石墨烯在超級電容器中的應(yīng)用研究國內(nèi)外文獻(xiàn)綜述目錄TOC\o"1-3"\h\u32438石墨烯在超級電容器中的應(yīng)用研究國內(nèi)外文獻(xiàn)綜述 179081.1石墨烯的特點及制備方法 136091.2石墨烯及其復(fù)合材料在超級電容器電極中的應(yīng)用 21.1石墨烯的特點及制備方法石墨烯是由單層sp2雜化的碳原子構(gòu)成的蜂巢狀晶體材料，其厚度極小——相當(dāng)于頭發(fā)直徑的1/200000，是其他維數(shù)碳材料的基本單元ADDINEN.CITE<EndNote><Cite><Author>Geim</Author><Year>2007</Year><RecNum>95</RecNum><DisplayText><styleface="superscript">[44]</style></DisplayText><record><rec-number>95</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618750090">95</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Geim,A.K.</author><author>Novoselov,K.S.</author></authors></contributors><titles><title>Theriseofgraphene</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>183-191</pages><volume>6</volume><number>3</number><dates><year>2007</year><pub-dates><date>Mar</date></pub-dates></dates><isbn>1476-1122</isbn><accession-num>WOS:000244570700015</accession-num><urls><related-urls><url><GotoISI>://WOS:000244570700015</url></related-urls></urls><electronic-resource-num>10.1038/nmat1849</electronic-resource-num></record></Cite></EndNote>[44]，其示意圖如圖1-7所示。石墨烯的硬度最強(qiáng)，同時有著令人滿意的物理及化學(xué)性能，比如其理論比表面積極大（2630m2g-1），電導(dǎo)率為1×108S/cm，楊氏模量約為1.1TPa等等ADDINEN.CITE<EndNote><Cite><Author>Bolotin</Author><Year>2008</Year><RecNum>96</RecNum><DisplayText><styleface="superscript">[45]</style></DisplayText><record><rec-number>96</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618751567">96</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bolotin,K.I.</author><author>Sikes,K.J.</author><author>Jiang,Z.</author><author>Klima,M.</author><author>Fudenberg,G.</author><author>Hone,J.</author><author>Kim,P.</author><author>Stormer,H.L.</author></authors></contributors><titles><title>Ultrahighelectronmobilityinsuspendedgraphene</title><secondary-title>SolidStateCommunications</secondary-title></titles><periodical><full-title>SolidStateCommunications</full-title><abbr-1>SolidStateCommun.</abbr-1><abbr-2>SolidStateCommun.</abbr-2></periodical><pages>351-355</pages><volume>146</volume><number>9-10</number><dates><year>2008</year><pub-dates><date>Jun</date></pub-dates></dates><isbn>0038-1098</isbn><accession-num>WOS:000256641500001</accession-num><urls><related-urls><url><GotoISI>://WOS:000256641500001</url></related-urls></urls><electronic-resource-num>10.1016/j.ssc.2008.02.024</electronic-resource-num></record></Cite></EndNote>[45]。對于石墨烯的理論研究已經(jīng)持續(xù)多年，自2004年Novoselov等人ADDINEN.CITE<EndNote><Cite><Author>Novoselov</Author><Year>2004</Year><RecNum>97</RecNum><DisplayText><styleface="superscript">[46]</style></DisplayText><record><rec-number>97</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618807737">97</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Novoselov,K.S.</author><author>Geim,A.K.</author><author>Morozov,S.V.</author><author>Jiang,D.</author><author>Zhang,Y.</author><author>Dubonos,S.V.</author><author>Grigorieva,I.V.</author><author>Firsov,A.A.</author></authors></contributors><titles><title>Electricfieldeffectinatomicallythincarbonfilms</title><secondary-title>Science</secondary-title></titles><periodical><full-title>Science</full-title></periodical><pages>666-669</pages><volume>306</volume><number>5696</number><dates><year>2004</year><pub-dates><date>Oct22</date></pub-dates></dates><isbn>0036-8075</isbn><accession-num>WOS:000224756700045</accession-num><urls><related-urls><url><GotoISI>://WOS:000224756700045</url></related-urls></urls><electronic-resource-num>10.1126/science.1102896</electronic-resource-num></record></Cite></EndNote>[46]通過剝離高定向石墨獲得了獨立的單層石墨烯后，科學(xué)家對其進(jìn)行了多方研究，在制備方法上掀起了研究熱潮。