觸電阻，要求電解質(zhì)和電極材料緊密接觸；隔離物的電子電導要低，離子電導要高，以保證電解質(zhì)離子順利穿透。雙電層電容器是利用雙電極和電解質(zhì)組成的雙電層結構來實驗充放電儲能的。當在兩電極上施加電壓，電解質(zhì)被電離產(chǎn)生正負離子，由于電荷補償，正離子移向負電極，負離子移向正電極，這樣就在電極與電解質(zhì)界面處產(chǎn)生雙電層。由于這個雙電層是由相反電荷層構成，如同普通平板電容器一樣，但是此雙電層間距很小，是原子尺寸量級，因此電容比普通電容器大得多。法拉第贗電容器是與電極充電電位有關的電容器，其原理是電活性物質(zhì)在電極材料表面活體相中的二維或準二維空間上進行欠電位沉積，從而發(fā)生可逆的化學吸附、脫附或氧化還原反應。當電極在外加電場作用下時，電解液中離子發(fā)生遷移，擴散到電極與電解液界面處，發(fā)生電化學反應，從而進入到電極表面的活性氧化物體相中，實現(xiàn)電荷存儲，放電時，離子又回到電解液，釋放存儲的電荷，如此反復實現(xiàn)充放電。圖1超級電容器結構示意圖

電極材料是超級電容器實現(xiàn)電荷存儲并直接影響電容器的性能和生產(chǎn)成本的重要部分，其導電性和比表面積是重要參數(shù)，大的比表面積可以吸附更多的電解液離子，能夠存儲或者釋放更多的電荷。因此，對超級電容器的研究重點就放在了高比表面積、低成本和高導電率的電極材料上。從現(xiàn)在的研究進展看，可以作為超級電容器電極材料ADDINEN.CITEADDINEN.CITE.DATA[\o"Wang,2012#666"2,\o"江奇,2002#691"3]的主要有過渡金屬氧化物ADDINEN.CITE<EndNote><Cite><Author>龐旭</Author><Year>2009</Year><RecNum>692</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[4]</style></DisplayText><record><rec-number>692</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">692</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>龐旭</author><author>馬正青</author><author>左列</author></authors></contributors><auth-address>中南大學材料科學與工程學院;</auth-address><titles><title>Sn摻雜二氧化錳超級電容器電極材料</title><secondary-title>物理化學學報</secondary-title></titles><periodical><full-title>物理化學學報</full-title></periodical><pages>2433-2437</pages><number>12</number><keywords><keyword>超級電容器</keyword><keyword>二氧化錳</keyword><keyword>摻雜</keyword><keyword>二氧化錫</keyword><keyword>電極材料</keyword></keywords><dates><year>2009</year></dates><isbn>1000-6818</isbn><call-num>11-1892/O6</call-num><urls></urls><remote-database-provider>Cnki</remote-database-provider></record></Cite></EndNote>[\o"龐旭,2009#692"4]、有機導電聚合物以及碳納米管ADDINEN.CITE<EndNote><Cite><Author>王貴欣</Author><Year>2004</Year><RecNum>693</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[5]</style></DisplayText><record><rec-number>693</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">693</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>王貴欣</author><author>瞿美臻</author><author>陳利</author><author>于作龍</author></authors></contributors><auth-address>中國科學院成都有機化學研究所國家納米科學中心,中國科學院成都有機化學研究所國家納米科學中心,中國科學院成都有機化學研究所國家納米科學中心,中國科學院成都有機化學研究所國家納米科學中心成都610041,成都610041,成都610041,成都610041</auth-address><titles><title>碳納米管用作超級電容器電極材料</title><secondary-title>化學通報</secondary-title></titles><periodical><full-title>化學通報</full-title></periodical><pages>185-191+197</pages><number>03</number><keywords><keyword>碳納米管</keyword><keyword>超級電容器</keyword><keyword>電極材料</keyword></keywords><dates><year>2004</year></dates><isbn>0441-3776</isbn><call-num>11-1804/O6</call-num><urls></urls><remote-database-provider>Cnki</remote-database-provider></record></Cite></EndNote>[\o"王貴欣,2004#693"5]、活性炭ADDINEN.CITE<EndNote><Cite><Author>楊常玲</Author><Year>2010</Year><RecNum>694</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[6]</style></DisplayText><record><rec-number>694</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