高容量锂离子电池电极材料研究的新进展课件

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1、高容量锂离子电池电极材料研究的新进展课件 Exploration research of new cathode materials with high capacity for Li-ion batteryYong YangState Key Lab of Physical Chemistry of Solid Surface,Xiamen UniversityChina高容量锂离子电池电极材料研究的新进展课件Whatare the major players of the cathode materials Electrode materialsHigh energy densityHig

2、h power densityLayered oxide cathode materialsPolyanion:LFePO4,Spinel,LiMn2O4High energy densityLi2FeMnSiO4;Organic-typeFluorides高容量锂离子电池电极材料研究的新进展课件Further improvement of layered oxide-based cathode materials1)Nickel-based layered cathode materials:Lattice-dopingSurface coating1)H.S.Liu,et al;Elect

3、rochimica Acta,2004,49:1151-1159;Solid State Ionics,2004,166:317-3252)Z.R.Zhang,et al;J Power Sources,2004,129(1):101-106;J.Phys.Chem.B;2004,108,17546-17552 2)Li-rich Li-Ni-Co-Mn-O system;Very promising system,still more study are needed.E.g.first cycle efficiency,rate capability,safety issues,how c

4、hoose suitable anode systems.高容量锂离子电池电极材料研究的新进展课件LiLi(1-x)/3Mn(2-x)/3Nix/3Co3/xO2 Cathode0501001502002503002.02.53.03.54.04.5Voltage/VSpecific Capacity/mAh/g pristine AlF3 coating0.1 CCharge/discharge at 18 mA/g,2.0 4.8 V The initial discharge capacity is 249 mAh/g,about 100 mAh/g higher than that o

5、f LiCoO2.0501001502002503003502.02.53.03.54.04.55.02nd249 mAh/g324.5 mAh/gVoltage/V as-prepared1stCapacity/mAh/g高容量锂离子电池电极材料研究的新进展课件Layered Oxide-type Cathode MaterialsGas evolution,e.g.O2,CO2High capacity cathode materialsCharging to high voltage 高容量锂离子电池电极材料研究的新进展课件050100150200250300350-0.50.00.51

6、.01.52.02.53.03.03.54.04.55.0AlF3-coatedVoltage/VIon current/10-11 A/gTime/minO2(m/e=32)050100150200250300350-0.50.00.51.01.52.02.53.03.03.54.04.55.0O2Voltage/VIon current/10-11 A/gTime/min(m/e=32)pristine0501001502002503003500123453.03.54.04.55.0Voltage/VIon current/10-11 A/gTime/minCO2(m/e=44)AlF3

7、-coated0501001502002503003500123453.03.54.04.55.0(m/e=44)Voltage/VIon current/10-11 A/gTime/minpristineCO2 AlF3 coating layer provides a buffer layer to make oxygen atoms with high activity combine together to form O2 molecules with low oxidation capability to electrolytes.1/45 times高容量锂离子电池电极材料研究的新

8、进展课件Advantages:Low cost excellent thermal stability no oxygen evolved at low amount Li+intercalatedDisadvantages:Lower capacity and low electronic conductivityPhosphate should be developed as High Power Density and Safe Cathode Materials Polyanion compounds(i.e.LiFePO4)with stable framework is one o

9、f the excellent candidate as new generation cathode materials in lithium-ion batteries高容量锂离子电池电极材料研究的新进展课件Olivine type:LiMPO4 (PO4)3-Orthosilicates:Li2MSiO4 (SiO4)4-The redox potential of Mn+/n+1 can be modulated by the coordinated polyanion group Lower inductive effects of silicate anions compared

10、with phosphate anion,but higher inductive effects than oxide anion is expected.高容量锂离子电池电极材料研究的新进展课件Theo.(mAh g-1)Exp.(mAh g-1)LiCoO2274140LiNiO2275200LiNi1-xCoxO2275170180LiNi1/2Mn1/2O2280180190LiFePO4170150Li2FeSiO4331165 Li2MnSiO4333209(1st cycle)Li2MnxFe1-xSiO4332235(x=0.5)高容量锂离子电池电极材料研究的新进展课件A n

