三维有序大孔Fe_2SiO_4/SiO_2@C锂离子电池负极纳米玻璃陶瓷-碳复合材料制备及电化学性能
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摘要
以聚苯乙烯(PS)胶晶作为铸模,采用纳米铸造工艺及后续煅烧的方法合成了三维有序大孔Fe_2SiO_4/SiO_2@C纳米玻璃陶瓷锂离子电池负极材料。溶胶-凝胶工艺产生的凝胶在650℃氩气氛炉中煅烧后,Fe_2SiO_4纳米晶体从含铁元素的SiO_2基玻璃中结晶析出,形成由Fe_2SiO_4纳米晶体、铁离子(Fe3+)修饰的玻璃态SiO_2和非晶碳组成的三维有序大孔纳米玻璃陶瓷。在50 m A·g~(-1)电流密度下进行充放电时,其放电容量可达450 m Ah·g~(-1)以上,电流密度增加到250 m A·g~(-1)时可逆放电容量仍旧稳定地保持在260 m Ah·g~(-1),而具有同样有序大孔结构和含碳量的非晶态SiO_2@C材料的放电比容量在50 m A·g~(-1)电流密度时仅为15 m Ah·g~(-1)。这些结果表明,Fe_2SiO_4纳米晶体及Fe~(3+)有助于SiO_2基玻璃陶瓷实现可逆储锂过程。
A three-dimensionally ordered macroporous(3DOM) Fe_2SiO_4/SiO_2@C nano-glass-ceramic as an anode material for lithium-ion battery is successfully synthesized using a polystyrene(PS) colloidal crystal nano-casting and post-calcination.After a gel is calcined at 650 ℃ under an argon atmosphere, Fe_2SiO_4nanocrystals grow from iron-containing SiO_2-based glass, resulting in 3DOM nano-glass-ceramic consisted of Fe_2SiO_4nanocrystals, Fe3 +-doped glassy SiO_2 and amorphous carbon.The resultant 3DOM Fe_2SiO_4/SiO_2@C nano-glass-ceramic exhibits a highly reversible discharge capacity up to 450 m Ah·g~(-1)at a current density of 50 m A·g~(-1), and 260 m Ah·g~(-1)at250 m A·g~(-1)in the voltage range of 0.05~3.0 V, while the 3DOM amorphous SiO_2@C composite with same porous structure only delivers 15 m Ah·g~(-1)at 50 m A·g~(-1).Compared to the 3DOM amorphous SiO_2@C composite, the 3DOM Fe_2SiO_4/SiO_2@C nano-glass-ceramic anode exhibits a significantly improved capacity and high-rate performancse.These results mean that the Fe_2SiO_4and Fe3 +can enhance reversible lithium storage capability and high-rate performances of SiO_2-based nano-glass-ceramics.
A three-dimensionally ordered macroporous(3DOM) Fe_2SiO_4/SiO_2@C nano-glass-ceramic as an anode material for lithium-ion battery is successfully synthesized using a polystyrene(PS) colloidal crystal nano-casting and post-calcination.After a gel is calcined at 650 ℃ under an argon atmosphere, Fe_2SiO_4nanocrystals grow from iron-containing SiO_2-based glass, resulting in 3DOM nano-glass-ceramic consisted of Fe_2SiO_4nanocrystals, Fe3 +-doped glassy SiO_2 and amorphous carbon.The resultant 3DOM Fe_2SiO_4/SiO_2@C nano-glass-ceramic exhibits a highly reversible discharge capacity up to 450 m Ah·g~(-1)at a current density of 50 m A·g~(-1), and 260 m Ah·g~(-1)at250 m A·g~(-1)in the voltage range of 0.05~3.0 V, while the 3DOM amorphous SiO_2@C composite with same porous structure only delivers 15 m Ah·g~(-1)at 50 m A·g~(-1).Compared to the 3DOM amorphous SiO_2@C composite, the 3DOM Fe_2SiO_4/SiO_2@C nano-glass-ceramic anode exhibits a significantly improved capacity and high-rate performancse.These results mean that the Fe_2SiO_4and Fe3 +can enhance reversible lithium storage capability and high-rate performances of SiO_2-based nano-glass-ceramics.