在本章中詳細(xì)介紹以下幾種文獻(xiàn)報道的典型制備方法：物理剝離法、SiC晶體外延生長法、CVD法、氧化石墨還原法等。圖1-7石墨烯及其構(gòu)建的不同維度碳材料的示意圖ADDINEN.CITE<EndNote><Cite><Author>Geim</Author><Year>2007</Year><RecNum>95</RecNum><DisplayText><styleface="superscript">[44]</style></DisplayText><record><rec-number>95</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618750090">95</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Geim,A.K.</author><author>Novoselov,K.S.</author></authors></contributors><titles><title>Theriseofgraphene</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>183-191</pages><volume>6</volume><number>3</number><dates><year>2007</year><pub-dates><date>Mar</date></pub-dates></dates><isbn>1476-1122</isbn><accession-num>WOS:000244570700015</accession-num><urls><related-urls><url><GotoISI>://WOS:000244570700015</url></related-urls></urls><electronic-resource-num>10.1038/nmat1849</electronic-resource-num></record></Cite></EndNote>[44]。（一）物理剝離法2004年Novoselov等人ADDINEN.CITE<EndNote><Cite><Author>Novoselov</Author><Year>2004</Year><RecNum>97</RecNum><DisplayText><styleface="superscript">[46]</style></DisplayText><record><rec-number>97</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618807737">97</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Novoselov,K.S.</author><author>Geim,A.K.</author><author>Morozov,S.V.</author><author>Jiang,D.</author><author>Zhang,Y.</author><author>Dubonos,S.V.</author><author>Grigorieva,I.V.</author><author>Firsov,A.A.</author></authors></contributors><titles><title>Electricfieldeffectinatomicallythincarbonfilms</title><secondary-title>Science</secondary-title></titles><periodical><full-title>Science</full-title></periodical><pages>666-669</pages><volume>306</volume><number>5696</number><dates><year>2004</year><pub-dates><date>Oct22</date></pub-dates></dates><isbn>0036-8075</isbn><accession-num>WOS:000224756700045</accession-num><urls><related-urls><url><GotoISI>://WOS:000224756700045</url></related-urls></urls><electronic-resource-num>10.1126/science.1102896</electronic-resource-num></record></Cite></EndNote>[46]通過生活中常見的膠帶沾剝出graphene。具體方法為：將1mm厚的高定向熱解石墨片進(jìn)行干燥，在氧等離子體中刻蝕出5μm的平臺（面積為20μm2–2mm2）后，壓在被感光抗蝕膜附著的玻璃基底上，烘焙，隨后通過膠帶反復(fù)沾剝。隨后將基底浸泡在丙酮中，殘留的石墨片會分散于丙酮中，將硅晶片放入，經(jīng)過去離子水和乙醇的清洗后超聲得到石墨烯。該方法雖然簡便，但卻比較耗費時間，并且所得石墨烯的質(zhì)量無法精確控制。（二）SiC晶體外延生長法這種制備方法首先要將SiC表面用H2刻蝕或者氧化，然后用電子束轟擊加熱到1000℃，用以除去SiC表面的含氧官能團(tuán)。然后加熱至1250–1450℃，加熱時間為1–20min。在這種高溫條件下，Si原子揮發(fā)后，C原子排列成環(huán)便可以得到石墨烯，通過改變反應(yīng)溫度可以控制石墨烯的厚度。相較于物理剝離法，這種制備方法所得石墨烯的質(zhì)量有所保證，不過該方法反應(yīng)溫度高、能耗大，不適用于大規(guī)模工廠生產(chǎn)ADDINEN.CITE<EndNote><Cite><Author>Sutter</Author><Year>2008</Year><RecNum>98</RecNum><DisplayText><styleface="superscript">[47]</style></DisplayText><record><rec-number>98</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618813421">98</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sutter,PeterW.</author><author>Flege,Jan-Ingo</author><author>Sutter,EliA.</author></authors></contributors><titles><title>Epitaxialgrapheneonruthenium</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>406-411</pages><volume>7</volume><number>5</number><dates><year>2008</year><pub-dates><date>May</date></pub-dates></dates><isbn>1476-1122</isbn><accession-num>WOS:000255257600023</accession-num><urls><related-urls><url><GotoISI>://WOS:000255257600023</url></related-urls></urls><electronic-resource-num>10.1038/nmat2166</electronic-resource-num></record></Cite></EndNote>[47]。