">694</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>楊常玲</author><author>孫彥平</author><author>邴雪飛</author><author>呂永根</author></authors></contributors><auth-address>東華大學化學化工與生物工程學院;太原理工大學化工系;東華大學材料科學與工程學院;</auth-address><titles><title>活性泡沫炭用于超級電容器電極材料</title><secondary-title>功能材料</secondary-title></titles><periodical><full-title>功能材料</full-title></periodical><pages>165-168</pages><number>01</number><keywords><keyword>超級電容器</keyword><keyword>泡沫炭</keyword><keyword>孔結構</keyword><keyword>充放電性能</keyword></keywords><dates><year>2010</year></dates><isbn>1001-9731</isbn><call-num>50-1099/TH</call-num><urls></urls><remote-database-provider>Cnki</remote-database-provider></record></Cite></EndNote>[\o"楊常玲,2010#694"6]、碳氣凝膠ADDINEN.CITE<EndNote><Cite><Author>孟慶函</Author><Year>2004</Year><RecNum>695</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[7]</style></DisplayText><record><rec-number>695</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">695</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>孟慶函</author><author>劉玲</author><author>宋懷河</author><author>凌立成</author></authors></contributors><auth-address>北京化工大學可控化學反應科學與技術基礎教育部重點實驗室,北京化工大學可控化學反應科學與技術基礎教育部重點實驗室,北京化工大學可控化學反應科學與技術基礎教育部重點實驗室,北京化工大學可控化學反應科學與技術基礎教育部重點實驗室北京100029,北京100029,北京100029,北京100029</auth-address><titles><title>炭氣凝膠為電極的超級電容器的研究</title><secondary-title>功能材料</secondary-title></titles><periodical><full-title>功能材料</full-title></periodical><pages>457-459</pages><number>04</number><keywords><keyword>炭氣凝膠</keyword><keyword>超級電容器</keyword><keyword>電化學性能</keyword></keywords><dates><year>2004</year></dates><isbn>1001-9731</isbn><call-num>50-1099/TH</call-num><urls></urls><remote-database-provider>Cnki</remote-database-provider></record></Cite></EndNote>[\o"孟慶函,2004#695"7]等多孔性炭材料。

作為新型碳材料的石墨烯（G），其物理結構穩(wěn)定、比表面積大、導電性良好，利用其他導電物質(zhì)對其進行改性、復合得到的G基復合物ADDINEN.CITE<EndNote><Cite><Author>Stankovich</Author><Year>2006</Year><RecNum>696</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[8]</style></DisplayText><record><rec-number>696</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">696</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Stankovich,S.</author><author>Dikin,D.A.</author><author>Dommett,G.H.B.</author><author>Kohlhaas,K.M.</author><author>Zimney,E.J.</author><author>Stach,E.A.</author><author>Piner,R.D.</author><author>Nguyen,S.T.</author><author>Ruoff,R.S.</author></authors></contributors><auth-address>Nguyen,ST NorthwesternUniv,DeptMechEngn,2145SheridanRd,Evanston,IL60208USA NorthwesternUniv,DeptMechEngn,Evanston,IL60208USA NorthwesternUniv,DeptChem,Evanston,IL60208USA PurdueUniv,SchMatEngn,WLafayette,IN47907USA PurdueUniv,BirckNanotechnolCtr,WLafayette,IN47907USA</auth-address><titles><title>Graphene-basedcompositematerials</title><secondary-title>Nature</secondary-title><alt-title>Nature