高比能鋰離子電池合金負極材料研究趙海雷

1、1 高比能二次鋰離子電池合金負極材料高比能二次鋰離子電池合金負極材料的研究及其規(guī)?；苽涞难芯考捌湟?guī)?；苽?No. 2006AA03Z231)2不同二次電池的性能對比3Application in microelectronics4 碳材料為目前碳材料為目前鋰離子電池常鋰離子電池常用的負極材料用的負極材料碳材料的理論比容量碳材料的理論比容量為為372 mAh/g372 mAh/g目前碳負極材料的實目前碳負極材料的實際比容量已經(jīng)非常接近際比容量已經(jīng)非常接近其理論比容量其理論比容量需要需要尋尋找新的、可以替代碳材料的高容量找新的、可以替代碳材料的高容量鋰鋰離子離子電電池池負負極材料極材料 SnS

2、n基合金材料引起了人們的極大關(guān)注基合金材料引起了人們的極大關(guān)注 它的理論比容量為：它的理論比容量為：Li22Sn5: 994 mAh/g 人們研究了許多人們研究了許多SnSn基合金體系基合金體系, , 如如: : SnSb, SnCu, SnCo, SnV, SnFe, etc.5 阻礙阻礙Sn基合金商業(yè)化的原因基合金商業(yè)化的原因 電極大的體積膨脹電極大的體積膨脹 采用納米顆粒的合金粉體采用納米顆粒的合金粉體 首次不可逆容量較高首次不可逆容量較高 (低的首次庫侖效率低的首次庫侖效率) New idea 具有納納/微復(fù)合結(jié)構(gòu)和內(nèi)微孔微復(fù)合結(jié)構(gòu)和內(nèi)微孔的顆粒顆粒SnCo powders6 傳統(tǒng)的合

3、成方法傳統(tǒng)的合成方法 從水溶液中的化學(xué)共沉淀從水溶液中的化學(xué)共沉淀 粉末冶金粉末冶金 電鍍的方法電鍍的方法 機械合金化的方法機械合金化的方法這些合成方法要么工藝復(fù)雜，要么不適宜大規(guī)模生產(chǎn)這些合成方法要么工藝復(fù)雜，要么不適宜大規(guī)模生產(chǎn)7 Carbothermal reduction Simple, cheap and mass productionSnO2 + 2C = Sn + 2CO(g) Sb2O3 + 3C = 2Sb + 3CO(g) CuO + C = Cu + CO(g) NiO + C = Ni + CO(g) CoO + C = Co + CO(g) Synthesis of

4、Sn-based Alloy Composite Powder02004006008001000-80-60-40-20020406080100120 G (kJ)Temp. (0C)SnO2+2C=Sn(l)+2CO6300C802004006008001000-120-100-80-60-40-200204060801004350C G (kJ)Temp. (0C)NiO+C=Ni+CO(g)-20002004006008001000-200-150-100-50050-250C G (kJ)Temp. (0C)CuO+C=Cu+CO(g)02004006008001000-300-250

5、-200-150-100-500501001502002504350C G (kJ)Temp. (0C)Sb2O3+3C=2Sb+3CO(g)02004006008001000-100-80-60-40-200204060801005000C G (kJ)Temp. (0C)CoO+C=Co+CO(g)Thermodynamic calculation for carbothermal reduction of metal oxides9Flow chartOxidesCarbonMixingFiringSievingTape castingAssembling cellXRDSEM, TEM

6、BETCharge/discharge cyclingCyclic voltammograms AC impedance10Sn-Sb system020406080100 Intensity (a.u.)2 (degree)SnSb850 , 2 h850 , 6 hTEM for single particle11SEM morphologies of SnSb alloy powders2 h4 h6 h8 h12Sn-Sb system05101520020040060080010001200Capacity (mAh/g)Cycle number (n) 2 h 6 h50mA/g1

7、00mA/g200mA/g0510152002004006008001000Capacity (mAh/g)Cycle number (n) 2h 6hMario Wachtler , J. Power Sources 105 (2002):151-160 13Sn-Sb system14Sn-Sb system0510152001002003004005006007008009001000 Specific Capacity (mAh/g)Cycle number (n) 0.3-1.2 V 0.01-0.8 V體積比容量是碳負極的體積比容量是碳負極的2倍。倍。020040060080010

8、00-0.20.00.20.40.60.81.01.21.41.61.8Voltage / V vs.Li+/LiSpecific capacity / mAh g-115Sn-Ni system1020304050607080050010001500200025003000350033333333333222111111111Intensity (a.u.)2 (degree)1 Sn 65-02962 Ni3Sn2 06-04143 Ni3Sn4 04-0845 116Sn-Ni systemZ.P. Guo , Z.W. Zhao, H.K. Liu, S.X. Dou, Carbon

9、43 (2005) 1392 Cycling performance of NiSn2 alloy composite electrode at constant current density of 100mAg-1 0246810 12 14 16 18 20 22 24 26050100150200250300350400450Specific capacity / mAhg-1Cycle number / n Charge Discharge17Sn-Sb-Ni system024681012141618200100200300400500600 Cycle number / nDis

10、charge capacity / mAhg-1 100 mAg-1 150 mAg-1 200 mAg-1900 , 2 hCycling performance18Sn-Co system020406080100050010001500200025003000 Intensity (a.u.)2 (degree)SnCo024681012141618200100200300400500600700800900Discharge capacity / mAhg-1Cycle number / n 50 mAg-1 500 mAg-1C. Mi, et al, J. Inorganic Che

11、mistry, 3 (2003) 283. 800, 2 h19Sn-Cu-Co system20Sn-Cu-Co system05101520-1000100200300400500600700800 Capacity(mAh/g)Cycle number(n)Sn5/3CuCoSn3CuCoSn4CuCo0510152025-1000100200300400500600700800Capacity(mAh/g)Cycle number(n) 0.01-0.7 V 0.01-1.5 V21Sn-Co-C024681012141618202224262830010020030040050060

12、0(a) Capacity/mAh g-1Cycle number CoSn2 charge CoSn2 discharge CoSn2C charge CoSn2C discharge CoSn2C10 charge CoSn2C10 discharge22Si-基負極材料的研究051015202530354001000200030004000 Specific Capcity (mAh/g)Cycle Number (n) delithiation lithiationCut-off：0.01-3.0VCurrent-density：250mA/g23Si-基負極材料的研究010203040500200400600800100012001400160018002000 Specific Capcity (mAh/g)Cycle number(n)lithiationdelithiatioin24致謝致謝 感謝國家感謝國家“863”高技術(shù)發(fā)展計劃對本項目高技術(shù)發(fā)展計劃對本項目的支持的支持 (No. 2006AA03Z231).25Depa