（三）化學(xué)氣相沉積法CVD法是如今工業(yè)化合成高質(zhì)量graphene的首選方案ADDINEN.CITE<EndNote><Cite><Author>deHeer</Author><Year>2007</Year><RecNum>99</RecNum><DisplayText><styleface="superscript">[48]</style></DisplayText><record><rec-number>99</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618813805">99</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>deHeer,WaltA.</author><author>Berger,Claire</author><author>Wu,Xiaosong</author><author>First,PhillipN.</author><author>Conrad,EdwardH.</author><author>Li,Xuebin</author><author>Li,Tianbo</author><author>Sprinkle,Michael</author><author>Hass,Joanna</author><author>Sadowski,MarcinL.</author><author>Potemski,Marek</author><author>Martinez,Gerard</author></authors></contributors><titles><title>Epitaxialgraphene</title><secondary-title>SolidStateCommunications</secondary-title></titles><periodical><full-title>SolidStateCommunications</full-title><abbr-1>SolidStateCommun.</abbr-1><abbr-2>SolidStateCommun.</abbr-2></periodical><pages>92-100</pages><volume>143</volume><number>1-2</number><dates><year>2007</year><pub-dates><date>Jul</date></pub-dates></dates><isbn>0038-1098</isbn><accession-num>WOS:000247947100015</accession-num><urls><related-urls><url><GotoISI>://WOS:000247947100015</url></related-urls></urls><electronic-resource-num>10.1016/j.ssc.2007.04.023</electronic-resource-num></record></Cite></EndNote>[48]。該方法以Cu、Ni等作為沉積底物，碳源常選擇甲烷、乙炔，在高溫下碳源會沉積在在基底表面，反應(yīng)結(jié)束后除去基底即可獲得高質(zhì)量的graphene。這種方法所制備的石墨烯具有完整的結(jié)構(gòu)、較高的質(zhì)量。然而這種方法所使用的設(shè)備昂貴，所使用的過渡金屬基底也會造成不可避免的浪費，因此在實驗室中采取這種方法制備graphene還有待商榷。（四）氧化石墨還原法氧化石墨還原法是文獻(xiàn)報道中應(yīng)用最多的方法，該方法的優(yōu)勢在于實驗條件簡單、成本低廉、產(chǎn)量效率高ADDINEN.CITE<EndNote><Cite><Author>Park</Author><Year>2008</Year><RecNum>100</RecNum><DisplayText><styleface="superscript">[49]</style></DisplayText><record><rec-number>100</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618817150">100</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Park,Sungjin</author><author>Lee,Kyoung-Seok</author><author>Bozoklu,Gulay</author><author>Cai,Weiwei</author><author>Nguyen,SonBinhT.</author><author>Ruoff,RodneyS.</author></authors></contributors><titles><title>Grapheneoxidepapersmodifiedbydivalentions-Enhancingmechanicalpropertiesviachemicalcross-linking</title><secondary-title>AcsNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>572-578</pages><volume>2</volume><number>3</number><dates><year>2008</year><pub-dates><date>Mar</date></pub-dates></dates><isbn>1936-0851</isbn><accession-num>WOS:000254408000027</accession-num><urls><related-urls><url><GotoISI>://WOS:000254408000027</url></related-urls></urls><electronic-resource-num>10.1021/nn700349a</electronic-resource-num></record></Cite></EndNote>[49]。在科學(xué)研究中常用改進(jìn)的Hummers法制備石墨烯ADDINEN.CITE<EndNote><Cite><Author>Sui</Author><Year>2013</Year><RecNum>32</RecNum><DisplayText><styleface="superscript">[50]</style></DisplayText><record><rec-number>32</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092257">32</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sui,Z.Y.</author><author>Cui,Y.</author><author>Zhu,J.H.</author><author>Han,B.H.</author></authors></contributors><auth-address>NationalCenterforNanoscienceandTechnology,Beijing100190,China.