沥青基炭材料:结构设计、制...法及其在储能中应用(英文)_刘慧超.pdf
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1、Cite this:NewCarbonMaterials,2023,38(3):459-477DOI:10.1016/S1872-5805(23)60743-7Pitch-based carbon materials:a review of their structural design,preparation and applications in energy storageLIUHui-chao,ZHUSheng*,CHANGYun-zhen,HOUWen-jing,HANGao-yi*(Institute of Molecular Science,Key Laboratory of M
2、aterials for Energy Conversion and Storage of Shanxi Province,Key Laboratory of Chemical Biologyand Molecular Engineering of Education Ministry,Shanxi University,Taiyuan 030006,China)Abstract:Becauseofitshighcarboncontentandeasygraphitization,pitchisapromisingprecursorforcarbonmaterials.Topro-duceca
3、rbonmaterialswiththedesiredperformance,itisnecessarytoovercometheinherentshortcomingsofpitch.Forexample,itscomplexcompositionandeasymeltingmakeitdifficulttocontrolthestructureoftheresultingcarbonmaterials.Recently,research-ershaveproposedseveralmethodstocontrolthestructureofcarbonmaterialsproducedfr
4、ompitchforenergystorageapplications.Thelatestadvancesinthestructuraldesignandpreparationofpitch-basedcarbonmaterialsforuseinenergystoragedevicessuchassupercapacitorsandalkalimetalionbatteriesarereviewed.Key words:Pitch;Carbonmaterials;Preparation;Structuraldesign;Energystorage1IntroductionThispaper
5、reviews the recent research pro-gressesofpitch-basedcarbonmaterialsasshowninFig.1.Inordertoobtainthecarbonmaterialswithcontrollablestructure,variouspreparationmethodsarefirstlyintroduced,suchassolventpartition,templateandpre-oxidationstrategies.Thematerialcharacterist-icsandstructureregulationmechan
6、ismofthesemeth-odsarealsothoroughlyanalyzed.Then,thepotentialapplicationsofpitch-basedporouscarboninenergystorage applications including supercapacitors(SCs)andalkalimetalionbatteriesaresummarized.Finally,theremainingchallengesandresearchprospectsinthefieldarediscussed.Withthe large-scale consumptio
7、n of fossil en-ergy,ithasbecometheresearchfocustosaveenergyanddeveloprenewableenergywhilerealizingthera-tionalandeffectiveutilizationoflimitedresources12.Inthedevelopmentandutilizationofrenewableen-ergy,carbonmaterialsplayacrucialrolebecausetheycanbewidelyusedaselectrodematerialsorimport-antcomponen
8、ts in energy storage systems.In prin-ciple,carbonmaterialscanbepreparedfromvariouscarbon-containingsources.Generally,peopletendtochooselow-cost precursors such as biomass,poly-mersandpitchtoproducevariouscarbonmaterials.Chinaisrichincoalresourcesandthecokingca-pacityranksfirstintheworld,theyieldofco
9、altarpitch(CTP)fromcokingindustryisabout50%-60%.Nowadays,the pitch is mainly used in traditionalfieldssuchasrefractory,adhesive,anti-corrosion,wa-terproofandroadbuildingmaterialsduetoitsgoodcorrosion resistance and cohesiveness36.However,theabove-mentionedtraditionalapplicationscanonlytransformpitch
10、intolowaddedvalueproducts.There-fore,newapplicationsareurgentlyneededtoexploreanddeveloptoconvertpitchintoproductswithhighvalue.Notably,pitchhasmeritsofhighcarboncon-tent,abundanceandinexpensiveprice,whichiscon-sideredaspromisingcandidatetoproducecarbonma-terials.Currently,preparationofcarbonmateria
11、lforenergy storage has become an important route fordeeputilizationofasphaltbecausepitchiseasytobegraphitized compared with biomass and syntheticpolymer79.Uptodate,avarietyofcarbonmaterialsincludingcarbonnanospheres,nanowires,nanosheetsand networks have been prepared from pitch1012.Theyhavebeenwidel
12、yevaluatedtouseaselectrodematerialforsupercapacitor(SCs),lithiumion,sodi-Received date:2023-02-10;Revised date:2023-05-11Corresponding author:ZHUSheng,Lecturer.E-mail:;HANGao-yi,Professor.E-mail:han_Author introduction:LIUHui-chao.E-mail:第38卷第3期新型炭材料(中英文)Vol.38No.32023年6月NEWCARBONMATERIALSJun.2023um
