钠离子电池电极材料研究进展

：2015-06-02。：2015-07-19。973(No.2011CB935900)，(No.21231005)。＊。E-mail：[e-mail]＊＊＊＊＊＊＊＊＊＊＊＊张宁刘永畅陈程成陶占良陈军＊(南开大学化学学院，先进能源材料化学教育部重点实验室，天津化学化工协同创新中心，天津300071)：，，，。，，，。。，，。：；；：O614.112：A：1001-4861(2015)09-1739-12DOI：10.11862/CJIC.2015.258ResearchonElectrodeMaterialsforSodium-IonBatteriesZHANGNingLIUYong-ChangCHENCheng-ChengTAOZhan-LiangCHENJun＊(KeyLaboratoryofAdvancedEnergyMaterialsChemistry(MinistryofEducation),CollaborativeInnovationCenterofChemicalScienceandEngineering,CollegeofChemistry,NankaiUniversity,Tianjin300071,China)Abstract:Sodiumionbatteries(SIBs)haverecentlyattractedmuchattentionbecauseoftheabundance,widedistributionandlowcostofNasource.However,Na+isheavierandlargerthanthatofLi+,limitingtheinsertionofandextractionofNa+intoandfromthehostmaterials.Thus,developingtheadvancedelectrodesmaterialsisthekeypointforSIBs.Inthisreview,wesummarizetheresearchdevelopmentofselectedelectrodematerialsofSIBs.ThisshouldshedlightontheR&DofadvancedelectrodematerialsofSIBs.Keywords:sodiumionbatteries;cathodematerial;anodematerial2080，(Sodiumionbatteries,SIBs)，，。，(1)，(1)。，Na+(NaMnO2)，()，，；。，：，2.64%，，。，(0.102nm)(0.069nm)，Na+，。，Na+/Na(-2.71VvsSHE)Li+/Li0.3V(-3.04VvsSHE)，，，[1-3]。，、31920159Vol．31No．91739-1750CHINESEJOURNALOFINORGANICCHEMISTRY31。，，、[4-5]。，，。，，，。2[3]，；()、(Sn，Sb，P)(/)。1Fig.1OperationprincipleofrechargeableSIBsduringchargeanddischarge1Table1SodiumversuslithiumcharacteristicsNaLiAtomicweight/(g·mol-1)236.94Cationradius/nm0.1020.069Eo/V(vsSHE)-2.71-3.04Meltingpoint/℃97.7180.5Abundance/%2.640.01DistributionWidedistribution70%inSouthAmericaPriceofcarbonates/(RMB·kg-1)~2~40Theoreticalcapacity/(ACoO2,mAh·g-1)2352742[3]Fig.2RelationshipbetweencapacityandvoltageforpresentelectrodematerialsinNa-ionbatteries[3]17409：11.1NaxMO2MO6，(Na+)MO6。DelmasNa+，，O3P2(3a~b)[6]。On：MO6，n()，OABCABC…。，Pn，Na+MO6，PABBAABBA…。NaCoO2LiCoO2，[7]。O3、O′3、P′3、P2NaxCoO2,P2-NaxCoO2[8]。DelmasNaxCoO2，NaxCoO2O3葑O′3葑P′3，[6]。XRD，P2-NaxCoO2，，NaNa+/VNa+(Na+)[9]。NaMnO2NaCoO2，(243mAh·g-1)[10]。O3P2，O2NaxMnO2[11-12]。NaxMnO2，，。，NaFeO2，NaCrO2，NaNiO2NaVxOy[13-16]。，。，FeNaNi0.5Mn0.5O2[Ni0.5Mn0.5]，O3-Na[Ni0.25Fe0.5Mn0.25]O2：140mAh·g-1(0.1C，2.1~3.9V)，1C5090.4%[17]。P2-Na2/3[Fe1/2Mn1/2]O2O3-Na[Fe1/2Mn1/2]O2[18]。P2-Na2/3[Fe1/2Mn1/2]O2，190mAh·g-1(13mA·g-1，1.5~4.2V)，3070%。O3-Na2/3[Fe1/2Mn1/2]O2110mAh·g-1。，。P2-Na2/3(Fe1/2Mn1/2)O2，195mAh·g-1(26mA·g-1)，8086%，P2-Na2/3(Fe1/2Mn1/2)O2[19]。，P2O3，P2，。Na+P2O3，Na+。，，。1.2NaxMO21971，HagenmullerNa0.44MnO2[20]，Mn4+Mn3+(MnO6)，Mn3+(MnO5)，S，(3c)。，Na0.44MnO2(121mAh·g-1)[21]。，，，。