采用固相烧结和球磨相结合的方法制备了锂离子电池负极复合材料Sn_(0.35-0.5x)Co_(0.35-0.5x)Zn_xC_0.30(摩尔分数x分别为0,0.05,0.10,0.15和0.20),考察了Zn添加量对材料结构和电化学性能的影响.烧结粉末样品的XRD分析表明,随着Zn含量的增多,在CoSn主相基础上,先形成少量CoSn_2相,随后形成少量Co_3Sn_2,Zn和Sn相.大部分Zn原子固溶于CoSn相.电性能分析表明,随着Zn含量的增加,首次放电容量和充放电效率都呈现先增加而后趋于稳定的趋势,当x=0.15时,首次放电容量和充放电效率都接近最大值,分别为343 mA·h/g和73.8%;经过25 cyc充放电后放电容量保持了首次放电容量的87.6%.这表明Zn原子固溶引起的晶格畸变和多种相生成导致相界数量的增多,加快了Li~+动力学扩散速度,从而显著改善了电化学性能.选择烧结粉末样品Sn_(0.275)Co_(0.275)Zn_(0.15)C_0.30进行球磨,晶粒和颗粒的细化使样品的放电容量显著提升,但对首次放电效率和循环性能改善不明显.
A series of Sn_(0.35-0.5x)Co_(0.35-0.5x)Zn_xCo_(0.30)(x=0, 0.05, 0.10, 0.15, 0.20) composites as novel anode materials used in lithium-ion batteries were synthesized from Sn, Co, Zn element powders and carbon black using solid-state sintering and ball milling, and the influences of Zn content on the structures and the electrochemical properties of those materials were analyzed. XRD data of the sintered powders illustrated that minor amount phase CoSn_2is formed firstly in the CoSn matrix phase with increasing content of Zn. Then, a little amounts of Co3Sn2, Zn and Sn are also precipitated. Most of Zn atoms dissolve into CoSn phase and lead to lattice distortion of the matrix. As a result, the lattice parameters a, c and unit cell volume V of CoSn phase are all reduced first and then enlarged with increasing content of Zn. Electrochemical analysis showed that the initial discharge capacity and initial charge-discharge efficiency are both improved first and then tended to stablility with increasing content of Zn, and as x=0.15, reach the maximums, discharge capacity after 25 charge-discharge cycles. The lattice distortion caused by Zn solution and the formation of multiphase are beneficial for accelerating the diffusion of Li~+ and enhancing the stability of structure, so the electrochemical properties are improved significantly. The sintered powder Sn_(0.275)Co_(0.275)Zn_(0.15)C_0.30 was milled for different times (t=10, 20 and 30 h), and it is shown that the refinements of grains and particles improved discharge capacity obviously, however, charge-discharge efficiency and cycle performance changed little.