Nature</alt-title></titles><periodical><full-title>Nature</full-title><abbr-1>Nature</abbr-1><abbr-2>Nature</abbr-2></periodical><pages>282-286</pages><volume>442</volume><number>7100</number><keywords><keyword>thin-filmparticles</keyword><keyword>graphiteoxide</keyword><keyword>electricalapplications</keyword><keyword>carbonnanotubes</keyword><keyword>nanoplatelets</keyword><keyword>polymers</keyword><keyword>gas</keyword></keywords><dates><year>2006</year><pub-dates><date>Jul20</date></pub-dates></dates><isbn>0028-0836</isbn><accession-num>WOS:000239122100034</accession-num><urls><related-urls><url><GotoISI>://WOS:000239122100034</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Stankovich,2006#696"8]已成為超級電容器電極材料研究的熱門方向。盡管G本身具有大比表面積和高電導率以及其穩(wěn)定的表面結構使其很難被電解液侵蝕，因此其適合作為超級電容器的電極材料，以獲得大的電容量；但是，納米級的G片層之間存在的較大的分子間作用力導致其易發(fā)生團聚而使得比表面積降低。為了克服這一缺點，人們試著采用各種無機、有機、金屬物質(zhì)對G或者氧化石墨烯（GO）進行表面改性和復合，以使G為基底的電極材料不僅能有高的導電性能，而且有盡可能大的比表面積。本文對近年來石墨烯基電極材料在三種不同類型超級電容器中的應用研究綜述如下。1.石墨烯基雙電層電容器石墨烯具有優(yōu)異的導電性、柔韌性、力學性能和很大的比表面積，自身可作為雙電層超級電容器的電極材料。但無論是石墨烯、氧化石墨烯還是還原氧化石墨烯（RGO），它們在制備過程中均容易發(fā)生堆疊，影響石墨烯材料在電解質(zhì)中的分散性和表面可浸潤性，降低了石墨烯材料的有效比表面積和電導率。因此，避免石墨烯堆疊是制備高能量密度和高功率密度石墨烯基超級電容器的技術難題之一。ZhangADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2011</Year><RecNum>697</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[9]</style></DisplayText><record><rec-number>697</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">697</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,K.</author><author>Mao,L.</author><author>Zhang,L.L.</author><author>Chan,H.S.O.</author><author>Zhao,X.S.</author><author>Wu,J.S.</author></authors></contributors><auth-address>Wu,Js NatlUnivSingapore,DeptChem,3SciDr3,Singapore117543,Singapore NatlUnivSingapore,DeptChem,Singapore117543,Singapore NatlUnivSingapore,DeptChem&BiomolEngn,Singapore117576,Singapore</auth-address><titles><title>Surfactant-intercalated,chemicallyreducedgrapheneoxideforhighperformancesupercapacitorelectrodes</title><secondary-title>JournalOfMaterialsChemistry</secondary-title><alt-title>JMaterChem JMaterChem</alt-title></titles><periodical><full-title>JournalofMaterialsChemistry</full-title></periodical><pages>7302-7307</pages><volume>21</volume><number>20</number><keywords><keyword>exfoliatedgraphiteoxide</keyword><keyword>x-rayphotoelectron</keyword><keyword>reduction</keyword><keyword>films</keyword><keyword>ultracapacitors</keyword><keyword>nanoplatelets</keyword><keyword>spectroscopy</keyword></keywords><dates><year>2011</year></dates><isbn>0959-9428</isbn><accession-num>WOS:000290167200037</accession-num><urls><related-urls><url><GotoISI>://WOS:000290167200037</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Zhang,2011#697"9]等將各種表面活性劑，如四丁基氫氧化銨、十六烷基三甲基溴化銨、十二烷基苯磺酸鈉等嵌入到氧化石墨烯片中，緩解氧化石墨烯在還原過程中的堆疊現(xiàn)象，使表面活性劑有效地存在于石墨烯和氧化石墨烯片中，促進了材料表面的浸潤性，使材料能夠很好地分散，提高了材料的比容量。研究結果表明，在2mol/L的H2SO4水溶液中，采用四丁基氫氧化銨作為表面活性劑制備的電極材料在1A/g電流密度下的比容量達到194F/g。