11、ovel cathode materials with more than one electron exchange:Li2MnSiO4 Rietveld plot of Li2MnSiO4/C composite.102030405060708090010002000300040005000600070008000900010000intensity2theta(deg)obs cal diffRF=3.14%RWP=4.21%orthorhombicPmn21a=6.308(3)b=5.377(7)c=4.988(9)Y.X.Li,Z.L.Gong,Y.Yang;J.Power Sour

12、ces,174(2),528-532,2007 Y.Yang,Y.X.Li,Z.L.Gong;Chinese Patent CN 2006100053290501001502002503001.01.52.02.53.03.54.04.55.0 150 mA/g 30 mA/g 5 mA/gVoltage/V vs.Li+/Li Specific Capacity/mAhg-1高容量锂离子电池电极材料研究的新进展课件Li2MnSiO4正极材料循环性能的研正极材料循环性能的研究究0501001502002501.21.41.61.82.02.22.42.62.83.03.23.43.63.84.

13、04.24.44.64.85.0 Votage/VCapacity/mAhg-1 a 1 cycle b 5 cycles c 10 cycles d 20 cycles e 40 cyclesabcdei=30mAg-10102030406080100120140160180200220240 充电放电Capacity/mAhg-1Cycle Numberi=30mAg-1Cyclic stability of Li2MnSiO4 material is poor!高容量锂离子电池电极材料研究的新进展课件The first charge/discharge profiles of Li2Mn

14、1-xFexSiO4/C at a current density of 10 mA g-1.*Z.L.Gong,Y.X.Li,Y.Yang,Electrochem.Solid-State Lett.9(2006)A542.0501001502002501.01.52.02.53.03.54.04.55.0d cba Voltage/V vs.Li+/LiSpecific capacity/mAh/gea:x=0.9b:x=0.7c:x=0.5d:x=0.2e:x=0 A capacity of 214 mAh/g(86%of the theoretical capacity,1.29 ele

15、ctrons per unit formula)was achieved for Li2MnxFe1-xSiO4(x=0.5)sample.Li2Mn1-xFexSiO4/C高容量锂离子电池电极材料研究的新进展课件 Cyclic performance of improved Li2Mn0.5Fe0.5SiO4 02468101214161820050100150200250300350 Cycle number Charge DischargeCapacity/mAh/gCurrent density：10mA/g(C/16)，Temperature：30 oC高容量锂离子电池电极材料研究的

16、新进展课件400030002000100004550556065707580859095100105110/cm-1 1 cycle 3 cycles 5 cycles10cycles 20 cycles 40 cycles4788709701431870cm-1 SiO44-40003500300025002000150010005000.400.350.300.250.200.150.100.050.00Wavenumbers/cm-1Intensity 73589010301115 abcdefcycle number:a:0,b:1,c:5,d:10,e:20,f:40SiO44-Si

17、O44-SiO32-高容量锂离子电池电极材料研究的新进展课件Charge 140mAh/gCharge 100mAh/gLi2MnSiO4(yx)ppm500-50-100-150-200Solid MAS 7Li NMR of Li2MnSiO4 at different charged statesFrom ex-situ NMR spectra,it is proposed that the rate of deintercalation of Li+at different sites are different,and some Li2SiO3 are newly formed高容量

18、锂离子电池电极材料研究的新进展课件Questions Can we get better cyclic performance in SiO44-framework with more than one electron for transition metal ions?What are main factors control the capacity and cyclic stability of the silicates materials?Whats the reaction step and mechanism for mixed system,i.e.Li2Fe1-xMnxSi

19、O4(0 x1)In-situ or ex-situ XAS,Solid MAS NMR,Mossbauer 高容量锂离子电池电极材料研究的新进展课件XRD pattern of Li2Fe0.5MnSiO4SEM images of Li2Fe0.5Mn0.5SiO4Structure and morphology of Li2Fe0.5Mn0.5SiO4/C高容量锂离子电池电极材料研究的新进展课件0501001502002503003501.52.02.53.03.54.04.55.0 1st cycle 2nd cycleVoltage(V)Specific capacity(mAh/g

