以高温固相法合成的尖晶石型LiMn2O4前驱体为研究对象,通过对离子筛和离子筛吸附产物的化学分析、X射线衍射图谱分析、热重分析、红外分析和滤液中锂交换量与锰损失量分析,提出并验证了离子筛和吸附产物化学组成式可由LixMn2O4（0≤x≤1）表达,其结构依然保持尖晶石结构,阐明了以盐酸为洗脱剂离子筛提锂过程的氧化还原反应机理,给出了完善的洗脱过程与吸附过程反应式。实验结果表明,洗脱和吸附过程不彻底是导致离子筛吸附量与饱和吸附量相差较大的原因,离子筛中Mn3＋歧化是离子筛发生溶损的主因;提出了关于尖晶石型离子筛提锂深入研究关键问题的建议。
LiMn2O4 precursor was prepared by high temperature solid-state method. Ghemlcal analysis, A-ray powder diffraction analysis, thermal analysis and infrared analysis of adsorbed and eluted products were characterized, and the corresponding relationships between lithium exchange capacity and manganese dissolved loss were investigated. The chemical compositions of adsorbed and eluted products may be expressed by Lix Mn2O4 (0≤x≤1), which was proposed and verified for the first time, and their structures remain spinel-type. Redox reaction mechanisms of the adsorption and elution process were described in detail when hydrochloric acid was eluent, and more prefect chemical reaction equations were given. The experimental results showed that elution and adsorption process were not thoroughly and completely result in adsorption capacity of ionic sieve was low compared with saturated adsorption, and the disproportionation of Mn^3+ leaded to manganese dissolved loss. Furthermore the guiding suggestions for the further researches on extracting lithium with ionic sieve were proposed.
参考文献
| [1] | 贺慧,程璇,张颖,杨勇.锂离子电池正极材料的研究进展[J].功能材料,2004(06):667-671. |
| [2] | Kuthanapillil M. Shaju;Peter G. Bruce .A Stoichiometric Nano-LiMn2O4 Spinel Electrode Exhibiting High Power and Stable Cycling[J].Chemistry of Materials: A Publication of the American Chemistry Society,2008(17):5557-5562. |
| [3] | 孙淑英,张钦辉,于建国.用MnO_2离子筛吸附剂从溶液中提取锂[J].无机化学学报,2010(04):567-572. |
| [4] | Hon Y M;Lin S P;Fung K Z et al.Synthesis and characterization of nano-LiMn2O4 powder by tartaric acid gel process[J].Journal of the European Ceramic Society,2002,22(05):653-660. |
| [5] | Wang L;Meng CG;Han M;Ma W .Lithium uptake in fixed-pH solution by ion sieves[J].Journal of Colloid and Interface Science,2008(1):31-40. |
| [6] | 綦鹏飞,朱桂茹,王铎,高从堦.锂离子筛的制备及其吸附性能研究[J].功能材料,2010(03):432-435. |
| [7] | Zhang Qinhui;Sun Shuying;Li Shaopeng et al.Nanostructure ion-sieves for lithium adsorption[J].Chemical Engineering Science,2007,62(18-20):4869-4874. |
| [8] | Kim Y S;No K S;Chung K S et al.Li^+ extraction reactions with apinel-type LiM0.5 Mn1.5 O4(M = Ti,Fe)and their electronic atructures[J].Materials Letters,2003,57(26-27):4140-4146. |
| [9] | 袁俊生,孟兴智,纪志永.尖晶石型锂离子筛吸附剂前驱体的合成研究[J].海湖盐与化工,2005(01):6-9. |
| [10] | Shen X M;Clearfield A .Phase transitions and ion exchange behavior of electrolytically prepared manganese dioxide[J].Journal of Solid State Chemistry,1986,64(03):270-282. |
| [11] | Hunter J C .Preparation of a new crystal from of manganese dioxide:X-MnO2[J].Journal of Solid State Chemistry,1981,39(02):142-147. |
| [12] | Ooi K;Miyai;Katoh S et al.Topotaetic Li^+ insertion to X-MnO2 in the aqueous phase[J].Langmuir,1989,5(01):150-157. |
| [13] | Feng Q;Miyai Y;Kanoh H et al.Li^+ extraction/inlithium manganese oxides.Characterization of redox-type and ion-exchange-type sites[J].Langmuir,1992,7(08):18611867. |
| [14] | 纪志永 .锂吸附剂的合成及其吸附性能研究[D].河北工业大学,2004. |
| [15] | 陈永熙,周立娟,郭丽萍,张楠,赵俊.锂锰氧化物中锰的平均化合价的测定研究[J].武汉理工大学学报,2001(10):1-3. |
| [16] | Ammundsen B;Jones D J;Roziere J et al.Mechanism of proton insertion and characterization of the proton Sites in lithium manganese spinels[J].Chemistry of Materials,1995,7(11):2151-2160. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%