Yoon等ADDINEN.CITE<EndNote><Cite><Author>Yoon</Author><Year>2013</Year><RecNum>698</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[10]</style></DisplayText><record><rec-number>698</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">698</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yoon,Y.</author><author>Lee,K.</author><author>Baik,C.</author><author>Yoo,H.</author><author>Min,M.</author><author>Park,Y.</author><author>Lee,S.M.</author><author>Lee,H.</author></authors></contributors><auth-address>Lee,H SungkyunkwanUniv,DeptChem,DeptEnergySci,NCRICtrSmartMolMemory,Suwon440746,SouthKorea SungkyunkwanUniv,DeptChem,DeptEnergySci,NCRICtrSmartMolMemory,Suwon440746,SouthKorea</auth-address><titles><title>Anti-SolventDerivedNon-StackedReducedGrapheneOxideforHighPerformanceSupercapacitors</title><secondary-title>AdvancedMaterials</secondary-title><alt-title>AdvMater AdvMater</alt-title></titles><periodical><full-title>AdvancedMaterials</full-title><abbr-1>AdvMater</abbr-1><abbr-2>Adv.Mater.</abbr-2></periodical><pages>4437-4444</pages><volume>25</volume><number>32</number><keywords><keyword>anti-solvents</keyword><keyword>non-stackedgrapheneoxide</keyword><keyword>highporosity</keyword><keyword>supercapacitor</keyword><keyword>graphiteoxide</keyword><keyword>electrochemicalcapacitors</keyword><keyword>exfoliation</keyword><keyword>films</keyword><keyword>ultracapacitors</keyword><keyword>electrodes</keyword><keyword>nanosheets</keyword><keyword>reduction</keyword><keyword>paper</keyword></keywords><dates><year>2013</year><pub-dates><date>Aug27</date></pub-dates></dates><isbn>0935-9648</isbn><accession-num>WOS:000327749600009</accession-num><urls><related-urls><url><GotoISI>://WOS:000327749600009</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Yoon,2013#698"10]將己烷作為反溶劑物質(zhì)加入到氧化石墨烯片的乙醇溶液中，制備得到不堆疊的褶皺氧化石墨烯片和還原氧化石墨烯片，有效地提高了還原氧化石墨烯的比表面積和孔隙率，分別為1435.4m2/g和4.1cm3/g，顯著提升了該材料作為雙電層電容器電極的性能。在6.0mol/L的KOH水溶液中、1A/g的電流密度下，比容量達236F/g；在30A/g的電流密度下，比容量仍然達到171.2F/g。Wang等ADDINEN.CITEADDINEN.CITE.DATA[\o"Wang,2012#699"11]將柔性石墨烯紙與炭黑納米粒子通過普通的真空抽濾方法制備了復合電極材料，由于炭黑納米粒子的存在，有效緩解了抽濾過程中石墨烯自發(fā)的堆疊過程，使制備的復合材料電化學性能超過了純石墨烯紙的7倍，其最大的能量密度可達26W·h/kg，功率密度達5.1kW/kg。石墨烯層間距的控制對于避免石墨烯片層的堆疊、充分發(fā)揮石墨烯優(yōu)異結構特性與電化學性能具有重要作用。Hantel等ADDINEN.CITE<EndNote><Cite><Author>Hantel</Author><Year>2012</Year><RecNum>700</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[12]</style></DisplayText><record><rec-number>700</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">700</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hantel,M.M.</author><author>Kaspar,T.</author><author>Nesper,R.</author><author>Wokaun,A.</author><author>Kotz,R.</author></authors></contributors><auth-address>Kotz,R PaulScherrerInst,ElectrochemLab,CH-5232Villigen,Switzerland PaulScherrerInst,ElectrochemLab,CH-5232Villigen,Switzerland ETH,InorganChemLab,CH-8092Zurich,Switzerland</auth-address><titles><title>PartiallyReducedGraphiteOxideasanElectrodeMaterialforElectrochemicalDouble-LayerCapacitors</title><secondary-title>Chemistry-aEuropeanJournal</secondary-title><alt-title>Chem-EurJ Chem-EurJ</alt-title></titles><periodical><full-title>Chemistry-aEuropeanJournal</full-title><abbr-1>Chem-eurJ</abbr-1><abbr-2>Chem-eur.J.