EDTA辅助合成Li_2MnSiO_4/C纳米复合锂离子电池正极材料及性能
|
摘要
以乙二胺四乙酸(EDTA)为配位剂,采用溶胶凝胶和溶剂热法相结合的方法合成了Li2MnSiO4/C纳米复合正极材料。经过EDTA配位的锂锰硅前驱体在氩气中经过700℃煅烧后,产生为颗粒尺寸约为50 nm的Li2MnSiO4/C纳米复合粉体。在0.1C=33mA·g-1进行充放电测试时,其首次充电和放电比容量分别为223和140 mAh·g-1,第5次循环放电比容量仍为138 mAh·g-1;电流密度升至0.2C=66 mA·g-1时,在第20次循环的放电比容量仍可稳定在80 mAh·g-1左右。这些结果表明,EDTA的配位作用可抑制杂相的形成,这种分散性相对较好的纳米复合粉体Li2MnSiO4正极材料表现出提高的循环稳定性。
Li2MnSiO4/C nanospheres were prepared by combining the sol-gel and solvothermal processing using ethylene diamine tetraacetic acid(EDTA) as a chelating agent. After calcined under Ar atmosphere at 700 ℃, the(Li, Mn, Si)precursor complexed by EDTA transformed into Li2MnSiO4/C nanocomposite particles approximately 50 nm in diameter. The initial charge and discharge specific capacities of the sample are 223 and 140 mAh·g-1 at a current density of 33 mA·g-1(0.1C), respectively, and fifth discharge specific capacity can be achieved 138 mAh·g-1. The discharge specific capacity still is stabilized at around 80 mAh·g-1at a current density of 66 mA· g-1(0.2C) after 20 cycles. These results indicate that EDTA can prevent secondary crystalline phase of forming during calcinations. Such well-dispersed nano-powder exhibits improved cycleability for Li2MnSiO4cathode.
Li2MnSiO4/C nanospheres were prepared by combining the sol-gel and solvothermal processing using ethylene diamine tetraacetic acid(EDTA) as a chelating agent. After calcined under Ar atmosphere at 700 ℃, the(Li, Mn, Si)precursor complexed by EDTA transformed into Li2MnSiO4/C nanocomposite particles approximately 50 nm in diameter. The initial charge and discharge specific capacities of the sample are 223 and 140 mAh·g-1 at a current density of 33 mA·g-1(0.1C), respectively, and fifth discharge specific capacity can be achieved 138 mAh·g-1. The discharge specific capacity still is stabilized at around 80 mAh·g-1at a current density of 66 mA· g-1(0.2C) after 20 cycles. These results indicate that EDTA can prevent secondary crystalline phase of forming during calcinations. Such well-dispersed nano-powder exhibits improved cycleability for Li2MnSiO4cathode.
引文
[1]Nytén A,Abouimrane A,Armand M,et al.Electrochem.Commun.,2005,7(2):156-160
[2]ZUO Peng-Jian(左朋建),WANG Zhen-Bo(王振波),YIN GePing(尹鸽平),et al.Materials Review(材料导报),2009,23(6):28-31
[3]Wu X Z,Jiang X,Huo Q S,et al.Electrochim.Acta,2012,80:50-55
[4]Bai J Y,Gong Z J,Lv D P,et al.J.Mater.Chem.,2012,22:12128-12132
[5]Fan X Y,Li Y,Wang J J,et al.J.Alloys Compd.,2010,493:77-80
[6]Dompablo Arroyo-de M E,Armand M,Tarascon J M,et al.Electrochem.Commun.,2006,8:1292-1294
[7]Islam S M.Phil.Trans.R.Soc.A,2010,368:3255-3267
[8]Dominko R.J.Power Sources,2008,184:462-468
[9]Dominko R,Bele M,Gabercek M,et al.Electrochem Commun.,2006,8:217-222
[10]Shao B,Abe Y,Taniguchi I.Powder Technol.,2013,235:1-8
[11]Li Y X,Gong Z L,Yang Y.J.Power Sources,2007,174(2):528-532
[12]Liu S,Xu J,Li D Z,et al.J.Power Sources,2013,232:258-263
[13]Liu J,Xu H Y,Jiang X L,et al.J.Power Sources,2013,231:39-43
[14]Aravindan V,Ravi S,Kim W S,et al.J.Colloid Interface Sci.,2011,355:472-477
[15]WEI Yi(魏怡),WANG Li-Juan(王利娟),YAN Ji(闫继),et al.Acta Phys.-Chim.Sin.(物理化学学报),2011,27(11):2587-2592