</auth-address><titles><title>Preparationofthree-dimensionalgrapheneoxide-polyethylenimineporousmaterialsasdyeandgasadsorbents</title><secondary-title>ACSAppliedEnergyMaterials</secondary-title></titles><periodical><full-title>ACSAppliedEnergyMaterials</full-title><abbr-1>ACSAppl.EnergyMater.</abbr-1><abbr-2>ACSAppl.EnergyMater.</abbr-2></periodical><pages>9172-9</pages><volume>5</volume><number>18</number><keywords><keyword>Adsorption</keyword><keyword>CarbonDioxide/*chemistry</keyword><keyword>ColoringAgents/*chemistry</keyword><keyword>Gases/*chemistry</keyword><keyword>Graphite/*chemistry</keyword><keyword>Kinetics</keyword><keyword>Oxides/chemistry</keyword><keyword>Polyethyleneimine/*chemistry</keyword><keyword>Porosity</keyword><keyword>SurfaceProperties</keyword><keyword>Temperature</keyword></keywords><dates><year>2013</year><pub-dates><date>Sep25</date></pub-dates></dates><isbn>1944-8252(Electronic) 1944-8244(Linking)</isbn><accession-num>23977948</accession-num><urls><related-urls><url>/pubmed/23977948</url></related-urls></urls><electronic-resource-num>10.1021/am402661t</electronic-resource-num></record></Cite></EndNote>[50]：將70mLH2SO4（98wt.%）、3g石墨粉依次倒入燒瓶中，充分溶解后轉(zhuǎn)移到冰水浴中。在攪拌的過程中加入KMnO4（少量多次，1.5h內(nèi)加完即可），過程中溫度需控制在20℃以下。隨后將冰塊取出，溫度升至35℃后攪拌大約1h，可以看到反應(yīng)物呈稠膏狀（棕褐色），之后緩慢加入140mL去離子水，保持10min，待到溶液顏色不發(fā)生變化時加入500mL蒸餾水進(jìn)行稀釋，再加入20mLH2O2（30wt.%）去除未反應(yīng)的KMnO4，此時溶液為明黃色。最后用HCl溶液（3wt.%）和去離子水進(jìn)行數(shù)次離心洗滌，經(jīng)過真空冷凍干燥之后得到氧化石墨烯（GO）。為了避免混淆，需在此說明：本文中通過GO還原得到的還原氧化石墨烯（rGO），也稱其為石墨烯。1.2石墨烯及其復(fù)合材料在超級電容器電極中的應(yīng)用1.2.1石墨烯電極材料與AC和CNTs的儲能機(jī)理相似，石墨烯同樣是很好的EDLC電極材料。在上一節(jié)的介紹中，我們知道EDLC比電容值的提高依賴于超級電容器的厚度以及電極材料的比表面積。而超級電容器的厚度減小相對困難，而選擇比表面積大的電極材料則為最佳選擇。石墨烯的理論比表面積大、電導(dǎo)率高，并且通過氧化還原法制備的GO以及rGO上的含氧官能團(tuán)具有較強(qiáng)的親水性，因此其超級電容器性能要遠(yuǎn)遠(yuǎn)優(yōu)于其他碳材料ADDINEN.CITE<EndNote><Cite><Author>Sun</Author><Year>2011</Year><RecNum>101</RecNum><DisplayText><styleface="superscript">[51]</style></DisplayText><record><rec-number>101</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618832533">101</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Yiqing</author><author>Wu,Qiong</author><author>Shi,Gaoquan</author></authors></contributors><titles><title>Graphenebasednewenergymaterials</title><secondary-title>Energy&EnvironmentalScience</secondary-title></titles><periodical><full-title>Energy&EnvironmentalScience</full-title><abbr-1>EnergyEnviron.Sci.</abbr-1><abbr-2>EnergyEnviron.Sci.</abbr-2></periodical><pages>1113-1132</pages><volume>4</volume><number>4</number><dates><year>2011</year><pub-dates><date>Apr</date></pub-dates></dates><isbn>1754-5692</isbn><accession-num>WOS:000289001400003</accession-num><urls><related-urls><url><GotoISI>://WOS:000289001400003</url></related-urls></urls><electronic-resource-num>10.1039/c0ee00683a</electronic-resource-num></record></Cite></EndNote>[51]。為了充分提高石墨烯電極材料的比表面積，許多科研工作聚焦于制備三維石墨烯水凝膠應(yīng)用于超級電容器。