</abbr-2></periodical><pages>9125-9136</pages><volume>18</volume><number>29</number><keywords><keyword>aproticelectrolytes</keyword><keyword>cyclicvoltammetry</keyword><keyword>electrochemistry</keyword><keyword>graphene</keyword><keyword>graphiteoxide</keyword><keyword>x-ray-diffraction</keyword><keyword>grapheneoxide</keyword><keyword>pyrolytic-graphite</keyword><keyword>differentialcapacitance</keyword><keyword>electrical-conductivity</keyword><keyword>propylenecarbonate</keyword><keyword>thermalreduction</keyword><keyword>energydensity</keyword><keyword>supercapacitor</keyword><keyword>activation</keyword></keywords><dates><year>2012</year><pub-dates><date>Jul</date></pub-dates></dates><isbn>0947-6539</isbn><accession-num>WOS:000306221900035</accession-num><urls><related-urls><url><GotoISI>://WOS:000306221900035</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Hantel,2012#700"12]通過控制真空熱還原的加熱速度和還原溫度，獲得不同層間距的石墨烯和含不同氧官能團的石墨烯，并將其用作超級電容器的電極材料。研究發(fā)現(xiàn)，其電極比電容與石墨烯的層間距、石墨烯上的含氧官能團和使用的電解質(zhì)均有很大的關系，當層間距為0.43nm，己腈作為溶劑時，其比電容達到了220F/g，組成對稱超級電容器時其比電容達到了195F/g。楊曉偉等ADDINEN.CITE<EndNote><Cite><Author>Yang</Author><Year>2011</Year><RecNum>701</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[13]</style></DisplayText><record><rec-number>701</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">701</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yang,X.W.</author><author>Qiu,L.</author><author>Cheng,C.</author><author>Wu,Y.Z.</author><author>Ma,Z.F.</author><author>Li,D.</author></authors></contributors><auth-address>Li,D MonashUniv,ARC,CtrExcellenceElectromatSci,DeptMatEngn,Clayton,Vic3800,Australia MonashUniv,ARC,CtrExcellenceElectromatSci,DeptMatEngn,Clayton,Vic3800,Australia ShanghaiJiaoTongUniv,DeptChemEngn,Shanghai200240,PeoplesRChina</auth-address><titles><title>OrderedGelationofChemicallyConvertedGrapheneforNext-GenerationElectroconductiveHydrogelFilms</title><secondary-title>AngewandteChemie-InternationalEdition</secondary-title><alt-title>AngewChemIntEdit AngewChemIntEdit</alt-title></titles><periodical><full-title>AngewandteChemie-internationalEdition</full-title><abbr-1>AngewChemIntEdit</abbr-1><abbr-2>Angew.Chem.Int.Edit.</abbr-2></periodical><pages>7325-7328</pages><volume>50</volume><number>32</number><keywords><keyword>conductivematerials</keyword><keyword>filtration</keyword><keyword>graphene</keyword><keyword>hydrogels</keyword><keyword>stimulusresponse</keyword><keyword>oxide</keyword><keyword>sheets</keyword><keyword>platform</keyword><keyword>functionalization</keyword><keyword>nanosheets</keyword><keyword>paper</keyword></keywords><dates><year>2011</year></dates><isbn>1433-7851</isbn><accession-num>WOS:000293840400021</accession-num><urls><related-urls><url><GotoISI>://WOS:000293840400021</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Yang,2011#701"13]利用化學轉化石墨烯在水溶液中的高分散性，采用過濾的方法在濾膜和溶液界面可控制備了石墨烯片層定向分布的化學轉換石墨烯水凝膠（chemicallyconvertedgraphene，CCG），獲得了石墨烯片層之間π-π吸引力和溶劑化的排斥力之間的平衡點，具有良好的力學強度，可以直接作為超級電容器的電極應用。