20、)i=5 mA/g 0501001502002501.01.52.02.53.03.54.04.55.0 1st cycle 2nd cycleVoltage(V)Specific capacity(mAh/g)i=10 mA/g 0501001502001.01.52.02.53.03.54.04.55.0 1st cycle 2nd cycleVoltage(V)Specific capacity(mAh/g)i=150 mA/g Electrochemical performances of Li2 Fe0.5Mn0.5SiO4The initial two cycles at 5 mA

21、/g between 1.5 and 4.8 V.The initial two cycles at 10 mA/g between 1.5 and 4.8 V.The initial two cycles at 150 mA/g between 1.5 and 4.8 V.高容量锂离子电池电极材料研究的新进展课件01234567891011050100150200250 5 mA/g 10 mA/g150 mA/g Li2MnSiO4 at 5 mA/gSpecific capacity(mAh/g)Cyclic numberCyclic performances of Li2Fe0.5Mn

22、0.5SiO4 at 5,10 and 150 mA/g,and Li2MnSiO4 at 5 mA/g高容量锂离子电池电极材料研究的新进展课件0306090 120 150 180 210 240 270 3001.62.02.42.83.23.64.04.44.8jihfgbedcVoltage(V)Specific capacity(mAh/g)ai=20 mA/g,1.5-4.8 VElectrode Reaction Mechanism Study-In-situ XANESThe first charge-discharge curves of Li2Fe0.5Mn0.5SiO4

23、during in-situ measurementSSRF Shanghai,China上海同步辐射光源上海同步辐射光源高容量锂离子电池电极材料研究的新进展课件7110712071307140715071600.00.40.81.21.62.0 Li2Mn0.5Fe0.5SiO4 charge 3.8 V charge 4.2 V charge 4.6 V charge 4.8 V FeO Fe2O3 Absorption Coefficient(a.u.)Energy(eV)In-situ Fe K-edge XANES spectra during the first charging

24、process高容量锂离子电池电极材料研究的新进展课件65406550656065706580659066000.00.51.01.5654065456550655565600.00.30.60.91.21.5 Li2Fe0.5Mn0.5SiO4 charge 3.8 V charge 4.2 V charge 4.6 V charge 4.8 V MnO Mn2O3 Absorption Coefficient(a.u.)Energy(eV)Absorption Coefficient(a.u.)Energy(eV)Li2Fe0.5Mn0.5SiO4 charge 3.8 V charge

25、4.2 V charge 4.6 V charge 4.8 V MnO Mn2O3In-situ Mn K-edge XANES spectra during the first charging process高容量锂离子电池电极材料研究的新进展课件6545.06545.56546.06546.56547.06547.56548.06548.56549.06549.56550.01.2 1.8 2.4 3.0 3.6 4.2 4.87120.07120.57121.07121.57122.07122.57123.07123.57124.07124.57125.0 Absorption edg

26、e(eV)Absorption edge(eV)Step voltage(V)Fe K edgeFeO(7120.37 eV)Fe2O3(7123.08 eV)charge4.8 4.2 3.6 3.0 2.4 1.8 1.2 Mn K edge discharge MnO(6545.37 eV)Mn2O3(6548.74 eV)Evolution of absorption edge of Fe and Mn of Li2Mn0.5Fe0.5SiO4 in the first charging and discharging processes.高容量锂离子电池电极材料研究的新进展课件Nan

27、o-structured Li2FeSiO4 with excellent rate capabilities and cyclic stability102030405060708090 2 Theta(o)Space group:OrthorhombicPmn21 X-ray diffraction patterns of the carbon coated Li2FeSiO4.Insert:TEM image of the material.Z.L.Gong,Y.X.Li,G.N.He,J.Li,Y.Yang*Electrochem.Solid State Lett.,11,A60-63

28、(2008).高容量锂离子电池电极材料研究的新进展课件Nanostructured characteristic of the Li2FeSiO4 make it as high-rate cathode materials feasible高容量锂离子电池电极材料研究的新进展课件The inverse of the magnetic susceptibility with temperature agrees well with paramagnetism for pure sample.The arrow point out the anomalies characteristics of

29、 an antiferromagnetic ordering of Li2FeSiO4 below TN=20 K.The curve agree well with Curie-Weiss law in the whole paramagnetic region.高容量锂离子电池电极材料研究的新进展课件Electrochemical performance of the Li2FeSiO4 cathodes at different cycles0501001502001.01.52.02.53.03.54.04.55.0 1st 2nd 10th Specific capacity(mAh

