基于转化反应机制的锂离子电池电极材料研究进展

*2211162010LKHX03、2010QNB04、2010QNB05、ON090237CX10B-153Z2011-02-242011-05-17。、。ProgressofElectrodeMaterialsEntailingConversionReactionforLi-ionBatteriesWuChaoCuiYongliZhuangQuanchao*XuShoudongShenMingfangShiYueliSunZhiLi-ionBatteriesLabSchoolofMaterialsScienceandEngineeringChinaUniversityofMiningandtechnologyXuzhou221116AbstractThedevelopmentofelectrodematerialsentailingconversionreactionswereveryimportantmethodsforimprovingtheperformanceofLi-ionbatteriesespeciallyforimprovingitsreversiblecapacityuponcycling．InthispapertheprogressesoftheuseoftransitionmetalcompoundsthatreactwithLithroughconversionreactionsasbothpositiveandnegativeelectrodematerialsinLi-ionbatterieswerereviewedthemechanismsoftheconversionreactionswereintroducedandseveralfactorscurrentlyhandicappingtheapplicabilityofelectrodematerialsentailingconversionreactionswerealsodiscussed．Emphasiswasputontheelectrochemicalbehaviorthepropertiesofelectrode/electrolyteinterfacesandthemethodsforimprovingtheperformanceofthesetransitionmetalcompoundsentailingconversionreactions．Atlastthedirectionsoffutureresearchofelectrodematerialsthroughconversionreactionswereputforward．KeywordsLi-ionbatteriesConversionreactionsTransitionmetalcompounds、、Mp3、、。、、、。、LiCoO212。2000Tarascon《Nature》3d3～9。3d·4101·20117411http//．hxtb．org、10～19。、FeF3、NiF2、FeS2、CoS2NiP2。2～42021。22～29。。1。1“”。mnLi++MnXm+mne－mLinX+nM01MM=Fe3+、Ni2+、Cu2+、Mn6+、Cr3+XF－、O2－、P3－M00。LinXLinX/M0LinX/M0MnXm30。LinXLiFLi2OLiF3LiO2.5LiFLi2O6.1V、5V。LiFLi2O0.01～4.5V、。。。。LinX。2、、、、。、、。1、。·5101·http//．hxtb．org20117411122Fig．1Schematicofdifferentbetweeninteractionandcoversion221、31Tab．1EMFvaluesspecificcapacityandspecificenergyforsomesimplebinarytransitionmetalcompounds31MeXzVmAh/gWh/kg2Li+Me2+Xz→zLi2/zX+MeMnF21.925771108MnO1.03756779MnS1.144616705FeF22.665711519FeO1.617461201FeS1.756101068CoF22.8545531578CoO1.87151287NiF22.965541640NiO1.957181400CuF23.555281874CuO2.256741517CuS256111223Li+Me3+Xz→zLi3/zX+MeVF31.867451386V2O30.94510731014CrF32.287381683Cr2O31.0910581153MnF32.657191905Mn2O31.4310181455FeF32.747121951Fe2O31.6310071641BiF33.13302945Bi2O32.17345749·6101·20117411http//．hxtb．org2.1LiLi。。。206070。FeF3、NiF2、CuF2。。2.1.1FeF3、、。1997Arai32FeF324.5～2.5V200mAh/g2.5～1.5V400mAh/g。Li33Badway34～36FeF31、FeF3+Li++e－→LiFeF34.5～2.5V2LiFeF3+2Li++2e－→Fe+3LiF2.5～1.5V34.5～2.5VFeF3LiFeF32.5～1.5VLiFeF3FeLiFFeF3/C。Makimura37HRTEMFeF3FeLiF。Li383FeF31.0～4.5V100mA/g10FeF3742mAh/g547mAh/gFeF323.5～2.0V1.7～1.0V。Yamakawa39xLi+=0.25～0.5Li+ALi0.5FeF3FeF3ReO3xLi+=0.5～1Fe3+Fe2+LiFeF3xLi+=1.0～3.0Li+FeFeLiFeF3LiFFe。