在此基礎上，為了確保實際應用中石墨烯電極內(nèi)部的片層網(wǎng)絡結構，采用毛細管壓縮過程（capillarycompressionprocedure），以CCG為前驅(qū)體，先通過真空過濾形成CCG膜，再將CCG膜浸潤在不同比例的揮發(fā)性/非揮發(fā)性物質(zhì)混合溶液中，通過毛細壓縮作用，非揮發(fā)性物質(zhì)、硫酸或離子液體（EMIMBF4）與水置換進入石墨烯片層間形成液體介導的致密性石墨烯基薄膜（如EM-CCG）（圖2）。圖2軟化學法制備EM-CCG薄膜過程示意圖圖3EM-CCM薄膜與干CCG膜的形貌與基本性質(zhì)ADDINEN.CITE<EndNote><Cite><Author>楊德志</Author><Year>2014</Year><RecNum>722</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[14]</style></DisplayText><record><rec-number>722</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">722</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>楊德志</author><author>沈佳妮</author><author>楊曉偉</author><author>馬紫峰</author></authors></contributors><auth-address>上海交通大學電化學與能源技術研究所;DepartmentofMaterialsEngineering,MonashUniversity;</auth-address><titles><title>石墨烯基超級電容器研究進展</title><secondary-title>儲能科學與技術</secondary-title></titles><periodical><full-title>儲能科學與技術</full-title></periodical><pages>1-8</pages><number>01</number><keywords><keyword>石墨烯</keyword><keyword>超級電容器</keyword><keyword>導電聚合物</keyword><keyword>金屬氧化物</keyword><keyword>能量密度</keyword><keyword>功率密度</keyword></keywords><dates><year>2014</year></dates><isbn>2095-4239</isbn><call-num>10-1076/TK</call-num><urls></urls><remote-database-provider>Cnki</remote-database-provider></record></Cite></EndNote>[\o"楊德志,2014#722"14]（a）-（f）EM-CCG膜（ρ=0.069，0.39，0.65，0.97，1.25g/cm3）和干CCG膜（ρ=1.49g/cm3）SEM圖；（g）嵌入EMIMBF4體積分數(shù)與CCG堆積密度及估算的石墨烯片層間距關系；（h）EM-CCG薄膜電導率和內(nèi)阻由于進入石墨烯片層的離子液體與水/離子液體混合比例有關，不同EMIMBF4體積比將形成堆積密度和石墨烯片層間距不同的EM-CCG薄膜，其電導率及內(nèi)阻也不相同，所制備EM-CCG薄膜基本形貌與性質(zhì)如圖3所示。除了避免石墨烯材料的堆疊外，要制備高性能石墨烯基超級電容器，如何實現(xiàn)孔隙率高、致密性好、有效比表面積大和離子遷移電阻低是另一關鍵問題。Wang等ADDINEN.CITE<EndNote><Cite><Author>Wang</Author><Year>2013</Year><RecNum>703</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[15]</style></DisplayText><record><rec-number>703</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">703</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wang,Z.L.</author><author>Xu,D.</author><author>Wang,H.G.</author><author>Wu,Z.</author><author>Zhang,X.B.</author></authors></contributors><auth-address>Zhang,XB ChineseAcadSci,ChangchunInstApplChem,StateKeyLabRareEarthResourceUtilizat,Changchun130022,PeoplesRChina ChineseAcadSci,ChangchunInstApplChem,StateKeyLabRareEarthResourceUtilizat,Changchun130022,PeoplesRChina UnivChineseAcadSci,Beijing100049,PeoplesRChina</auth-address><titles><title>InSituFabricationofPorousGrapheneElectrodesforHigh-PerformanceEnergyStorage</title><secondary-title>AcsNano</secondary-title><alt-title>AcsNano