以钛铁矿为原料,经机械活化-盐酸浸出得到水解钛渣和富铁浸出液；用H2O2将水解钛渣中的Ti配位溶出,得到配位浸出液,并以其为反应物制备纳米级片状的过氧钛化合物；该过氧钛化合物经洗涤、煅烧制备得到纳米级片状的TiO2,其纯度高达99.31％(质量分数).将过氧钛化合物与Li2CO3混合,球磨后煅烧合成性能优良的锂离子电池负极材料Li4Ti5O12.以富铁浸出液为原料,经选择性沉淀制备含少量Al和Ti的FePO4·xH2O,并以其为前驱体制备了Al-Ti掺杂的LiFePO4.该LiFePO4在1C和2C倍率下的首次放电比容量分别达151.3和140.1(mA·h)/g,循环100次之后容量无衰减.该方法也可用于钛白粉副产品硫酸亚铁的回收利用,制备性能优异的LiFePO4.
参考文献
| [1] | Ohzuku T.;Yamamoto N.;Ueda A. .ZERO-STRAIN INSERTION MATERIAL OF LI[LI1/3TI5/3]O-4 FOR RECHARGEABLE LITHIUM CELLS[J].Journal of the Electrochemical Society,1995(5):1431-1435. |
| [2] | K. Zaghib;M. Simoneau;M. Armand;M. Gauthier .Electrochemical study of Li_4Ti_5O_12 as negative electrode for Li-ion polymer rechargeable batteries[J].Journal of Power Sources,1999(0):300-305. |
| [3] | Padhi AK.;Goodenough JB.;Nanjundaswamy KS. .PHOSPHO-OLIVINES AS POSITIVE-ELECTRODE MATERIALS FOR RECHARGEABLE LITHIUM BATTERIES[J].Journal of the Electrochemical Society,1997(4):1188-1194. |
| [4] | Synthesis of carbon-coated LiFePO_4 nanoparticles with high rate performance in lithium secondary batteries[J].Journal of Power Sources,2010(11):3661. |
| [5] | WOLFENSTINE J;LEE U;ALLEN J L .Electrical conductivity and rate-capability of Li4Ti5O12 as a function of heat-treatment atmosphere[J].Journal of Power Sources,2006,154(01):287-289. |
| [6] | GAO J;JIANG C;YING J;WAN C .Preparation and characterization of high-density spherical Li4Ti5O12 anode material for lithium secondary batteries[J].Journal of Power Sources,2006,155(02):364-367. |
| [7] | Seo Hee Ju;Yun Chan Kang .Characteristics of spherical-shaped Li4Ti5O12 anode powders prepared by spray pyrolysis[J].The journal of physics and chemistry of solids,2009(1):40-44. |
| [8] | SHIN-ICHI NISHIMURA;GENKI KOBAYASHI;KENJI OHOYAMA .Experimental visualization of lithium diffusion in Li_xFePO4[J].Nature materials,2008(9):707-711. |
| [9] | Y. Hu;M. M. Doeff;R. Kostecki .Electrochemical Performance of Sol-Gel Synthesized LiFePO_4 in Lithium Batteries[J].Journal of the Electrochemical Society,2004(8):A1279-A1285. |
| [10] | WANG Y;WANG J;YANG J;NULI Y .High-rate LiFePO4 electrode material synthesized by a novel route from FePO4@4H2O[J].Advanced Functional Materials,2006,16:2135-2140. |
| [11] | Hui-ping Liu;Zhi-xing Wang;Xin-hai Li;Hua-jun Guo;Wen-jie Peng;Yun-he Zhang;Qi-yang Hu .Synthesis And Electrochemical Properties Of Olivine Lifepo_4 Prepared By A Carbothermal Reduction Method[J].Journal of Power Sources,2008(2):469-472. |
| [12] | Jun-chao Zheng;Xin-hai Li;Zhi-xing Wang;Hua-jun Guo;Shao-yun Zhou .Lifepo_4 With Enhanced Performance Synthesized By A Novel Synthetic Route[J].Journal of Power Sources,2008(2):574-577. |
| [13] | Zhu BQ;Li XH;Wang ZX;Guo HJ .Novel synthesis of LiFePO4 by aqueous precipitation and carbothermal reduction[J].Materials Chemistry and Physics,2006(2/3):373-376. |
| [14] | 王志兴,伍凌,李新海,胡启阳,郭华军,彭文杰,张云河.LiFePO4的前驱体制备与性能[J].功能材料,2008(04):614-617. |
| [15] | Muxina Konarova;Izumi Taniguchi .Preparation of carbon coated LiFePO4 by a combination of spray pyrolysis with planetary ball-milling followed by heat treatment and their electrochemical properties[J].Powder Technology: An International Journal on the Science and Technology of Wet and Dry Particulate Systems,2009(1/2):111-116. |