引文
[1]Szczech J R,Jin S.Energy Environ.Sci.,2011,4:56-72
[2]FU Ping-Ping(伏萍萍),SONG Ying-Jie(宋英杰),ZHANG Hong-Fang(张宏芳),et al.Chinese J.Inorg.Chem.(无机化学学报),2006,22(10):1823-1827
[3]Hwa Y,Kim W S,Hong S H,et al.Electrochim.Acta,2012,71:201-205
[4]Kim H,Seo M,Park M H,et al.Angew.Chem.Int.Ed.,2010,49:1-5
[5]Yang Z C,Guo J C,Xu S M,et al.Electrochem.Commun.,2013,28:40-43
[6]Chan C K,Peng H,Liu G,et al.Nat.Nanotechnol.,2008,3:31-35
[7]Chockla A M,Harris J T,Akhavan V A,et al.J.Am.Chem.Soc.,2011,133:20914-20921
[8]Wen Z,Lu G H,Mao S,et al.Electrochem.Commun.,2013,29:67-70
[9]Kim W S,Hwa Y,Shin J H,et al.Nanoscale,2014,6:4297-4302
[10]Guo B K,Shu J,Wang Z X,et al.Electrochem.Commun.,2008,10:1876-1878
[11]Liang Y,Cai L,Chen L,et al.Nanoscale,2015,7:3971-3975
[12]Yao Y,Zhang J,Xue L,et al.J.Power Sources,2011,196:10240-10243
[13]Chang W S,Park C M,Kim J H,et al.Energy Environ.Sci.,2012,5:6895-6899
[14]Wang J,Zhao H L,He J C,et al.J.Power Sources,2011,196:4811-4815
[15]Favors Z,Wang W,Bay H H,et al.Sci.Rep.,2014,4:4605
[16]Yan N,Wang F,Zhong H,et al.Sci.Rep.,2013,3:1568
[17]Li D L,Zhang L Y,Yao X.J.Non-Cryst.Solids,2008,354:1774-1779
[18]Li D L,Kong L B,Zhang L Y,et al.J.Non-Cryst.Solids,2000,271:45-55
[19]Li D L,Tian M,Xie R,et al.J.Alloys Compd.,2014,582:88-95
[20]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
[21]Li D L,Xie R,Tian M,et al.J.Mater.Chem.A,2014,2:4375-4383
[22]Li D L,Zhang W,Sun R,et al.Nanoscale,2016,8:12202-12214
[23]Li D L,Tian M,Xie R,et al.Nanoscale,2014,6:3302-3308
[24]Cui J F,Qing C X,Zhang Q T,et al.Ionics,2014,20(1):23-28
[25]Li D L,Yong H T H,Xie R,et al.RSC Adv.,2014,4(67):35541-35545
[26]Zhang Q T,Ge S W,Xue H T,et al.RSC Adv.,2014,4:58260-58264
[27]Yamashita T,Hayes P.Appl.Surf.Sci.,2008,254:2441-2449
[28]Nakatsuka Y,Akamatsu H,Murai S,et al.Jpn.J.Appl.Phys.,2014,53:1-5
[29]Wang J,Li D L,Fan X Y,et al.J.Alloys Compd.,2012,516:33-37
[30]Xu X,Cao R,Jeong S,et al.Nano Lett.,2012,12:4988-4991
[31]Xiong Q Q,Lu Y,Wang X L,et al.J.Alloys Compd.,2012,536:219-225
[32]Tsai T L,Markgraf S A,Dieckmann R.J.Cryst.Growth,1996,169:759-763
[33]Konon M Y,Stolyar S V.Glass Phys.Chem.,2015,41:665-667
[34]Shuan F,Zhou S,Chan Y,et al.J.Non-Cryst.Solids,1982,52:435-445
