采用共沉淀-高温固相法合成正极材料LiNi0．7 Mn0．3 O 2,利用 X 射线衍射分析(XRD)表征其结构、扫描电子显微镜(SEM)表征其形貌、X 射线光电子能谱(XPS)表征其价态,最终确定了该材料最佳烧成温度为820℃.研究表明,该温度下合成的 LiNi0．7 Mn0．3 O 2具有典型的α-NaFeO 2型层状结构,颗粒形貌呈类球形且分布均匀；XPS 数据表明,LiNi0．7 Mn0．3 O 2中的 Ni 主要以＋3价形态存在,Mn 主要以＋4价形态存在.室温条件下以0．2 C 倍率在2．75~4．35 V 的电压范围内充放电,首次放电比容量高达188．9 mAh/g,70次循环后容量保持率为95．2％.
Layered cobalt free nickel rich LiNi0.7 Mn0.3 O 2 cathode material was synthesized via co-precipitation and high temperature sintering in this study.The optimum synthesis condition for LiNi0.7 Mn0.3 O 2 cathode material was investigated in detail.The crystal structure,morphology,valence state of elements and electrochemical performance for LiNi0.7 Mn0.3 O 2 cathode material were characterized and tested by means of powder X-ray dif-fraction (XRD),scanning electron microscopy (SEM),X-ray photoelectron spectroscopy (XPS)and galvanos-tatic charge/discharge test separately.The optimum sintering temperature for LiNi0.7 Mn0.3 O 2 cathode material was 820 ℃.The sample synthesized at optimum sintering temperature has a typical α-NaFeO 2 layered structure and homogeneous spherical morphology.XPS results suggest that Ni3 + and Mn4+ exist mainly in this sample. The initial discharge specific capacity of the material was 188.1 mAh/g at 0.2 C in the voltage range of 2.75-4.35 V,and even after 70 cycles,it still maintains 95.2% of the initial discharge specific capacity.
参考文献
| [1] | 胡晨,刘韩星,甘小燕,欧阳世翕.锂离子电池正极材料锂镍复合氧化物的合成及性能研究[J].功能材料,2004(z1):1851-1853,1856. |
| [2] | Megahed S;Scrosati B .Lithium-ion rechargeable batteries[J].Journal of Power Sources,1994,5 1(1):79-104. |
| [3] | Kyung-Keun Lee;Won-Sub Yoon;Kwang-Bum Kim .Thermal behavior and the decomposition mechanism of electrochemically delithiated Li_1-xNiO_2[J].Journal of Power Sources,2001(0):321-325. |
| [4] | Doron Aurbach;Alexander Schechter .Changes in the resistance of electrolyte solutions during contact with lithium electrodes at open circuit potential that reflect the Li surface chemistry[J].Electrochimica Acta,2001(15):2395-2400. |
| [5] | 梅佳,张骞,钟盛文,张淑静,初旭光,李月涛,刘庆国.Co、Mn包覆镍基材料LiNi0.90CO0.05Mn0.05O2的烧结温度与性能研究[J].电源技术,2007(05):376-381. |
| [6] | Ying J;Wan C;Jiang C et al.Preparation and character-ization of high-density spherical LiNi0.8 Co0.2 O 2 cathode material for lithium secondary batteries[J].Journal of Power Sources,2001,99(1-2):78-84. |
| [7] | 汤宏伟,朱志红,常照荣,陈中军.高密度锂离子电池正极材料LiNi0.8Co0.2O2合成的研究[J].功能材料,2007(06):945-946,951. |
| [8] | Periasamy P;Kim H S;Na S H et al.Synthesis and characterization of LiNi0.8 Co0.2 O 2 prepared by a combus-tion solution method for lithium batteries[J].Journal of Power Sources,2004,132(1):213-218. |
| [9] | Corina Taubert;Meike Fleischhammer;Margret Wohffahrt-Mehrens;Ulrich Wietelmann;Thorsten Buhrmester .LiBOB as Electrolyte Salt or Additive for Lithium-Ion Batteries Based on LiNi_(0.8)Co_(0.15)Al_(0.05)O_2/Graphite[J].Journal of the Electrochemical Society,2010(6):A721-A728. |