13、ionandpotassiumionbatteries1315.Pitchcanbedividedintopetroleumasphaltandcoaltarasphaltduetodifferentsourcesandprocessesof production.Generally,CTP contains polycyclicaromatic hydrocarbons,while the large polycyclicaromatichydrocarbonsareprovedtobeeasilyconver-tedintothegraphitestructure1618.However,
14、thepitchpossesses complex chemical compositions,whichhaveanegativeimpactonregulatingthestructureandcomposition of the final carbon products.In the1970s,researchersusedorganicsolventstosegmentthecomplexpitchcomponentsbasedontheprincipleofsimilarsolubilityintosolublesubstancesindiffer-ent solvents by
15、using the organic solvents ofquinoline,toluene,petroleum ether,n-hexanol,car-bondisulfideandsoon.Then,thesubstancewithsim-ilarcomponentandstructureissubsequentlystudied1921.The other feature for pitch is thermo-plastic,that is,when the temperature reaches thesofteningpointofpitch,thepitchwillchangef
16、romsolidtoliquid.Duetotheexistenceoftheabove-men-tioned characteristics,it is difficult to control thestructureofthefinalcarbonmaterialduringthecon-versionprocessofpitch.Therefore,templatessuchasmagnesiumoxide,calciumoxide,silicondioxideandmoltensalts,areintroducedintothesystemtoregu-latetheporestru
17、ctureandmorphologyofpitch-basedcarbon materials2224.In addition to the templatemethod,oxidationstrategyhasalsobeendevelopedtopreparepitch-based porous carbon.During the pro-cess,functionalgroupswillbeintroducedintothemo-leculesofpitchtoincreasetheirreactionactivity.Sub-sequently,themoleculesreactwit
18、heachothertoformmacromolecules with similar structure to graphite,thusthestructuralstabilityoftheintermediateproducthas been enhanced as the phase change is avoidedduringpyrolysisprocess2527.Sincethatthemorpho-logyofcarbonmaterialscanbewellcontrolled,thepitch-oxidation method has become an important
19、strategytopreparecarbonmaterials.Electrochemical energy storage performance ofcarbon materials is strongly depended on the porestructure,surfacepropertyandspecificsurfacearea.Poreengineeringandheteroatomdopingareeffectivestrategiesto improve the electrochemical perform-anceofcarbonmaterials2829.Fort
20、heporeengineer-ing,itisessentialtocontroltheporestructuresinclud-ingporevolume,diameteranditsdistribution.Gener-ally,therearemicropores,mesoporesandmacroporesexistinthecarbonmaterialsforenergystorage.Themicroporesplayamajorroleinthespecificsurfaceareaofcarbonmaterialsandcanproviderichactivesitesfore
21、lectrolyteionadsorption,whereasthemicro-porespreventrapiddiffusionofelectrolyteions.Com-paratively,mesopores can supply high-speed chan-nels for ion transmission and diffusion.Macroporeswith larger size can be used as the storage tank ofelectrolyte ions to shorten the diffusion distance ofelectrolyt
22、eions,whereastheymakelesscontributiontothespecificsurfaceareaofcarbonmaterials3031.Uptodate,thehierarchicalporouscarbonmaterialswith micropores,mesopores and macropores havebeensynthesizedbythetemplate,activationmethod,solventpartitionandpre-oxidationmethods.Inaddi-tiontoporeengineering,introduction
23、ofheteroatoms(e.g.,oxygen,nitrogen,sulfur,phosphorusandboron,etc.)intocarbonmaterialscannotonlyimprovethehydrophilicitytopromotethechargetransferontheelectrode/electrolyte interface,but also increase thePitchSupercapacitorsPotassium-ion batteriesLithium-ion batteriesSodium-ion batteriesChemical oxid
24、ationHard templateSoft templateMolten saltPre-oxidationTemplate methodSolvent partitionOxidation methodFig.1Schematicillustrationofsynthesisstrategyofpitch-basedporouscarbonandtheirapplicationsinenergystorage460新型炭材料(中英文)第38卷pseudo-capacitanceof carbon materials through re-versibleredoxreactions32.2
25、Pre-treatingprocess 2.1 Solvent partition methodCTPisakindofmixturecomposedofpolycyc-licaromatichydrocarbonsandtheirderivatives3335.ThecommonsolventsegmentationmethodisusedtodivideCTPintothecomponentswithsimilarstruc-tureandcharacteristics(e.g.,volatilityandsofteningpoint).Theprincipleisthateachcomp
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