Sn~(4+)掺杂对正极材料Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2性能的影响
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摘要
采用共沉淀法合成掺杂的Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3-x)Sn_xO_2的正极材料,通过X射线光谱、扫描电镜、充放电测试等技术对Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3-x)SnxO_2材料的结构、形貌、电化学性能进行表征。结果表明,采用共沉淀法Sn4+能有效掺杂进正极材料Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3)O_2的体相结构。掺杂量x=0.04时,在2.8~4.2V、0.2C倍率下掺杂的正极材料首次充放电比容量为138.5mA·h/g,30次循环后的容量保持率为96.96%。掺杂Sn4+对Li_(1/3)Ni_(1/3)Co_(1/3) Mn_(1/3)O_2正极材料改性后,材料仍保持典型的α-NaFeO_2层状结构,且晶型良好,表明Sn4+掺杂能够有效改善材料的电化学性能。
The anode material of Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3-x)Sn_xO_2 was synthesized by a coprecipitation method and the structure,morphology and electrochemical properties were characterized by XRD,SEM and charge-discharge test technology.The results showed that the first charge-discharge specific capacity was 138.5 mA·h/g and the capacity rate was 96.96% after 30 cycles when doping anode material ratio was 0.2C,x = 0.04 and the voltage was 2.8-4.2 V.The modified materials could remain typical layer structure ofα-NaFeO_2 and the structure of crystals was good,indicating the electrochemical properties were improved after doping Sn4+.
The anode material of Li_(1/3)Ni_(1/3)Co_(1/3)Mn_(1/3-x)Sn_xO_2 was synthesized by a coprecipitation method and the structure,morphology and electrochemical properties were characterized by XRD,SEM and charge-discharge test technology.The results showed that the first charge-discharge specific capacity was 138.5 mA·h/g and the capacity rate was 96.96% after 30 cycles when doping anode material ratio was 0.2C,x = 0.04 and the voltage was 2.8-4.2 V.The modified materials could remain typical layer structure ofα-NaFeO_2 and the structure of crystals was good,indicating the electrochemical properties were improved after doping Sn4+.
引文
[1]PARK J H,CHO J H,KIM S B,et al.A novel ionconductive protection skin based on polyimide gel polymer electrolyte:application to nanoscale coating layer of high voltage LiNi1/3Co1/3Mn1/3O2cathode materials for lithium-ion batteries[J].Journal of Materials Chemistry,2012,22(14):12574-12581.
[2]YANG C F,HUANG J J,HUANG L,et al.Electrochemical performance of LiCo1/3 Mn1/3Ni1/3O2hollow spheres as cathode material for lithium ion batteries[J].Journal of Power Sources,2013,226:219-222.
[3]王海权,胡志强,于洋,等.尖晶石型锰酸锂的复合掺杂改性[J].大连工业大学学报,2014,33(5):364-367.
[4]LEE S,PARK S S.Atomistic simulation study of mixed-metal oxide(LiNi1/3Co1/3Mn1/3O2)cathode material for lithium-ion battery[J].Journal of Physical Chemistry C,2012,116(10):6484-6489.
[5]WU F,WANG M,SU Y F,et al.A novel method for synthesis of layered LiNi1/3Mn1/3Co1/3O2as cathode material for lithium-ion battery[J].Journal of Power Sources,2010,195(8):2362-2367
[6]ZENG Y W.Investigation of LiNi1/3Co1/3Mn1/3O2cathode particles after 300discharge/charge cycling in a lithium-ion battery by analytical TEM[J].Journal of Power Sources,2008,183(1):316-324.
[7]GAO P,LI Y H,LIU H D,et al.Improved high rate capacity and lithium diffusion ability of LiNi1/3Co1/3Mn1/3O2 with ordered crystal structure[J].Journal of the Electrochemical Society,2012,159(4):A506-A513.
[8]ZHU J X,VO T,LID S,et al.Crystal growth of Li[Ni1/3Co1/3Mn1/3]O2as a cathode material for highperformance lithium ion batteries[J].Crystal Growth and Design,2012,12(3):1118-1123.
[9]TODOROV Y M,NUMATA K.Effects of the Li:(Mn+Co+Ni)molar ratio on the electrochemical properties of LiMn1/3Co1/3 Ni1/3 O2 cathode material[J].Electrochimica Acta,2004,50(2/3):495-499.
[10]FEGUS J W.Recent developments in cathode materials for lithium ion batteries[J].Journal of Power Sources,2010,195(4):939-954.
[11]熊礼龙,徐友龙,陶韬.Ge4+、Sn4+掺杂尖晶石LiMn2O4的合成与电化学表征[J].物理化学学报,2013,29(4):763-769.
[12]OHZUKU T,MAKIMURA Y.Layered lithium insertion material of LiCo1/3Ni1/3Mn1/3O2for lithiumion batteries[J].Chemistry Letters,2001,30(7):642-643.
