金属学报  2007, Vol. 43 Issue (8): 818-822

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脉冲激光沉积制备的HT-LiCoO2薄膜中Li离子表观扩散的研究

张耀;钟志源;朱敏

华南理工大学机械学院

PITT investigation of apparent diffusion of lithium-ion through PLD-deposited HT-LiCoO2 films

ZHANG Yao;Chi-Yuen CHUNG;

华南理工大学机械学院

张耀; 钟志源; 朱敏 . 脉冲激光沉积制备的HT-LiCoO2薄膜中Li离子表观扩散的研究[J]. 金属学报, 2007, 43(8): 818-822 .
, , . PITT investigation of apparent diffusion of lithium-ion through PLD-deposited HT-LiCoO2 films[J]. Acta Metall Sin, 2007, 43(8): 818-822 .

摘要 参考文献 相关文章 Metrics 全文: PDF(582 KB)   摘要: 采用脉冲激光沉积(PLD)方法在镀Pt的Si衬底上制备了LiCoO2薄膜, 运用XRD、Raman光谱、SEM和循环伏安等方法对其结构与电化学性能进行表征, 在此基础上着重采用电位间歇滴定技术(PITT)对其Li离子表观扩散进行了分析. 结果表明,600℃制备的LiCoO2薄膜为HT-LiCoO2相, 呈柱状晶结构, 平均晶粒尺寸在100 nm以下, 结晶度高, 并且具有明显的[001]择优取向, 但少量缺Li. 伏安循环曲线表明, 该LiCoO2薄膜具有良好的电化学可逆性, 但只在3.9 V(vs Li)附近出现一对氧化还原峰. PITT测试表明, PLD方法制备的HT-LiCoO2薄膜的Li离子扩散系数在10-8—10-9 cm2/s, 与其它方法(如射频磁控溅射)制备的HT-LiCoO2薄膜相比, 扩散系数高1—2个数量级; 并且PLD方法制备的HT-LiCoO2薄膜中Li离子扩散系数与相变有关, 在两相共存区, 由于相界钉扎的作用, Li离子扩散系数比其它区域小1—2个数量级. 关键词 ： LiCoO2,  脉冲激光沉积(PLD),  薄膜电池     Abstract：In this work, LiCoO2 films were prepared with the pulsed laser deposition (PLD) method. Their structure was characterized by X-ray diffraction, Raman spectra and Scanning electron microscopy and their electrochemical properties were evaluated with cyclic voltammetry (CV). Results showed that LiCoO2 films prepared with PLD at 600℃ had a well-crystallized columnar HT-LiCoO2 structure with the average grain size less than 100nm and with a strong [001] preferred orientation, while these films contain trace amount of Co3O4. CV tests indicated that PLD-deposited HT-LiCoO2 films had good electrochemical reversibility but only a pair of redox peaks near 3.9V(vs Li) were observed in the cyclic voltammograms. Thereafter, emphasis was laid on the study of apparent diffusion of lithium-ion through LiCoO2 films using the potentiostatic intermittent titration technique (PITT). PITT measurements revealed that the lithium-ion diffusion coefficient of PLD-deposited HT-LiCoO2 films reached 10-8~10-9cm2s-1, 1-2 orders of magnitude faster than those prepared by other methods including R.F. magnetron sputtering and, in the voltage range between 3.85~3.95V(vs Li), the lithium-ion diffusion coefficient of PLD-deposited HT-LiCoO2 films was 1-2 orders of magnitude lower than other voltage ranges. The former should be ascribed to the grain refinement of PLD-deposited HT-LiCoO2 films and existence of many voids, while the later may due to the hindrance arising from phase boundary movement. Key words： LiCoO2    pulsed laser deposition    thin film battery    lithium ion diffusion 收稿日期: 2006-12-04      ZTFLH:  O484.4   服务 把本文推荐给朋友 加入引用管理器 E-mail Alert RSS 作者相关文章 张耀 钟志源 朱敏 44.8K 链接本文: https://www.ams.org.cn/CN/      或      https://www.ams.org.cn/CN/Y2007/V43/I8/818 [1]Reimers J N,Dahn J R.J Electrochem Soc,1992;39:2091 [2]Bueno P R,Leite E R.J Phys Chem,2003;107B:8868 [3]Wang B,Bates J B,Hart F X,Sales B C,Zuhr R A, Robertson J D.J Electrochem Soc,1996;143:3203 [4]Polo da Fonseca N,Davalos J,Kleinke M,Fantini M C A, Gorenstein A.J Power Sources,1999;81-82:575 [5]Kim W S.J Power Sources,2004;134:103 [6]Liao C L,Fung K Z.J Power Sources,2004;128:263 [7]Iriyama Y,Inaba M,Abe T,Ogumi Z.J Power Sources, 2001;94:175 [8]Julien C,Camacho-Lopez M A,Alarcon L E,Poniatowski E H.Mater Chem Phys,2001;68:210 [9]Perkins J D,Bahn C S,McGraw J M,Parilla P A,Ginley D S.J Electrochem Soc,2001;148A:1302 [10]Bouwman P J,Boukamp B A,Bouwmeester H J M,Not- ten P H L.J Electrochem Soc,2002;149A:699 [11]Tang S,Lu L,Lai M O.Philos Mag,2005;85:2831 [12]Xia H,Lu L,Ceder G.J Alloys Compd,2006;417:304 [13]Cho S I,Yoon S G.J Electrochem Soc,2002;149A:1584 [14]Kushida K,Kuriyama K.J Cryst Growth,2002;237-239: 612 [15]Kim K W,Woo S I,Choi K H,Han K S,Park Y J.Solid State Ionics,2003;159:25 [16]Chen C H,Kelder E M,Jak M J G,Schoonman J.Solid State Ionics,1996;86-88:1301 [17]Shin H C,Pyun S I.Electrochim Acta,2001;46:2477 [18]Xia H,Lu L,Ceder G.J Power Sources,2006;159:1422 [19]Montella C.Electrochim Acta,2006;51:3102 [20]Wen C J,Boukamp B A,Huggins R A.J Electrochem Soc, 1979;126:2258 [21]Aurbach D,Levi M D,Levi E,Teller H,Markovsky B, Salitra G,Heider U,Heider L.J Electrochem Soc,1998; 145:3024 [22]Peng W J,Li X H,Wang Y Y,Wang Z X,Guo H J.J Cent South Univ(Sci Technol),2004;35:568 (彭文杰，李新海，王云燕，王志兴，郭华军．中南大学学报(自然科学版)，2004；35：568) [1] 李飞; 胡克鳌; 李建林; 张栋; 吴桢干 . 凝胶燃烧法合成LiCoO2超细粉体的研究[J]. 金属学报, 2002, 38(2): 140-144 . Viewed Full text Abstract Cited   Shared      Discussed