Xu等人ADDINEN.CITE<EndNote><Cite><Author>Xu</Author><Year>2010</Year><RecNum>102</RecNum><DisplayText><styleface="superscript">[52]</style></DisplayText><record><rec-number>102</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618834606">102</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xu,Yuxi</author><author>Sheng,Kaixuan</author><author>Li,Chun</author><author>Shi,Gaoquan</author></authors></contributors><titles><title>Self-AssembledGrapheneHydrogelviaaOne-StepHydrothermalProcess</title><secondary-title>AcsNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>4324-4330</pages><volume>4</volume><number>7</number><dates><year>2010</year><pub-dates><date>Jul</date></pub-dates></dates><isbn>1936-0851</isbn><accession-num>WOS:000280364800094</accession-num><urls><related-urls><url><GotoISI>://WOS:000280364800094</url></related-urls></urls><electronic-resource-num>10.1021/nn101187z</electronic-resource-num></record></Cite></EndNote>[52]采用一步水熱還原獲得自組裝石墨烯水凝膠（SGH），所得SGH的機(jī)械強(qiáng)度約125GPa，楊氏模量約1.1TPa，并表現(xiàn)出較高的比電容，所制備的水凝膠實物照片以及SEM圖如圖1-8所示。圖1-8一步水熱法制備的自組裝石墨烯水凝膠的(a-b)實物照片和(c)SEM圖像ADDINEN.CITE<EndNote><Cite><Author>Xu</Author><Year>2010</Year><RecNum>102</RecNum><DisplayText><styleface="superscript">[52]</style></DisplayText><record><rec-number>102</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618834606">102</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xu,Yuxi</author><author>Sheng,Kaixuan</author><author>Li,Chun</author><author>Shi,Gaoquan</author></authors></contributors><titles><title>Self-AssembledGrapheneHydrogelviaaOne-StepHydrothermalProcess</title><secondary-title>AcsNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>4324-4330</pages><volume>4</volume><number>7</number><dates><year>2010</year><pub-dates><date>Jul</date></pub-dates></dates><isbn>1936-0851</isbn><accession-num>WOS:000280364800094</accession-num><urls><related-urls><url><GotoISI>://WOS:000280364800094</url></related-urls></urls><electronic-resource-num>10.1021/nn101187z</electronic-resource-num></record></Cite></EndNote>[52]。在超級電容器電極的制備中，通常不會用到一整塊水凝膠，僅僅裁剪一小片?？紤]到超級電容器中的活性材料為平面層、制備的水凝膠內(nèi)部可能會不均勻等因素，因此直接制備石墨烯水凝膠膜也不失為一種較好的方法。Liu等人ADDINEN.CITE<EndNote><Cite><Author>Liu</Author><Year>2018</Year><RecNum>41</RecNum><DisplayText><styleface="superscript">[53]</style></DisplayText><record><rec-number>41</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092258">41</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liu,Daoqing</author><author>Li,Qianwei</author><author>Zhao,Huazhang</author></authors></contributors><titles><title>Electrolyte-assistedhydrothermalsynthesisofholeygraphenefilmsforall-solid-statesupercapacitors</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>11471-11478</pages><volume>6</volume><number>24</number><dates><year>2018</year></dates><isbn>2050-7488 2050-7496</isbn><urls></urls><electronic-resource-num>10.1039/c8ta02580k</electronic-resource-num></record></Cite></EndNote>[53]通過電解質(zhì)輔助的水熱法合成了rGO水凝膠膜。在經(jīng)過水熱處理后，還原多孔石墨烯薄膜(rHGFs)保持了其柔韌性、完整性和孔隙率，在三電極體系中比電容達(dá)到260Fg-1。其制備流程、實物圖像如圖1-9所示。圖1-9電解質(zhì)輔助水熱法制備的rGO水凝膠膜(a)制備流程示意圖和(b-d)實物照片ADDINEN.CITE<EndNote><Cite><Author>Liu</Author><Year>2018</Year><RecNum>41</RecNum><DisplayText><styleface="superscript">[53]</style></DisplayText><record><rec-number>41</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092258">41</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liu,Daoqing</author><author>Li,Qianwei</author><author>Zhao,Huazhang</author></authors></contributors><titles><title>Electrolyte-assistedhydrothermalsynthesisofholeygraphenefilmsforall-solid-statesupercapacitors</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>11471-11478</pages><volume>6</volume><number>24</number><dates><year>2018</year></dates><isbn>2050-7488 2050-7496</isbn><urls></urls><electronic-resource-num>10.1039/c8ta02580k</electronic-resource-num></record></Cite></EndNote>[53]。