硅业副产物四氯化硅在离子液体中溶解—电沉积的研究
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摘要
研究多晶硅工业的主要副产品四氯化硅(SiCl_4)在离子液体中的溶解、电沉积过程。结果表明,SiCl_4在离子液体中的溶解度随温度升高而降低,离子液体的导电率随温度升高而增加。在阴离子为[TNf_2]的情况下,阳离子为[N_(1114)]的季铵盐类离子液体比咪唑类[Bmim]离子液体具有更好的SiCl_4溶解度和导电性。SiCl_4在季铵盐类离子液体的溶解度随烷基主链长度增加而增大,随侧链长度增加而降低。[N_(1114)][TNf_2]和SiCl_4之间形成C-Cl、Si-O和C-Si键,在[N_(1114)][TNf_2]-SiCl_4体系中S_i~(4+)的还原电位为-2.2V。在温度25℃、SiCl_4浓度0.3mol/L、电流密度20A/m~2、电解时间2h的条件下可电沉积得到较为致密的硅薄膜,呈球形颗粒状分布。
Dissolution and electrodeposition process of silicon tetrachloride(SiCl_4)in ionic liquids were investigated.The results show that solubility of SiCl_4in ionic liquid drops with increase of temperature,and conductivity of ionic liquid rises with increase of temperature.When anion is[TNf_2],quaternary ammonium ionic liquid with cation of[N_(1114)]has better solubility of SiCl_4and conductivity than that of imidazole[Bmim]ionic liquid.Solubility of SiCl_4in quaternary ammonium ionic liquid rises with increase of alkyl backbone length,and drops with increase of side chain length.C-Cl,Si-O and C-Si bonds are formed between[N_(1114)][TNf_2]and SiCl_4.Reduction potential of Si ~(4+)in[N_(1114)][TNf_2]-SiCl_4system is-2.2V.Dense silicon film with spherical particle distribution can be obtained by electrowinning at temperature of 25℃,concentration of SiCl_4of 0.3mol/L,current density of 20A/m~2,and electrolysis time of 2h.
Dissolution and electrodeposition process of silicon tetrachloride(SiCl_4)in ionic liquids were investigated.The results show that solubility of SiCl_4in ionic liquid drops with increase of temperature,and conductivity of ionic liquid rises with increase of temperature.When anion is[TNf_2],quaternary ammonium ionic liquid with cation of[N_(1114)]has better solubility of SiCl_4and conductivity than that of imidazole[Bmim]ionic liquid.Solubility of SiCl_4in quaternary ammonium ionic liquid rises with increase of alkyl backbone length,and drops with increase of side chain length.C-Cl,Si-O and C-Si bonds are formed between[N_(1114)][TNf_2]and SiCl_4.Reduction potential of Si ~(4+)in[N_(1114)][TNf_2]-SiCl_4system is-2.2V.Dense silicon film with spherical particle distribution can be obtained by electrowinning at temperature of 25℃,concentration of SiCl_4of 0.3mol/L,current density of 20A/m~2,and electrolysis time of 2h.
引文
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[2]ZHANG J W,YIN X X,XIN Y N,et al.Numerical investigation on three-dimensional dispersion and conversion behaviors of silicon tetrachloride release in the atmosphere[J].Journal of Hazardous Materials,2015,288:1-16.
[3]张妙鹤,唐安江,韦德举.太阳能级多晶硅生产工艺的比较研究[J].广州化工,2015,43(2):10-12.
[4]吕咏梅.四氯化硅工业应用研究进展[J].氯碱工业,2008,44(5):17-25.
[5]NISHIMURA Y,FUKUNAKA Y,NISHIDA T,et al.Electrodeposition of Si thin film in a hydrophobic roomtemperature molten salt[J].Electrochemical and SolidState Letters,2008,11(9):D75-D79.
[6]CARDIANO P,MINEO P G,NERI F,et al.A new application of ionic liquids:Hydrophobic properties of tetraalkylammonium-based poly(ionic liquid)s[J].Journal of Materials Chemistry,2008,18(11):1253-1260.
[7]王军.离子液体的性能及应用[M].北京:中国纺织出版社,2007:122-134.
[8]田鹏.离子液体的物理化学性质[J].沈阳师范大学学报(自然科学版),2011,29(2):129-137.
[9]孙杰,明庭云,钱慧璇.BMIMPF6离子液体中铜沉积的电化学行为[J].高等学校化学学报,2018,39(7):1497-1502.
[10]郑勇,郑永军,武卫明,等.乙酰胺型离子液体在铝电沉积中的应用研究[J].有色金属(冶炼部分),2017(9):15-18.
[11]郑勇,王倩,郑永军,等.微纳米铝在氯铝酸离子液体中的电沉积规律[J].有色金属(冶炼部分),2017(10):32-35.
[12]苗睿瑛,张小伟,李雅翀,等.离子液体中电沉积稀土金属的研究现状[J].有色金属(冶炼部分),2018(6):39-44.
[13]SARMA P R L,RAMAMOHAN T R,VENKATACHALAMS,et al.Vibrational modes in electrodeposited amorphous silicon:FT-IR analysis[J].Journal of Materials Science,1992,27(17):4762-4771.
[14]ABEDIN S Z E,BORISSENKO N,ENDRES F.Electrodeposition of nanoscale silicon in a room temperature ionic liquid[J].Electrochemistry Communications,2004,6(5):510-514.
[15]ZHANG J L,CHEN S,ZHANG H,et al.Electrodeposition of crystalline silicon directly from silicon tetrachloride in ionic liquid at low temperature[J].Rsc Advances,2016,6(15):12061-12067.
[16]李亚琼.离子液体电沉积制备单质硅的研究[D].沈阳:东北大学,2009.
[17]赵忠奎,袁冰,李宗石,等.环境友好的离子液体及其在付-克反应中的应用[J].中国基础科学,2004,6(1):19-25.
[18]王少坤,王兰云,徐永亮,等.阴、阳离子影响离子液体溶解甲烷性能的研究进展[J].环境工程,2016,34(2):164-169.
[19]张跃宏,李亚琼,李斌川,等.SiCl4/TMAC-PC体系电沉积硅的研究[J].有色金属(冶炼部分),2015(5):66-70.