AcsNano</alt-title></titles><periodical><full-title>ACSNano</full-title><abbr-1>ACSnano</abbr-1></periodical><pages>2422-2430</pages><volume>7</volume><number>3</number><keywords><keyword>energystoragehighpower</keyword><keyword>insitusynthesis</keyword><keyword>synergisticeffect</keyword><keyword>graphene</keyword><keyword>lithium-ionbatteries</keyword><keyword>nitrogen-dopedgraphene</keyword><keyword>hollowcarbonnanospheres</keyword><keyword>high-ratecapability</keyword><keyword>paperelectrodes</keyword><keyword>ultrafast-charge</keyword><keyword>anodematerials</keyword><keyword>listorage</keyword><keyword>capacity</keyword><keyword>oxide</keyword></keywords><dates><year>2013</year><pub-dates><date>Mar</date></pub-dates></dates><isbn>1936-0851</isbn><accession-num>WOS:000316846700060</accession-num><urls><related-urls><url><GotoISI>://WOS:000316846700060</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Wang,2013#703"15]制備了兼具多孔分層結構、高導電性的內(nèi)在網(wǎng)絡和雜環(huán)原子摻雜的石墨烯電極，在80A/g的電流密度下，其能量密度達322W·h/kg，功率密度達116kW/kg，充放電循環(huán)3000次后幾乎沒有遞減。Luan等ADDINEN.CITE<EndNote><Cite><Author>Luan</Author><Year>2013</Year><RecNum>704</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[16]</style></DisplayText><record><rec-number>704</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">704</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Luan,V.H.</author><author>Tien,H.N.</author><author>Hoa,L.T.</author><author>Nguyen,T.M.H.</author><author>Oh,E.S.</author><author>Chung,J.</author><author>Kim,E.J.</author><author>Choi,W.M.</author><author>Kong,B.S.</author><author>Hur,S.H.</author></authors></contributors><auth-address>Luan,VH UnivUlsan,SchChemEngn,Daehakro93,Ulsan680749,SouthKorea UnivUlsan,SchChemEngn,Ulsan680749,SouthKorea KCCCentResInst,AdvEnergyMatTeam,KyonggiDo446912,SouthKorea</auth-address><titles><title>Synthesisofahighlyconductiveandlargesurfaceareagrapheneoxidehydrogelanditsuseinasupercapacitor</title><secondary-title>JournalOfMaterialsChemistryA</secondary-title><alt-title>JMaterChemA JMaterChemA</alt-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>208-211</pages><volume>1</volume><number>2</number><keywords><keyword>nanoplatelets</keyword><keyword>composites</keyword><keyword>films</keyword></keywords><dates><year>2013</year></dates><isbn>2050-7488</isbn><accession-num>WOS:000314631700007</accession-num><urls><related-urls><url><GotoISI>://WOS:000314631700007</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Luan,2013#704"16]通過石墨烯與乙二胺聯(lián)氨還原形成了電導率高、比表面積大和3D結構穩(wěn)定的氧化石墨烯氣凝膠，該氣凝膠電導率達到1351S/m，比表面積為745m2/g，斷裂強度達到10.3MPa，比電容達到232F/g。2.石墨烯基法拉第準電容器石墨烯雖然可以單獨作為超級電容器電極材料，但其理論比容量僅有329F/g，限制了該材料的大規(guī)模應用ADDINEN.CITE<EndNote><Cite><Author>Cranford</Author><Year>2011</Year><RecNum>705</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[17]</style></DisplayText><record><rec-number>705</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">705</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cranford,S.W.</author><author>Buehler,M.J.