|
- 2015
富锂锰基层状正极材料0.6Li[Li1/3Mn2/3]O2?0.4LiNixMnyCo1-x-yO2(x < 0.6,y > 0)的制备及性能研究
|
Abstract:
摘要 采用碳酸盐共沉淀法合成出前驱体,然后通过高温固相法制备了富锂锰基材料0.6Li[Li1/3Mn2/3]O2?0.4LiNixMnyCo1-x-yO2(x < 0.6,y > 0). 使用扫描电镜(SEM)、X射线衍射(XRD)以及电化学方法等手段进行了表征. 高温原位XRD测试结果表明,随着温度和Ni含量增加,材料的晶胞参数发生较大变化,温度达800 oC时,高Ni组成的材料阳离子混排现象严重,并伴有尖晶石相生成. 电性能测试结果表明,在充放电电压为2.0 ~ 4.6 V、电流密度20 mA?g-1条件下,低Ni含量材料表现出较好的电化学性能,首周放电容量达260.1 mA?g-1,首次效率为83.2%,经过50次循环后放电容量保持率高达99.7%,且在电池循环过程中,放电电压平台下降较少.
Lithium-rich manganese based cathode materials 0.6Li[Li1/3Mn2/3]O2?0.4LiNixMnyCo1-x-yO2 (x < 0.6, y > 0) were synthesized by carbonate co-precipitation and high temperature solid-state reaction. The structures and morphologies of the as-prepared materials were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM). The results of high temperature in-situ XRD test show that the lattice parameters change significantly with increasing temperature and Ni content. The cation mixing gets serious and the spinel phase appears in the high Ni content samples when the temperature is up to 800 oC. Under voltages ranging from 2.0 to 4.6 V, the lower Ni content sample has the highest discharge capacity of 260.1 mA?g-1 (the initial coulombic efficiency of 83.2%) at current density of 20 mA?g-1, and the discharge capacity retention is up to 99.7% with the relatively smaller voltage decay after 50 cycles
[1] | Guo X J, Li Y X, Zheng M. Structural and electrochemical characterization of xLi[Li1/3Mn2/3]O2?(1-x)Li[Ni1/3Mn1/3Co1/3]O2 (0≤x≤0.9) as cathode materials for lithium ion batteries[J]. Journal of Power Sources, 2008, 184(2): 414-419. |
[2] | Kang S H, Thackeray M M. Stabilization of xLi2MnO3?(1-x)LiMO2 electrode surfaces (M = Mn, Ni, Co) with mildly acidic, fluorinated solutions[J]. Journal of the Electrochemical Society, 2008, 155(4): A269-A275. |
[3] | Wu Y, Mantithiram A. High capacity of surface-modified layered Li[Li(1-x)/3 Mn(2-x)/3Nix/3Cox/3]O2 cathodes with low irreversible capacity loss[J]. Electrochemical and Solid State Letters, 2006, 9(5): A221-A224. |
[4] | Borggel V, Markevich E, Aurbach D, et al. On the application of ionic liquids for rechargeable Li batteries: High voltage systems[J]. Journal of Power Sources, 2009, 189(1): 331-336. |
[5] | Lopez H A, Venkatachalam S, Kumat S, et al. Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling. US: US8389160B2[P]. 2013. |
[6] | Yang Y(杨越), Xu S M(徐盛明), Weng Y Q(翁雅青), et al. Preparation and characterization of xLi2MnO3?(1-x)Li( Ni1/3Co1/3Mn1/3)O2(x = 0.2, 0.4, 0.6) cathode materials synthesized by hydroxide co-precipitation method[J]. Journal of Functional Materials(功能材料), 2013, 19(44): 2878-2887. |
[7] | Armstrong A R, Holzapfel M. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2[J]. Journal of the American Chemical Society, 2006, 128(26): 8694-8698. |
[8] | Wang J, Qiu B, Cao H L, et al. Electrochemical properties of 0.6Li[Li1/3Mn2/3]O2?0.4LiNixMnyCo1-x-yO2 cathode materials for lithium-ion batteries[J]. Journal of Power Sources, 2012, 218: 128-133. |
[9] | Mohanty D, Kalnaus S, Roberta A, et al. Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction[J]. Journal of Power Sources, 2013, 229: 239-248. |
[10] | Shin S S, Sun Y K, Amine K. Synthesis and electrochemical properties of Li[Li(1-2x)/3NixMn(2-x)/3]O2 as cathode materials for lithium secondary batteries[J]. Journal of Power Sources, 2002, 112(2): 634-638. |
[11] | Yu L Y, Qiu W H, Lian F, et al. Understanding the phenomenon of increasing capacity of layered 0.65Li[Li1/3Mn2/3]O2?0.35Li(Ni1/3Co1/3Mn1/3)O2[J]. Journal of alloys and compounds, 2009, 471(1/2): 317-321. |
[12] | Liu X Q, Guo Z M. Synthesis of spherical Li1.167Ni0.2Co0.1Mn0.533O2 as cathode material for lithium-ion battery via co-precipitation[J]. Materials International, 2012, 22(2): 126-129. |
[13] | Kima J H, Park M S, Songa J H, et al. Effect of aluminum fluoride coating on the electrochemical and thermal properties of 0.5Li2MnO3?0.5LiNi0.5Co0.2Mn0.3O2 composite material[J]. Journal of Alloys and Compounds, 2012, 517: 20-25. |
[14] | Stoyanova R, Zhecheva E, Vassilev S, et al. Mn4+ environment in lavered Li[Mg0.5-xNixMn0.5]O2 oxides monitored by EPR spectroscopy[J]. Journal of Solid State Chemistry, 2006, 179(2): 378-388. |
[15] | Armstrong A R, Holzapfel M, Novak P, et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2[J]. Journal of America Chemistry Society, 2006, 128(26): 8694-8698. |
[16] | Lu Z, Dahn J R, Nahm K S, et al. Understanding the anomalous capacity of Li[NiLiMn]O cells using in situ X-ray diffraction and electrochemical studies[J]. Journal of the Electrochemical Society, 2002, 149(7): A815-A822. |
[17] | Zhang K C(张克从),Zhang L H(张乐慧). Science and technology of crystal growth[M]. Bejing: Science Press(科学出版社), 1997: 70-81. |
[18] | Lu Z, Beaulieu L Y, Donaberger. R A. Synthesis, structure, and electrochemical behavior of Li[NixLi1/3-2x/3Mn2/3-x/3]O2[J]. Journal of the Electrochemical Society, 2002, 149(6): A778-A791. |
[19] | Robertson A. D, Bruce P G, Kim J K, et al. Overcapacity of Li[NixLi1/3-2x/3Mn2/3-x/3]O2 electrodes[J]. Electrochemical and Solid State Letters, 2004, 7(9): A294-A298. |
[20] | Lee D K, Park S H, Amine K, et al. High capacity Li[Li0.2Ni0.2Mn0.6]O2 cathode materials via a carbonate co-precipitation method[J]. Journal of Power Sources, 2006, 162(2): 1346-1350. |
[21] | Sun Y K, Noh H J, Yoon C S, et al. Effect of Mn content in surface on the electrochemical properties of core-shell structured cathode materials[J]. Journal of the Electrochemical Society, 2012, 159(1): A1-A5. |