[13]YABUUCHI N,OHZUKU T.Novel lithium insertion material of Li[Ni1/3Co1/3Mn1/3]O2for advanced lithium-ion batteries[J].Journal of Power Sources,2003,119/120/121(1/2):171-174.
[14]SHAJU K M,SUBBA G V,CHOWDARI B V R.Performance of layered LiNi1/3Co1/3Mn1/3O2as cathode for Li-ion batteries[J].Electrochimica Acta,2002,48(2):145-151.
[15]CHOI J,MANTHIAM A.Role of chemical and structural stabilities on the electrochemical properties of layered LiNi1/3Mn1/3Co1/3O2 cathodes[J]Journal of the Electrochemical Society,2005,152(9):A1714-A1718.
[16]LIAO L,WANG X Y,LUO X F,et al.Synthesis and electrochemical properties of layered cathode Li[Ni0.333Mn0.293Al0.04]O2-xFx materials prepared by the sol-gel method[J].Journal of Power Sources,2006,160(1):657-661.
[17]KIM G H,MYUNG S T,KIM H S,et al.Synthesis of spherical Li[Ni(1/3-z)Co(1/3-z)Mn(1/3-z)Mgz]O2 as positive electrode material of lithium-ion battery[J].Electrochimica Acta,2006,51(12):2447-2453.
[2]YANG C F,HUANG J J,HUANG L,et al.Electrochemical performance of LiCo1/3 Mn1/3Ni1/3O2hollow spheres as cathode material for lithium ion batteries[J].Journal of Power Sources,2013,226:219-222.
[3]王海权,胡志强,于洋,等.尖晶石型锰酸锂的复合掺杂改性[J].大连工业大学学报,2014,33(5):364-367.
[4]LEE S,PARK S S.Atomistic simulation study of mixed-metal oxide(LiNi1/3Co1/3Mn1/3O2)cathode material for lithium-ion battery[J].Journal of Physical Chemistry C,2012,116(10):6484-6489.
[5]WU F,WANG M,SU Y F,et al.A novel method for synthesis of layered LiNi1/3Mn1/3Co1/3O2as cathode material for lithium-ion battery[J].Journal of Power Sources,2010,195(8):2362-2367
[6]ZENG Y W.Investigation of LiNi1/3Co1/3Mn1/3O2cathode particles after 300discharge/charge cycling in a lithium-ion battery by analytical TEM[J].Journal of Power Sources,2008,183(1):316-324.
[7]GAO P,LI Y H,LIU H D,et al.Improved high rate capacity and lithium diffusion ability of LiNi1/3Co1/3Mn1/3O2 with ordered crystal structure[J].Journal of the Electrochemical Society,2012,159(4):A506-A513.
[8]ZHU J X,VO T,LID S,et al.Crystal growth of Li[Ni1/3Co1/3Mn1/3]O2as a cathode material for highperformance lithium ion batteries[J].Crystal Growth and Design,2012,12(3):1118-1123.
[9]TODOROV Y M,NUMATA K.Effects of the Li:(Mn+Co+Ni)molar ratio on the electrochemical properties of LiMn1/3Co1/3 Ni1/3 O2 cathode material[J].Electrochimica Acta,2004,50(2/3):495-499.
[10]FEGUS J W.Recent developments in cathode materials for lithium ion batteries[J].Journal of Power Sources,2010,195(4):939-954.
[11]熊礼龙,徐友龙,陶韬.Ge4+、Sn4+掺杂尖晶石LiMn2O4的合成与电化学表征[J].物理化学学报,2013,29(4):763-769.
[12]OHZUKU T,MAKIMURA Y.Layered lithium insertion material of LiCo1/3Ni1/3Mn1/3O2for lithiumion batteries[J].Chemistry Letters,2001,30(7):642-643.
[13]YABUUCHI N,OHZUKU T.Novel lithium insertion material of Li[Ni1/3Co1/3Mn1/3]O2for advanced lithium-ion batteries[J].Journal of Power Sources,2003,119/120/121(1/2):171-174.
[14]SHAJU K M,SUBBA G V,CHOWDARI B V R.Performance of layered LiNi1/3Co1/3Mn1/3O2as cathode for Li-ion batteries[J].Electrochimica Acta,2002,48(2):145-151.
[15]CHOI J,MANTHIAM A.Role of chemical and structural stabilities on the electrochemical properties of layered LiNi1/3Mn1/3Co1/3O2 cathodes[J]Journal of the Electrochemical Society,2005,152(9):A1714-A1718.
[16]LIAO L,WANG X Y,LUO X F,et al.Synthesis and electrochemical properties of layered cathode Li[Ni0.333Mn0.293Al0.04]O2-xFx materials prepared by the sol-gel method[J].Journal of Power Sources,2006,160(1):657-661.
[17]KIM G H,MYUNG S T,KIM H S,et al.Synthesis of spherical Li[Ni(1/3-z)Co(1/3-z)Mn(1/3-z)Mgz]O2 as positive electrode material of lithium-ion battery[J].Electrochimica Acta,2006,51(12):2447-2453.