参考文献
| [1] | Shen D,Yang S B,Zhang S K.Chem Ind Eng Prog,2007; 27:1894(沈丁,杨绍斌,张淑凯.化工进展,2007;27:1894) |
| [2] | Wolfenstine J,Campos S.Mater Lett,2002; 57:24 |
| [3] | Wang G,Lu Z W,Gao X P,Liu X J,Wang J Q.J Power Sources,2009; 189:655 |
| [4] | Wang G X,Ahn J H,Lindsay M J,Sun L,Bradhurst D H.Dou S X,Liu H K.J Power Sources,2001; 97-98:211 |
| [5] | Liu Y,Xie J Y,Takeda,Yang J.J Appl Electrochem,2002; 32:687 |
| [6] | Lee K T,Jung Y S,Oh S M.J Am Chem Soc,2003; 125:5652 |
| [7] | Kumar T P,Ramesh R,Lin Y Y,Fey G T K.Electrochem Commun,2004; 6:520 |
| [8] | Noh M J,Kwon Y J,Lee H J,Cho J P,Kim Y J,Kim M G.Chem Mater,2005; 17:1926 |
| [9] | Wu F,Li Y H,Wu C,Mu D B,Bai Y,Wu S X.Chin J Inorg Chem,2009; 25:7(吴锋,李艳红,吴川,穆道斌,白莹,吴生先.无机化学学报,2009;25:7) |
| [10] | Guo K M,Shi P F,Cheng X Q.New Chem Mater,2008; 36(9):90(郭昆明,史鹏飞,程新群.化工新型材料,2008;36(9):90) |
| [11] | Wang H Q,Yan Z X,Li Q Y,Zhang A N,Dai Q F.New Chem Mater,2007; 35(8):8(王红强,颜志雄,李庆余,张安娜,代启发.化工新型材料,2007;35(8):8) |
| [12] | Zheng M S,Song H H,Zhang S Y,Chen X H.Chin J Power Sources,2004; 28:334(郑妙生,宋怀河,章颂云,陈晓红.电源技术,2004;28:334) |
| [13] | Sony Corporation.CN Pat,200510107034.1,2006(索尼公司.中国专利,200510107034.1,2006) |
| [14] | Guilmen P,Guyot P,Marchai G.Phys Lett,1985; 109A:174 |
| [15] | Todd A D W,Mar R E,Dahn J R.J Electrochem Soc,2006; 153A:1998 |
| [16] | Todd A D W,Mar R E,Dahn J R.J Electrochem Soc,2007; 154A:597 |
| [17] | Dahn J R,Mar R E.Abouzlid A.J Electrochem Soc,2006; 153A:361 |
| [18] | Shen D.Master Dissertation,Liaoning Technical University,Fuxin,2009(沈丁.辽宁工程技术大学硕士学位论文,阜新,2009) |
| [19] | Matsushita Electric Industrial Co,Ltd.,US Pat,20040062990,2004 |
| [20] | Dean J A.Lange 's Handbook of Chemistry.12th ed,New York:McGraw-Hill,1992:2-2 |
| [21] | Pan J S,Tong J M,Tian M B.Fundamentals of Materials Science and Engineering.Beijing:Tsinghua University Press,2007:167(潘金生,仝健民,田民波.材料科学与基础.北京:清华大学出版社,2007:167) |
| [22] | Hassoun J,Mulas G,Panero S,Scrosati B.Electrochem Commun,2007; 9:2075 |
| [23] | Ionica-Bousquet C M,lippens P E,Aldon L,OlivierFourcade J,Jumas J C.Chem Mater,2006; 18:6442 |
| [24] | Li H,Wang Z X,Huang X J,Chen L Q.Physics,2008; 6:416(李泓,王兆翔,黄学杰,陈立泉.物理,2008;6:416) |
| [25] | Wang Z,Tian W H,Li X G.Acta Phys-Chim Sin,2006; 22:752(王忠,田文怀,李星国.物理化学学报,2006;22:752) |
| [26] | Guo H,Zhao H L,Jia X D,Xue L,Qiu W H.Electrochim Acta,2007; 52:4853 |
| [27] | Jin Y P,Guo B,Wang E D.Chin J Nonferrous Met,2007; 17:1490(金永平,郭斌,王尔德.中国有色金属学报,2007;17:1490) |
| [28] | Ren R,Wu Y C,Tang W M,Wang F T,Zhang Z Y.Acta Phys Sin,2008; 57:5774(任榕,吴玉程,汤文明,汪峰涛,郑治祥.物理学报,2008;57:5774) |
| [29] | Yang J,Takeda Y,Imanishi N,Yamamoto O.J Electrochem Soc,1999; 146:4009 |
| [30] | He Z Q,Li X H,Xiong L Z,Wu X M,Xiao Z B,Ma M Y.Chin J Inorg Chem,2005; 21:170(何则强,李新海,熊利芝,吴显明,肖卓炳,麻明友.无机化学学报,2005;21:170) |
| [31] | Zhang J J,Xia Y Y.J Electrochem Soc,2006; 153A:1466 |
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