然而，純石墨烯基EDLCs由于石墨烯片層的不可逆團(tuán)聚以及其雙電層電荷儲存的內(nèi)在限制，所制備器件的容量和能量密度相對較低ADDINEN.CITE<EndNote><Cite><Author>Jiang</Author><Year>2013</Year><RecNum>7</RecNum><DisplayText><styleface="superscript">[54]</style></DisplayText><record><rec-number>7</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092257">7</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jiang,Hao</author><author>Lee,PooiSee</author><author>Li,Chunzhong</author></authors></contributors><titles><title>3Dcarbonbasednanostructuresforadvancedsupercapacitors</title><secondary-title>Energy&EnvironmentalScience</secondary-title></titles><periodical><full-title>Energy&EnvironmentalScience</full-title><abbr-1>EnergyEnviron.Sci.</abbr-1><abbr-2>EnergyEnviron.Sci.</abbr-2></periodical><pages>41-53</pages><volume>6</volume><number>1</number><dates><year>2013</year><pub-dates><date>Jan</date></pub-dates></dates><isbn>1754-5692</isbn><accession-num>WOS:000312337700004</accession-num><urls><related-urls><url><styleface="underline"font="default"size="100%"><GotoISI>://WOS:000312337700004</style></url></related-urls></urls><electronic-resource-num>10.1039/c2ee23284g</electronic-resource-num></record></Cite></EndNote>[54]，故而更多的科研工作還是研究石墨烯基復(fù)合材料。1.2.2石墨烯/過渡金屬氧化物復(fù)合電極材料考慮到石墨烯超級電容器的一些不足，研究人員通過復(fù)合贗電容材料提高其性能，過渡金屬氧化物就走進(jìn)了人們的視野中。由于石墨烯片層的不可逆團(tuán)聚阻礙了電解質(zhì)離子的傳輸，而過渡金屬氧化物的納米粒子能夠嵌入graphene片層內(nèi)部，以達(dá)到防止graphene聚集的目的。同時，二者的復(fù)合電極通常比單一材料電極的比電容值高ADDINEN.CITE<EndNote><Cite><Author>Su</Author><Year>2012</Year><RecNum>103</RecNum><DisplayText><styleface="superscript">[55]</style></DisplayText><record><rec-number>103</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618895397">103</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Su,Y.Z.</author><author>Li,S.</author><author>Wu,D.Q.</author><author>Zhang,F.</author><author>Liang,H.W.</author><author>Gao,P.F.</author><author>Cheng,C.</author><author>Feng,X.L.</author></authors></contributors><titles><title>Two-DimensionalCarbon-CoatedGraphene/MetalOxideHybridsforEnhancedLithiumStorage</title><secondary-title>AcsNano</secondary-title></titles><periodical><full-title>ACSNano</full-title></periodical><pages>8349-8356</pages><volume>6</volume><number>9</number><dates><year>2012</year><pub-dates><date>Sep</date></pub-dates></dates><isbn>1936-0851</isbn><accession-num>WOS:000309040600089</accession-num><urls><related-urls><url><GotoISI>://WOS:000309040600089</url></related-urls></urls><electronic-resource-num>10.1021/nn303091t</electronic-resource-num></record></Cite></EndNote>[55]，MnO2因其出色的特點備受關(guān)注。比如，Zhang等人ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2016</Year><RecNum>104</RecNum><DisplayText><styleface="superscript">[56]</style></DisplayText><record><rec-number>104</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618896529">104</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Ningshuang</author><author>Fu,Chaopeng</author><author>Liu,Dan</author><author>Li,Yanling</author><author>Zhou,Haihui</author><author>Kuang,Yafei</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">Three-DimensionalPompon-likeMnO</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">/GrapheneHydrogelCompositeforSupercapacitor</style></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>804-811</pages><volume>210</volume><dates><year>2016</year><pub-dates><date>Aug20</date></pub-dates></dates><isbn>0013-4686</isbn><accession-num>WOS:000380746100095</accession-num><urls><related-urls><url><GotoISI>://WOS:000380746100095</url></related-urls></urls><electronic-resource-num>10.1016/j.electacta.2016.06.004</electronic-resource-num></record></Cite></EndNote>[56]通過水熱法制備了不同比例的rGO/MnO2水凝膠，隨后制備成不同的超級電容器電極，其制備流程如圖1-10所示。