| [16] | Hui Yang;Xing-Long Wu;Min-Hua Cao .Solvothermal Synthesis of LiFePO4 Hierarchically Dumbbell-Like Microstructures by Nanoplate Self-Assembly and Their Application as a Cathode Material in Lithium-Ion Batteries[J].The journal of physical chemistry, C. Nanomaterials and interfaces,2009(8):3345-3351. |
| [17] | Liu, H;Xie, JY;Wang, K .Synthesis and characterization of LiFePO4/(C+Fe2P) composite cathodes[J].Solid state ionics,2008(27/32):1768-1771. |
| [18] | Nonglak Meethong;Yu-Hua Kao;Scott A. Speakman;Yet-Ming Chiang .Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties[J].Advanced functional materials,2009(7):1060-1070. |
| [19] | CHUNG S Y;BLOKING J T;CHIANG Y M .Electronically conductive phospho-olivines as lithium storage electrodes[J].Nature Materials,2002,1(02):123-128. |
| [20] | Shahua Huang;Zhaoyin Wen;Zhonghua Gu;Xiujian Zhu .Preparation and cycling performance of Al{sup}(3+)and F{sup}- co-substituted compounds Li{sub}4Al{sub}xTi{sub{(5-x)F{sub}yO{sub}(12-y)[J].Electrochimica Acta,2005(20):4057-4062. |
| [21] | 莫畏;邓国珠;罗方承.钛冶金[M].北京:冶金工业出版社,1998:118-125. |
| [22] | Wu, L;Li, XH;Wang, ZX;Guo, HJ;Wang, XJ;Wu, FX;Fang, J;Wang, ZG;Li, LJ .A novel process for producing synthetic rutile and LiFePO4 cathode material from ilmenite[J].Journal of Alloys and Compounds: An Interdisciplinary Journal of Materials Science and Solid-state Chemistry and Physics,2010(1):271-278. |
| [23] | Ling Wu;Xinhai Li;Zhixing Wang .Preparation of synthetic rutile and metal-doped LiFePO4 from ilmenite[J].Powder Technology: An International Journal on the Science and Technology of Wet and Dry Particulate Systems,2010(3):293-297. |
| [24] | 伍凌 .综合利用钛铁矿制备锂离子电池正极材料LiFePO4和负极材料Li4Ti5O12的研究[D].中南大学,2011. |
| [25] | Feixiang Wu;Xinhai Li;Zhixing Wang .Hydrogen peroxide leaching of hydrolyzed titania residue prepared from mechanically activated Panzhihua ilmenite leached by hydrochloric acid[J].International Journal of Mineral Processing,2011(1/2):106-112. |
| [26] | Feixiang Wu;Xinhai Li;Zhixing Wang .Preparation of TiO2 nanosheets and Li4Ti5O_(12) anode material from natural ilmenite[J].Powder Technology: An International Journal on the Science and Technology of Wet and Dry Particulate Systems,2011(1/3):192-198. |
| [27] | LI C;LIANG B;WANG H .Preparation of synthetic mtile by hydrochloric acid leaching of mechanically activated Panzhihua ilmenite[J].Hydrometallurgy,2008,91(1/4):121-129. |
| [28] | Xiaojuan Wang;Xinhai Li;Zhixing Wang .Preparation and characterization of Li4Ti5O_(12) from ilmenite[J].Powder Technology: An International Journal on the Science and Technology of Wet and Dry Particulate Systems,2010(2/3):198-202. |
| [29] | DUNNINGTON F P .On metatitanic acid and the estimation of titanium by hydrogen peroxide[J].Journal of the American Chemical Society,1891,13(07):210-211. |
| [30] | SCHWARZENBACH G;MUEHLEBACH J;MUELLER K .Peroxo complexes of titanium[J].Inorganic Chemistry,1970,9(11):2381-2390. |