</author></authors></contributors><auth-address>Cranford,SW MIT,CtrMatSci&Engn,77MassachusettsAve,Cambridge,MA02139USA MIT,CtrMatSci&Engn,Cambridge,MA02139USA MIT,DeptCivil&EnvironmEngn,LabAtomist&MolMech,Cambridge,MA02139USA</auth-address><titles><title>Packingefficiencyandaccessiblesurfaceareaofcrumpledgraphene</title><secondary-title>PhysicalReviewB</secondary-title><alt-title>PhysRevB PhysRevB</alt-title></titles><periodical><full-title>PhysicalReviewB</full-title><abbr-1>PhysRevB</abbr-1><abbr-2>Phys.Rev.B</abbr-2></periodical><volume>84</volume><number>20</number><keywords><keyword>carbonnanotubeelectrodes</keyword><keyword>molecular-dynamics</keyword><keyword>electrochemicalcapacitors</keyword><keyword>suspendedgraphene</keyword><keyword>elasticproperties</keyword><keyword>bilayergraphene</keyword><keyword>nanoribbons</keyword><keyword>graphite</keyword><keyword>sheets</keyword><keyword>oxide</keyword></keywords><dates><year>2011</year><pub-dates><date>Nov22</date></pub-dates></dates><isbn>1098-0121</isbn><accession-num>WOS:000297295600004</accession-num><urls><related-urls><url><GotoISI>://WOS:000297295600004</url></related-urls></urls><language>English</language></record></Cite></EndNote>[\o"Cranford,2011#705"17]。如何既利用石墨烯優(yōu)異的性能又突破石墨烯的理論比容量是石墨烯基電極材料的應用難題。通過對石墨烯進行官能團修飾改性以及制備石墨烯基復合電極材料，構建法拉第準電容器已經(jīng)成為該領域研究熱點之一。2.1官能團修飾石墨烯基電極Khanra等ADDINEN.CITE<EndNote><Cite><Author>Khanra</Author><Year>2012</Year><RecNum>706</RecNum><DisplayText><styleface="superscript"font="TimesNewRoman">[18]</style></DisplayText><record><rec-number>706</rec-number><foreign-keys><keyapp="EN"db-id="z59ttr5dqa95sje22eop0reb9xff09axvrsf">706</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Khanra,P.</author><author>Kuila,T.</author><author>Bae,S.H.</author><author>Kim,N.H.</author><author>Lee,J.H.</author></authors></contributors><auth-address>Lee,JH ChonbukNatlUniv,DeptBINFusTechnol,WCUProgramme,Jeonju561756,Jeonbuk,SouthKorea ChonbukNatlUniv,DeptBINFusTechnol,WCUProgramme,Jeonju561756,Jeonbuk,SouthKorea ChonbukNatlUniv,DeptHydrogen&FuelCellEngn,Jeonju561756,Jeonbuk,SouthKorea</auth-address><titles><title>Electrochemicallyexfoliatedgrapheneusing9-anthracenecarboxylicacidforsupercapacitorapplication</title><secondary-title>JournalOfMaterialsChemistry</secondary-title><alt-title>JMaterChem JMaterChem</alt-title></titles><periodical><full-title>JournalofMaterialsChemistry</full-title></periodical><pages>24403-24410</pages><volume>22</volume><number>46</number><keywords><keyword>carbonnanotube</keyword><keyword>greenapproach</keyword><keyword>oxide</keyword><keyword>electrodes</keyword><keyword>transparent</keyword><keyword>capacitors</keyword><keyword>graphite</keyword><keyword>films</keyword><keyword>nanoparticles</keyword><keyword>polyaniline</keyword></keywords><dates><year>2012</year><pub-dates><date>Dec14</date></pub-dates></dates><isbn>0959-9428</isbn><accession-num>WOS:0003