| [10] | Cheralathan K K;Kang N Y;Hun S U P et al.Prepa-ration of spherical LiNi0.80 Co0.15 Mn0.05 O 2 lithium-ion cathode material by continuous co-precipitation[J].Jour-nal of Power Sources,2010,195(5):1486-1494. |
| [11] | R. Kostecki;F. McLarnon .Local-Probe Studies of Degradation of Composite LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 Cathodes in High-Power Lithium-Ion Cells[J].Electrochemical and solid-state letters,2004(10):A380-A383. |
| [12] | Zhaolin Liu;Aishui yu;Jim Y. Lee .Synthesis and characterization of LiNi_1-x-yCo_xMn_yO_2 as the cathode materials of secondary lithium batteries[J].Journal of Power Sources,1999(0):416-419. |
| [13] | N. V. Kosova;E. T. Devyatkina;V. V. Kaichev .LiNi_(1-x-y)CO_xMn_yO_2 (x = y = 0.1, 0.2, 0.33) Cathode Materials Prepared Using Mechanical Activation: Structure, State of Ions, and Electrochemical Performance[J].Inorganic materials,2007(2):185-193. |
| [14] | Yang-Kook Sun;Dong-Ju Lee;Yun Jung Lee .Cobalt-Free Nickel Rich Layered Oxide Cathodes for Lithium-Ion Batteries[J].ACS applied materials & interfaces,2013(21):11434-11440. |
| [15] | D. Mohanty;P. Paudel;H. Gabrisch .Microstructure and magnetic behavior of compounds in the solid solution system Li [Ni1-xMnx] O2 (x=0.3, 0.5, 0.7)[J].Solid state ionics,2010(19/20):914-920. |
| [16] | Yoon WS.;Grey CP.;Balasubramanian M.;Yang XQ.;McBreen J. .In situ X-ray absorption spectroscopic study on LiNi0.5Mn0.5O2 cathode material during electrochemical cycling[J].Chemistry of Materials,2003(16):3161-3169. |
| [17] | Van der Ven A;Ceder G .Ordering in Li-x(Ni0.5Mn0.5)O-2 and its relation to charge capacity and electrochemical behavior in rechargeable lithium batteries[J].Electrochemistry communications,2004(10):1045-1050. |
| [18] | XIONG XiaoQin,JIANG Yan,XIA ShengAn,ZHANG WuXing,Yuan LiXia,LIU ShanTang,HUANG YunHui.Synthesis and modification of well-ordered layered cathode oxide LiNi2/3Mn1/3O2[J].科学通报（英文版）,2010(30):3419-3423. |
| [19] | Quine TE.;Armstrong AR.;Robertson AD.;Bruce PG.;Duncan MJ. .Layered LixMn1-yNiyO2 intercalation electrodes[J].Journal of Materials Chemistry: An Interdisciplinary Journal dealing with Synthesis, Structures, Properties and Applications of Materials, Particulary Those Associated with Advanced Technology,2000(12):2838-2841. |
| [20] | Gover R;Kanno R;Mitchell B et al.The effects of sin-tering time on the structure and electrochemical proper-ties of Li(Ni0.8 Co0.2)O 2[J].Journal of Power Sources,2000,90(1):82-88. |
| [21] | Ohzuku T;Ueda A;Nagayama M .Electrochemistry and structural chemistry of LiNiO 2(R3m)for 4 volt seconda-ry lithium cells[J].Journal of The Electrochemical Socie-ty,1993,140(7):1862-1870. |
| [22] | Thackeray MM. .STRUCTURAL CONSIDERATIONS OF LAYERED AND SPINEL LITHIATED OXIDES FOR LITHIUM ION BATTERIES[J].Journal of the Electrochemical Society,1995(8):2558-2563. |