30、/g)Voltage(V)1.54.8 V versus Li+/Li;1/16 CZ.L.Gong,Y.X.Li,G.N.He,J.Li,Y.Yang*Electrochem.Solid State Lett.,11,A60-63(2008).高容量锂离子电池电极材料研究的新进展课件05010015012345C/1610 C 5 C2 C Specific capacity(mAh/g)Voltage(V)C/1610 C5 C2 CExcellent rate-performance of the silicate cathode materialsZ.L.Gong,Y.X.Li,G.N

31、.He,J.Li,Y.Yang*Electrochem.Solid State Lett.,11,A60-63(2008).Reasons:Porous nanostructure,and improved electronic conductivity through carbon connection.高容量锂离子电池电极材料研究的新进展课件01020304050020406080100120140160180200 2 C 5 C10 C Cycle numberDischarge Capacity(mAh/g)Excellent cyclic stability of Li2FeSiO

32、40204060800204060801001201401601802002C10C Cycle numberDischarge Capacity(mAh/g)2C5C高容量锂离子电池电极材料研究的新进展课件050100 150 200 250 300 350 400 450-10-8-6-4-20246810 ExoDSC/(mW/mg)Temperature/oC uncycle Charge to 4.8 VLi2FeSiO4+ElectrolyteNo extra heat give off during heating process!高容量锂离子电池电极材料研究的新进展课件 At

33、our synthesis conditions,two modifications of Li2CoSiO4(,and)which are derivatives of low temperature Li3PO4 were obtained.a:;Oorthorhombic and space-group Pmn21.b:orthorhombic The XRD profiles of the Li2CoSiO4 powers prepared at different conditions.Co-silicates-Li2CoSiO4 L.Gong,Y.X.Li,Y.Yang;J Pow

34、er Sources,2007,174(2),524-527,S.Q.Wu,J.H.Zhang,Z.Z.Zhu and Y.Yang,Curr.Appl.Phys.2007,7,611高容量锂离子电池电极材料研究的新进展课件The temperature dependence of the inverse molar magnetic susceptibility 1/m for Li2CoSiO4 powers prepared at 873 K.The magnetization curves M(H)at 2 K for Li2CoSiO4 powers prepared at 873

35、K.Magnetic property高容量锂离子电池电极材料研究的新进展课件Galvanostatic chargedischarge curves for Li2CoSiO4-based cathodes at current rate 16 mA/g.Electrochemical performance高容量锂离子电池电极材料研究的新进展课件space-group:Pmn21SiO4-MO4LiO4SiO4-MO4Corrugated layerStructure of Li2MSiO4Reference:1)S.Q.Wu,et al;Computational Materials S

36、cience,2009,44,1243-1251 O Co-OO Si-O高容量锂离子电池电极材料研究的新进展课件 A series of silicates cathode materials such as Li2FeSiO4,LiFexMn1-xSiO4,Li2CoSiO4 with and without carbon coating have been synthesized,some of them could achieve more than 1-1.6 Li+reversible exchange.e.g.Li2Mn0.5Fe0.5SiO4 with 235 mAh/g ha

37、s been achieved.We have made a carbon-coated nanostructured Li2FeSiO4 material with excellent rate performance,it shows a promise as cathode materials for high-power lithium-ion batteries.Phase-pure Li2CoSiO4 has been prepared successfully and its physical properties and electrochemical performance

38、were characterized.高容量锂离子电池电极材料研究的新进展课件Some commentsnWe have made some promising progress about silicates in the last few years,but due to several phases or even impurity may be formed during the synthesis,we need to refine our synthesis route and get well-controlled and phase-purifed products with

39、satisfied electrochemical performance.nSilicates system is quite complex than we imagine,we need to more techniques to characterize it,esp.in-situ techniques for characterization of intercalation/de-intercalation process including bulk and local crystal and electronic structure,高容量锂离子电池电极材料研究的新进展课件Acknowledgement National Natural Science Foundation of China(NNSFC,Grant No.20873115 and no.90606015)Ministry of Science and Technology,China(Grant No.2007CB9702)Xiamen University高容量锂离子电池电极材料研究的新进展课件