[16]Aricoa S,Bruce P,Scrosati B,et al.Nat.Mater.,2005,4:366-377
[17]Li D L,Kong L B,Zhang L Y,et al.J.Non-Cryst.Solids,2000,271:45-55
[18]LI Dong-Lin(李东林),TIAN Miao(田苗),LI Qian(李倩),et al.Chinese J.Inorg.Chem.(无机化学学报),2013,29(9):1903-1908
[19]Li D L,Tian M,Xie R,et al.J.Alloys Compd.,2014,582:88-95
[20]Wang J,Li D L,Fan X Y,et al.J.Alloys Compd.,2012,516:33-38
[21]JIANG Wei(姜炜),LI Feng-Sheng(李凤生),CHEN LingYun(陈令允),et al.Acta Phys.-Chim.Sin.(物理化学学报),2005,21(2):182-186
[22]XI Guo-Xi(席国喜),LIU Yu-Min(刘玉民),QI Shi-Mei(戚世梅),et al.Bull.Chin.Ceram.Soc.(硅酸盐通报),2009,28(1):194-199
[23]ZHU Chen-Fei(朱承飞),XUE Jin-Hua(薛金花),WANG Li(王李),et al.Chinese J.Inorg.Chem.(无机化学学报),2010,26(7):1165-1170
[24]Di Noto V,Münchow V,Vittadello M,et al.Macromol.Chem.Phys.,2002,203:1211-1216
[25]Li D Y,Zhang L Y,Yao X.J.Non-Cryst.Solids,2008,354:1774-1778
[26]Dompablo Arroyo y de M E,Amador U,Gallardo-Amores J M,et al.J.Power Sources,2009,189:638-642
[27]Li D L,Zhou H S,Honma I.Chem.Commun.,2005,41:5187-5189
[28]Li D L,Zhou H S,Honma I.Nat.Mater.,2004,3:65-72
[29]Li D L,Tian M,Xie R,et al.Nanoscale,2014,6:3302-3308
[2]ZUO Peng-Jian(左朋建),WANG Zhen-Bo(王振波),YIN GePing(尹鸽平),et al.Materials Review(材料导报),2009,23(6):28-31
[3]Wu X Z,Jiang X,Huo Q S,et al.Electrochim.Acta,2012,80:50-55
[4]Bai J Y,Gong Z J,Lv D P,et al.J.Mater.Chem.,2012,22:12128-12132
[5]Fan X Y,Li Y,Wang J J,et al.J.Alloys Compd.,2010,493:77-80
[6]Dompablo Arroyo-de M E,Armand M,Tarascon J M,et al.Electrochem.Commun.,2006,8:1292-1294
[7]Islam S M.Phil.Trans.R.Soc.A,2010,368:3255-3267
[8]Dominko R.J.Power Sources,2008,184:462-468
[9]Dominko R,Bele M,Gabercek M,et al.Electrochem Commun.,2006,8:217-222
[10]Shao B,Abe Y,Taniguchi I.Powder Technol.,2013,235:1-8
[11]Li Y X,Gong Z L,Yang Y.J.Power Sources,2007,174(2):528-532
[12]Liu S,Xu J,Li D Z,et al.J.Power Sources,2013,232:258-263
[13]Liu J,Xu H Y,Jiang X L,et al.J.Power Sources,2013,231:39-43
[14]Aravindan V,Ravi S,Kim W S,et al.J.Colloid Interface Sci.,2011,355:472-477
[15]WEI Yi(魏怡),WANG Li-Juan(王利娟),YAN Ji(闫继),et al.Acta Phys.-Chim.Sin.(物理化学学报),2011,27(11):2587-2592
[16]Aricoa S,Bruce P,Scrosati B,et al.Nat.Mater.,2005,4:366-377
[17]Li D L,Kong L B,Zhang L Y,et al.J.Non-Cryst.Solids,2000,271:45-55
[18]LI Dong-Lin(李东林),TIAN Miao(田苗),LI Qian(李倩),et al.Chinese J.Inorg.Chem.(无机化学学报),2013,29(9):1903-1908
[19]Li D L,Tian M,Xie R,et al.J.Alloys Compd.,2014,582:88-95
[20]Wang J,Li D L,Fan X Y,et al.J.Alloys Compd.,2012,516:33-38
[21]JIANG Wei(姜炜),LI Feng-Sheng(李凤生),CHEN LingYun(陈令允),et al.Acta Phys.-Chim.Sin.(物理化学学报),2005,21(2):182-186
[22]XI Guo-Xi(席国喜),LIU Yu-Min(刘玉民),QI Shi-Mei(戚世梅),et al.Bull.Chin.Ceram.Soc.(硅酸盐通报),2009,28(1):194-199
[23]ZHU Chen-Fei(朱承飞),XUE Jin-Hua(薛金花),WANG Li(王李),et al.Chinese J.Inorg.Chem.(无机化学学报),2010,26(7):1165-1170
[24]Di Noto V,Münchow V,Vittadello M,et al.Macromol.Chem.Phys.,2002,203:1211-1216
[25]Li D Y,Zhang L Y,Yao X.J.Non-Cryst.Solids,2008,354:1774-1778
[26]Dompablo Arroyo y de M E,Amador U,Gallardo-Amores J M,et al.J.Power Sources,2009,189:638-642
[27]Li D L,Zhou H S,Honma I.Chem.Commun.,2005,41:5187-5189
[28]Li D L,Zhou H S,Honma I.Nat.Mater.,2004,3:65-72
[29]Li D L,Tian M,Xie R,et al.Nanoscale,2014,6:3302-3308