，LiuNa4Mn9O18，128mAh·g-1(0.1C，2.0~4.0V)，0.5C1000，77%，[22]。，Na0.61Ti0.48Mn0.52O2，0.2C86mAh·g-1(3(a)O3(b)P2(c)Fig.3StructuralpatternsofO3-phase(a),P2-Phase(b)andTunnel-Phase(c)1741311.5~4.0V),10081%[23]。1.3，，。NaFePO4，NASICONNa3V2(PO4)3，(Na2MP2O7andNa4M3(PO4)2P2O7)，(NaVPO4F，Na2MPO4F，Na3(VOx)2(PO4)2F3-2x)(M=Fe，Co，etal.)，4。1.3.1NaFePO4NaFePO4，，Na+，。NaFePO4(4a)154mAh·g-1，2.9V(vsNa/Na+)。Na+，。NaFePO4。Nazar(≤100℃),NH4[Mn1-xMx]PO4·H2O(M=Fe，Ca，Mg)Na[Mn1-xMx]PO4[24]。LiFePO4LiFePO4，NaFePO4。0.1C，100mAh·g-1，100，90%[25]。，NaFePO4Na[26]。，，FePO4，。142mAh·g-1，20095%。1.3.2NASICONNa3V2(PO4)3NASICON(Nasuperionicconductor)，。NASICON，MO66PO4NASICON，Na+Mrepresentstransionmetals4Fig.4Crystalstructuresofvariouspolyanion-basedcathodematerials17429(4b)。Na3V2(PO4)3，3.4V，2Na，117mAh·g-1。，Na3V2(PO4)3[27]。Na3V2(PO4)3@C(NanoNVP@C)，0.5C，104.3mAh·g-1。5C94.9mAh·g-1，70092.1mAh·g-1(5)[28]。Na3V2(PO4)3/C，40C61.5mAh·g-1(2.3~3.9V),30000，50%[29]。NASICON，，。，(Fe，Mn，Ni)NASICON，。1.3.3，NaVPO4F，Na2MPO4F(M=Fe，Co)，Na3V2(PO4)2F3，Na3(VOx)2(PO4)2F3-2x(0≤x≤1)。VPO4NaFNaVPO4F(82mAh·g-1)，，3.7V，3050%[30]。NaVPO4F，0.1C97.8mAh·g-1，2089%[31]。Na3V2(PO4)2F3(4c)2Na+，3.9V，128mAh·g-1。Na3V2(PO4)2F3FO，Na3(VOx)2(PO4)2F3-2x(0≤x≤1)[32-33]。O，Na3(VOx)2(PO4)2F3-2x，V4+V3+。，F，，。Na3(VO0.8)2(PO4)2F1.4，3.8V，(~600mWh·g-1)[32]。Na2FePO4F(4d)，5(a)Na3V2(PO4)3@CTEM,(b)0.5C，,(c)5C，Na3V2(PO4)3@CFig.5(a)TEMimageofthenanoNVP@C,(b)Typicalchargeanddischargeprofilesat0.5C,(c)SpecificreversiblecapacityversuscyclenumberfornanoNVP@Cat5Cratefor700cycles[28]：1743313.0V，135mAh·g-1[34]。，Na2CoPO4F100mAh·g-1，4.3V，Na2MPO4F(M=Fe，Co，Mn)[35]。Na2MP2O7(M=Fe，Mn，Co)，(4e)，(4f)。，，Na2FeP2O7Na2MnP2O7，，Na2CoP2O7。Na2FeP2O782mAh·g-1，Na3.0V[36]。，Na2CoP2O7Na2MnP2O7，3.0V3.65V[37-38]。(100mAh·g-1)，。1.4KFe[Fe(CN)6]，，，。KxNiFe(CN)6NaK，[39]。AxMFe(CN)6(A=KNa；M=Ni、Cu、Fe、Mn、CoZn)[40]。，，CN-，。，，。，，，，，，[41-43]。，，，(Na2C6O6)，(Na4C8H2O6)[44]；，，-[45]。，，。，，，、。，、Na4C8H2O6(6)。，(1.6~2.8V)，(0.1~1.8V)。，1.8V，65Wh·kg-1，100，[44]。6(a)Na4C8H2O6,(b)(19mA·g-1),(c)(19mA·g-1)[44]Fig.6(a)ElectrochemicalredoxreactionmechanismofNa4C8H2O6,(b)Galvanostaticcharge/dischargevoltageprofilesofthefullcellsunderacurrentdensityof19mA·g-1,(c)CyclingandCoulombicefficiencycurvesat19mA·g-1[44]1744922.1，372mAh·g-1。，，，。，，Na。，240mAh·g-1(25mA·g-1，0~2V)，100200mAh·g-1[46]。，50mA·g-1，251mAh·g-1，400，206.3mAhg-1[47]。/，1A·g-1，1000250mAh·g-1，[48]。，(300mAh·g-1)，(~0VvsNa+/Na)，，。[49-51]，，Na2Ti3O7，Na2Ti6O13，Na4Ti5O12，Li4Ti5O12P2-Na0.66[Li0.22Ti0.78]O2。Na2Ti3O7(0.3V)，2Na+，177mAh·g-1[51]。P2-Na0.66[Li0.22Ti0.78]O2，212mA·g-1，1200，60mAh·g-1，[49]。，，2