| [31] | SCHWARZENBACH G .Structure of a chelated dinuclear peroxytitanium(Ⅳ)[J].Inorganic Chemistry,1970,9(11):2391-2397. |
| [32] | BAO N;SHEN L;FENG X;LU X .High quality and yield in potassium titanate whiskers synthesized by calcinations from hydrous titania[J].Journal of the American Ceramic Society,2004,87(03):326-330. |
| [33] | Feixiang Wu;Xinhai Li;Zhixing Wang .A novel method to synthesize anatase TiO_2 nanowires as an anode material for lithium-ion batteries[J].Journal of Alloys and Compounds: An Interdisciplinary Journal of Materials Science and Solid-state Chemistry and Physics,2011(8):3711-3715. |
| [34] | Feixiang Wu;Xinhai Li;Zhixing Wang;Huajun Guo;Ling Wu;Xunhui Xiong;Xiaojuan Wang .Inexpensive synthesis of anatase TiO_2 nanowires by a novel method and its electrochemical characterization[J].Materials Letters,2011(10):1514-1517. |
| [35] | WU F;WANG Z;LI X;GUO H .Hydrogen titanate and TiO2 nanowires as anode materials for lithium-ion batteries[J].Journal of Materials Chemistry,2011,21:12675-12681. |
| [36] | 马慧娟.钛冶金学[M].北京:冶金工业出版社,1982:31-58. |
| [37] | 郑俊超,李新海,王志兴,郭华军,王丹琴.制备过程pH值对FePO4·xH2O及LiFePO4性能的影响[J].中国有色金属学报,2008(05):867-872. |
| [38] | L.Q. Sun;R.H. Cui;A.F. Jalbout;M.J. Li;X.M. Pan;R.S. Wang;H.M. Xie .LiFePO_4 as an optimum power cell material[J].Journal of Power Sources,2009(1):522-526. |
| [39] | Ke Wang;Rui Cai;Tao Yuan;Xing Yu;Ran Ran;Zongping Shao .Process investigation, electrochemical characterization and optimization of LiFePO{sub}4/C composite from mechanical activation using sucrose as carbon source[J].Electrochimica Acta,2009(10):2861-2868. |
| [40] | Liu, ZL;Zhang, XH;Hong, L .Preparation and electrochemical properties of spherical LiFePO4 and LiFe0.9Mg0.1PO4 cathode materials for lithium rechargeable batteries[J].Journal of Applied Electrochemistry,2009(12):2433-2438. |
| [41] | G.X.Wang;S.Bewlay;S.A.Needham .Synthesis and Characterization of LiFePO_4 and LiTi_(0.01)Fe_(0.99)PO_4 Cathode Materials[J].Journal of the Electrochemical Society,2006(1):A25-A31. |
| [42] | 杨佳,李奎,汤爱涛,潘复生.钛铁矿资源综合利用现状与发展[J].材料导报,2003(08):44-46. |
| [43] | 孙康.钛提取冶金物理化学[M].北京:冶金工业出版社,2001:7-12. |
| [44] | 葛英勇;秦贵平 .利用七水硫酸亚铁生产-水硫酸亚铁及聚合硫酸铁[J].无机盐工业,1999,31(05):29-30. |
| [45] | 蔡传琦;曾昭仪;徐启利 .钛白废副硫酸亚铁生产氧化铁红颜料的方法[P].中国专利,ZL02148428.7,2002-12-04. |
| [46] | 黄平峰.用钛白副产硫酸亚铁生产氧化铁系列颜料[J].无机盐工业,2003(05):7-9. |
| [47] | Ling Wu;Xin-hai Li;Zhi-xing Wang;Ling-jun Li;Jun-chao Zheng;Hua-jun Guo;Qi-yang Hu;Jie Fang .Synthesis and electrochemical properties of metals-doped LiFePO_4 prepared from the FeSO_4·7H_2O waste slag[J].Journal of Power Sources,2009(1):681-684. |
| [48] | Ling Wu;Zhixing Wang;Xinhai Li;Huajun Guo;Lingjun Li;Xiaojuan Wang;Junchao Zheng .Cation-substituted LiFePO_4 prepared from the FeSO_(4.7)H_2O waste slag as apotential Li battery cathode material[J].Journal of Alloys and Compounds: An Interdisciplinary Journal of Materials Science and Solid-state Chemistry and Physics,2010(1/2):278-284. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%