兩者出色的協(xié)同作用使得電極的比電容值最大可達(dá)426.5Fg-1，高于石墨烯水凝膠電極（153.5Fg-1）和純MnO2電極（71.4Fg-1）?？梢园l(fā)現(xiàn)，兩者復(fù)合之后呈現(xiàn)“1+1>2”的效果，電容性能有了明顯提高?，F(xiàn)在越來越多的科研工作探索石墨烯/過渡金屬氧化物的新型復(fù)合材料。圖1-10rGO/MnO2水凝膠的制備流程示意圖及相應(yīng)的實物照片ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2016</Year><RecNum>104</RecNum><DisplayText><styleface="superscript">[56]</style></DisplayText><record><rec-number>104</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618896529">104</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Ningshuang</author><author>Fu,Chaopeng</author><author>Liu,Dan</author><author>Li,Yanling</author><author>Zhou,Haihui</author><author>Kuang,Yafei</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">Three-DimensionalPompon-likeMnO</style><styleface="subscript"font="default"size="100%">2</style><styleface="normal"font="default"size="100%">/GrapheneHydrogelCompositeforSupercapacitor</style></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>804-811</pages><volume>210</volume><dates><year>2016</year><pub-dates><date>Aug20</date></pub-dates></dates><isbn>0013-4686</isbn><accession-num>WOS:000380746100095</accession-num><urls><related-urls><url><GotoISI>://WOS:000380746100095</url></related-urls></urls><electronic-resource-num>10.1016/j.electacta.2016.06.004</electronic-resource-num></record></Cite></EndNote>[56]。1.2.3石墨烯/導(dǎo)電聚合物復(fù)合電極材料導(dǎo)電聚合物具有較大的電容，常常和石墨烯等雙電層電容材料進(jìn)行復(fù)合應(yīng)用在超級電容器中。石墨烯/聚苯胺復(fù)合材料逐漸走入人們的視野，頻頻出現(xiàn)在文獻(xiàn)報道中。例如，Wu等人ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2010</Year><RecNum>66</RecNum><DisplayText><styleface="superscript">[8]</style></DisplayText><record><rec-number>66</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1618576242">66</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Kai</author><author>Zhang,LiLi</author><author>Zhao,X.S.</author><author>Wu,Jishan</author></authors></contributors><titles><title>Graphene/PolyanilineNanofiberCompositesasSupercapacitorElectrodes</title><secondary-title>ChemistryofMaterials</secondary-title></titles><periodical><full-title>ChemistryofMaterials</full-title><abbr-1>Chem.Mater.</abbr-1><abbr-2>Chem.Mater.</abbr-2></periodical><pages>1392-1401</pages><volume>22</volume><number>4</number><dates><year>2010</year><pub-dates><date>Feb23</date></pub-dates></dates><isbn>0897-4756</isbn><accession-num>WOS:000274531300018</accession-num><urls><related-urls><url><GotoISI>://WOS:000274531300018</url></related-urls></urls><electronic-resource-num>10.1021/cm902876u</electronic-resource-num></record></Cite></EndNote>[8]以原位聚合的方式合成了GO/PANI納米纖維復(fù)合材料，隨后經(jīng)過肼還原成rGO/PANI。所制備的PANI纖維均勻的散布在rGO片層上或者內(nèi)部結(jié)構(gòu)中，從而阻止了石墨烯片層的聚集。不過通過原位聚合的路徑所合成的的材料多為粉末狀，需要用乙醇或者去離子水溶解、攪拌，然后滴涂在集流體上，這種制備電極的方式較為繁瑣，組裝超級電容器電極需要加入粘合劑，而且在滴涂的過程中也不可避免的會有額外損失。而將rGO/PANI直接做成膜材料則可以簡化制備、減少損失。Yu等人ADDINEN.CITE<EndNote><Cite><Author>Yu</Author><Year>2014</Year><RecNum>20</RecNum><DisplayText><styleface="superscript">[57]</style></DisplayText><record><rec-number>20</rec-number><foreign-keys><keyapp="EN"db-id="v0wx5ad0gffvrxee02ppspvetfaa9tsdtazt"timestamp="1617092257">20</key></foreign-keys><ref-typename="JournalArticle">17<