[35]Murawski L.J.Mater.Sci.,1982,17:2155-2163
[2]FU Ping-Ping(伏萍萍),SONG Ying-Jie(宋英杰),ZHANG Hong-Fang(张宏芳),et al.Chinese J.Inorg.Chem.(无机化学学报),2006,22(10):1823-1827
[3]Hwa Y,Kim W S,Hong S H,et al.Electrochim.Acta,2012,71:201-205
[4]Kim H,Seo M,Park M H,et al.Angew.Chem.Int.Ed.,2010,49:1-5
[5]Yang Z C,Guo J C,Xu S M,et al.Electrochem.Commun.,2013,28:40-43
[6]Chan C K,Peng H,Liu G,et al.Nat.Nanotechnol.,2008,3:31-35
[7]Chockla A M,Harris J T,Akhavan V A,et al.J.Am.Chem.Soc.,2011,133:20914-20921
[8]Wen Z,Lu G H,Mao S,et al.Electrochem.Commun.,2013,29:67-70
[9]Kim W S,Hwa Y,Shin J H,et al.Nanoscale,2014,6:4297-4302
[10]Guo B K,Shu J,Wang Z X,et al.Electrochem.Commun.,2008,10:1876-1878
[11]Liang Y,Cai L,Chen L,et al.Nanoscale,2015,7:3971-3975
[12]Yao Y,Zhang J,Xue L,et al.J.Power Sources,2011,196:10240-10243
[13]Chang W S,Park C M,Kim J H,et al.Energy Environ.Sci.,2012,5:6895-6899
[14]Wang J,Zhao H L,He J C,et al.J.Power Sources,2011,196:4811-4815
[15]Favors Z,Wang W,Bay H H,et al.Sci.Rep.,2014,4:4605
[16]Yan N,Wang F,Zhong H,et al.Sci.Rep.,2013,3:1568
[17]Li D L,Zhang L Y,Yao X.J.Non-Cryst.Solids,2008,354:1774-1779
[18]Li D L,Kong L B,Zhang L Y,et al.J.Non-Cryst.Solids,2000,271:45-55
[19]Li D L,Tian M,Xie R,et al.J.Alloys Compd.,2014,582:88-95
[20]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
[21]Li D L,Xie R,Tian M,et al.J.Mater.Chem.A,2014,2:4375-4383
[22]Li D L,Zhang W,Sun R,et al.Nanoscale,2016,8:12202-12214
[23]Li D L,Tian M,Xie R,et al.Nanoscale,2014,6:3302-3308
[24]Cui J F,Qing C X,Zhang Q T,et al.Ionics,2014,20(1):23-28
[25]Li D L,Yong H T H,Xie R,et al.RSC Adv.,2014,4(67):35541-35545
[26]Zhang Q T,Ge S W,Xue H T,et al.RSC Adv.,2014,4:58260-58264
[27]Yamashita T,Hayes P.Appl.Surf.Sci.,2008,254:2441-2449
[28]Nakatsuka Y,Akamatsu H,Murai S,et al.Jpn.J.Appl.Phys.,2014,53:1-5
[29]Wang J,Li D L,Fan X Y,et al.J.Alloys Compd.,2012,516:33-37
[30]Xu X,Cao R,Jeong S,et al.Nano Lett.,2012,12:4988-4991
[31]Xiong Q Q,Lu Y,Wang X L,et al.J.Alloys Compd.,2012,536:219-225
[32]Tsai T L,Markgraf S A,Dieckmann R.J.Cryst.Growth,1996,169:759-763
[33]Konon M Y,Stolyar S V.Glass Phys.Chem.,2015,41:665-667
[34]Shuan F,Zhou S,Chan Y,et al.J.Non-Cryst.Solids,1982,52:435-445
[35]Murawski L.J.Mater.Sci.,1982,17:2155-2163