Badway36FeLiFFeF3ReO3FeF2FeF2/CFeF3/CLixFeF30＜x＜1Fe3+→Fe2+3.5～2.8V3Li+Fe2+F2Fe3+F3。2.1.22060NiF2。NiF2。NiF2/C70℃2V35NiF21.5V33NiF20.7V28NiF22.96V。。2.1.3CoF2CoF3CoF3。4041CoF20.01～3.5V10A/cm2·7101·http//．hxtb．org20117411600mAh/g200mAh/g2.8V。CoF2+2Li++2e－→Co+2LiFLiF+Co→CoF+Li++e－。LiF6.1V0.01～3.5VLiF。LiFCoCoLiFCoLiFLiF。2.1.41970CuF2CuF2。CuOHFCuF2·2H2O25%CuF2。Amatucci42CuF2/MoO32.9V2V400mAh/g。43CuF2860mAh/g1.7V80%。CuF2+2Li+2e－Cu+2LiF4CuLiF。2.1.5BiF3、TiF3VF3。BiF3905Wh/kg7170Wh/LBiF。1978Fiordiponti44BiF320BiF32005Amatucci45BiF3/C4C188mAh/g2～4.5V45.45mA/g15190mAh/g。2.2NaCl3dNiO、CoO、CuO、FeOMnO2、Fe2O3、Fe3O4、Cr2O3、Co3O4、CuO700mAh/g。2.2.1α-Fe2O3、Fe3O4FeOα-Fe2O31007mAh/g、。α-Fe2O3208046～48。α-Fe2O31molα-Fe2O36mol49。Thackeray47α-Fe2O3LixFe2O30≤x≤2LixFe2O3Li2OFeα-Fe2O3、xLi++Fe2O3+xe－→LixFe2O30≤x≤25Li2Fe2O3+4Li++4e－→3Li2O+2Fe6α-Fe2O3、α-Fe2O3α-Fe2O3。Jain50α-Fe2O3α-Fe2O3α-Fe2O3。Liu51α-Fe2O31332mAh/g30753mAh/gα-Fe2O3Li+·8101·20117411http//．hxtb．orgLi+。Fe3O4FeOFeLi2OFe3O4FeO5253。2.2.2Co3O4、CoOCo3O4890mAh/g31015545556。α-Fe2O3Co3O4、。Wang57Co3O4、Co3O4、3Co3O4。0.01～3.0V1/5CCo3O4、Co3O4、3Co3O4、Co3O450680、866、611134mAh/g。Li+Co3O4Co3O4Co3O4Co3O4Co3O4Li+Li+Co3O4Co3O43Co3O4Li+3Co3O43Co3O43Co3O4。2.2.3CuOCu2OCuO20Li/CuO。CuOCu2OLi2OCuOCuOCuLi2O58CuOCu2O59CuOLixCuO0＜x＜260。CuOCu2O674mAh/g375mAh/gCuOCu2O。Debart12CuOCuOCuOCuⅡ1－xCuⅠxO1－x/20≤x≤0.4Cu2O0.4＜x＜0.8CuLi2O。。Wang61CuO789mAh/g100650mAh/g7.5CCuO430mAh/g372mAh/g。100CuOCuOLi+CuOCuO62。2.2.4Cr2O31058mAh/g、1.085V。Cr2O3900mAh/g。Li2O/CrCrOCr2O363。Cr2O3Cr2O3Cr2O3Li+。Cr2O3Li+Li+Cr2O3“”“”Li+Cr2O364。Cr2O3Cr2O36566。·9101·http//．hxtb．org201174112.2.5、、。MnO672、Mn2O68693、Mn3O69～714MnO157273。MnO21233mAh/gMnO2MnCr、Co、Cu。。Wu74γ-MnO2100γ-MnO2600mAh/gZhong73MnO150600mAh/g。2.2.6197075～77。MoO33、3MoO6。MoO3α-MoO3MoO61“”。MoO31117mAh/gMoO3。Lee78～80MoO31000mAh/g81MoO3MoO3295.1mAh/g15236.6mAh/g。2.3。TiS2MoS2208082～85。、、86～90。2.3.1FeS2、FeS、、20809091～93。FeS2FeLi2SFeS2Li2FeS2FeS2FeS94～97。2.3.2CoS2、CoS0.98、Co9S8、Co0.92S。CoS2CoS29899。COLi2S。Yan100CoS21.6～3.0VCoS2LixCoS20.02～3.0VCoS2CoLi2S。0.02～3.0VCoS21.6～3.0VCoS2。2.4。1617101102Co3N、Fe3N324～420mAh/gNi3N320～420mAh/gCrN301000mAh/g。Das103CoN0.005～3.0V0.33C760mAh/g80990mAh/g。33.12104～1061·0201·20117411http//．hxtb．org2。SEISEISEISEI30～90nm/651072～8nmLi2OLiF、Li3P。Li2OLiF、Li3P。2～8nm。Li2OLiF、Li3P。3.21SEI2。SEI。SEI、SEI。SEISEI。Zhang108Fe3O4/CTEMFe3O4SEI10nmFe3O420～50nmSEI。Fe3O4/C80%Fe3O425%。。。Nuli109ZnFe2O4AgAg0.37ZnFe2O480%ZnFe2O470%。、Li2OLiF、Li3P。Kang110～112Co3O4NiCo3O4/NiNiCo3O4。Co3O4/NiCo