| [23] | G.X. Wang;S.Zhong;D.H.Bradhurst;S.X.Dou;H.K.Liu .LiAlδNi1-δO2 solid solutions as cathodic materials for rechargeable lithium batteries[J].Solid state ionics,1999(3/4):271-277. |
| [24] | Rossen E;Jones C D W;Dahn J R .Structure and elec-trochemistry of Lix Mny Ni1-y O 2[J].Solid State Ionicis,1992,57(3):311-318. |
| [25] | Hirano A;Kanno R;Kawamoto Y et al.Neutron dif-fraction study of LiNi0.8 Mn0.2 O 2[J].Journal of Solid State Chemistry,1997,134(1):1-4. |
| [26] | Caurant D;Baffler N;Bianchi V et al.Preparation by a“chimie douce”route and characterization of(LiNiz Mn1-z O 2)(0.5≤z ≤1)cathode materials[J].Journal of Mate-rials Chemistry,1996,6(7):1149-1155. |
| [27] | Yang-Kook Sun;Bo-Ram Lee;Hyung-Ju Noh .A novel concentration-gradient Li[Ni_(0.83)Co_(0.07)Mn_(0.10)]O2 cathode material for high-energy lithium-ion batteries[J].Journal of Materials Chemistry: An Interdisciplinary Journal dealing with Synthesis, Structures, Properties and Applications of Materials, Particulary Those Associated with Advanced Technology,2011(27):10108-10112. |
| [28] | Yang-Kook Sun;Seung-Taek Myung;Byung-Chun Park .Synthesis of Spherical Nano-to Microscale Core-Shell Particles Li[(Ni_(0.8)Co_(0.1)Mn_(0.1))_(1-x)(Ni_(0.5)Mn_(0.5)_x]O_2 and Their Applications to Lithium Batteries[J].Chemistry of Materials: A Publication of the American Chemistry Society,2006(22):5159-5163. |
| [29] | Arai H.;Sakurai Y.;Yamaki J.;Okada S. .Thermal behavior of Li1-yNiO2 and the decomposition mechanism[J].Solid state ionics,1998(3/4):295-302. |
| [30] | Barton P T;Premchand Y D;Chater P A et al.Chemi-cal inhomogeneity,short-range order,and magnetism in the LiNiO 2-NiO solid solution[J].Chemistry-A Europe-an Journal,2013,43(19):14521-14531. |
| [31] | Amine K.;Yasuda H.;Fujita Y.;Tukamoto H. .A NEW THREE-VOLT SPINEL LI1+XMN1.5NI0.5O4 FOR SECONDARY LITHIUM BATTERIES[J].Journal of the Electrochemical Society,1996(5):1607-1613. |
| [32] | Shaju K M;Subba Rao G V;Chowdari B V R .Performance of layered Li(Ni1/3 Co1/3 Mn1/3)O2 as cathode for Li-ion bat-teries[J].Electrochimica Acta,2002,48(2):145151. |
| [33] | Kang S H;Kim J;Stoll M E et al.Layered Li(Ni0.5 -x Mn0.5 -x M2x)O 2(M=Co,Al,Ti,x =0,0.025)cathode materials for Li-ion rechargeable batteries[J].Journal of Power Sources,2002,112(1):41-48. |
| [34] | Yoncheva M;Stoyanova R;Zhecheva E et al.Electro-chemical performance and local cationic distribution in layered LiNi1/2 Mn1/2 O 2 electrodes for lithium ion batter-ies[J].Electrochimica Acta,2009,54(6):1694-1701. |
| [35] | Megahed S;Scrosati B .Lithium-ion rechargeable batter-ies[J].Journal of Power Sources,1994,5 1(1):79-104. |
| [36] | Song M Y;Lee D S;Park H R .Electrochemical properties of LiNi1-y Tiy O2 and LiNi0.975 M0.025 O2(M= Zn,Al,and Ti)synthesized by the solid-state reaction method[J].Mate-rials Research Bulletin,2012,47(4):1021-1027. |
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%