Ñ ³ PtRu/MWCNTs Þ PtRuNi/MWCNTs

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1 49 ¾ 6 Å Vol.49 No Ð Ò ACTA METALLURGICA SINICA Jun pp Ñ ³ /MWCNTs Þ Ni/MWCNTs Đ ² Ñ Æ» ¹½ ( Í ³ ÍÅ¹ Í, ) (Æ Á Í ÍÍ, Æ ) Ó Î ± / Ø (/MWCNTs) Ç / Ø (Ni/ MWCNTs) Ø Ë Ç, ÓÈ» µ ÝÃ X Ç X ÓÈÝ ĐÆ Ç À Ç ±. Ç ÂÓ /MWCNTs Ç Ni/MWCNTs Ø Ë ÇĐ O (ORR) Ç Â ÓË ÃÇ Ã. Ó, Ni/MWCNTs ORR ÇÓ Ó»¹Ø, Ó, Â Ó, Ó Ø, ¼ CO ÞÃÝ ÃÂ, ÍÀÂ ¾ Â ÇÓ Ë ÞÏÊ Ç. Â, Ni/MWCNTs ORR Ç Â ÓË Ã, ÍÑ¼ÝºÏ Ç MWCNTs Ó Î À O Ý ÐÙ Ï. Ú Ø Ë Ç, Ø,, ÇÓ, ÓË µ ÔØ Ü O646 «A ± Ü (2013) ELECTRODEPOSITION OF /MWCNTs AND Ni/MWCNTs AND THEIR PERFORMANCE IN DIRECT METHANOL FUEL CELLS ZHAO Yue, HONG Bo College of Environmental Science and Engineering, Ocean University of China, Tsingtao FAN Louzhen College of Chemistry, Beijing Normal University, Beijing Correspondent: HONG Bo, professor, Tel: (0532) , E mail: eselab@ouc.edu.cn Supported by National Natural Science Foundation of China (No ) and Fundamental Research Funds for the Central Universities (No ) Manuscript received , in revised form ABSTRACT catalyst has long application history in electrochemical field due to the wide prospect in direct methanol fuel cells (DMFCs), but its performance remains to be improved further. There are usually two ways to enhance the catalytic activity of bimetallic catalyst. One is to add the third metal into alloy; the other is to improve the properties of carbon support. In this work, and Ni nanoparticle clusters were electrochemically deposited on multi walled carbon nanotubes (MWCNTs) through a three step process, including an electrochemical treatment of MWC- NTs, electro oxidation of metal chloride to high valence of metal complex and an electro conversion of and Ni nanoparticle clusters on MWCNTs. The structure and elemental composition of the /MWCNTs and Ni/MWCNTs electrodes were characterized by transmission electron microscopy(tem), energy dispersive X ray spectroscopy(edx), X ray polycrystalline diffraction(xrd) and X ray photoelectron spectroscopy (XPS). The electrocatalytic properties of the /MWCNTs and Ni/MWCNTs electrodes for oxygen reduction reaction (ORR) and methanol oxidation were * Ê³ ÎÐ Ç Ð Ó Ä Ð Æ ²½«: , Å ²½«: Ï³ : ²,, 1981, ÖË DOI: /SP.J

2 700 Ì 49 ¾ investigated by cycle voltammetry (CV) method and current time (CT) method. The results showed that Ni/MWCNTs electrode exhibited a high I f /I b (the forward anodic peak/the reverse anodic peak current) value and an appreciably improved resistance to carbon monoxide (CO) poisoning in methanol solution, so a beneficial effect on the oxygen adsorption in dilute sulphuric acid solution was observed. The high electrocatalytic activity and good stability of Ni/MWCNTs was attributed to the synergetic effect of bifunctional catalysis, three dimension structure and oxygen functional groups which generated after electrochemical activation treatment on MWCNTs surface. The successful preparation of /MWCNTs and Ni/MWCNTs nanocomposites opens a new path for efficient dispersion of promising electrocatalysts in DMFCs. KEY WORDS nanoparticle composite, multi wall carbon nanotube, three dimension structure, fuel cell, electrocatalysis Đ, Ñ È Ì Ì ß Ã ÈÔ (DMFCs) [1 5] ² Æ ¹ [6 8]. ÑÌ Ì ß Ì Ä Å Ì ß ß, ÐÎ Đ Å ÐÂÐ ( Ñ È Ì Ì ßÝ ØÔ, Ê Å 0 / / 4+ Á, Ã Ä Ð [9] ), Î ÐÎ Đ Æ ÑÌ CO ßÄÞ ß ( DMFCs ØÌ ß).»Ò½Þ [10], «¼Ì Ã, Ð Ó O Å CO CO 2, Æ CO ß À. µ ÑÌ, Ì ß ¹Í Æ [11 13], ÄÞ¼ ², È Ç, ³, Æ, Ê ± ÄÞ ¾ß ¹º À [14,15]. «, ± Ò Ì ß Ì Ä ÜÈÂ Ð : ÎÅÒ Ì Ì [16,17], Đ ; Î ±Đ» ÄÞ. ĐµÈ, ĐÙ (MWC- NTs) Ä, Î ± ÐÕÈ± Ø Ä [18 20],» Î¹ Ì ß». ¹Ì» [21], Ô Ï ², MWCNTs ½ ÕÅ Â (3D) Ù ÉÆÉ, ½ Ù µèô¼ ± Ì ÄÈ ØÄ.» Ô Ï ² Å /MWCNTs È Ni/MWCNTs Ù ÌµÈ, ÔÉ¼ (TEM) ÞÄ (EDS) X (XRD) È X ÔÉÞ (XPS) Ì È Á. (CV) ÈÐÃÔ (CT)» /MWCNTs È Ni/MWCNTs (ORR) È Ã ÔÌ Ä È ØÄ, Å «/MWCNTs È Ni/MWCNTs ÁÅ. 1 ÝÖÓ Æ Å MWCNTs ²Å, Ü Æ 12 h. Na, Ï 6 h, Na Í. ßÅ : K 2 SO 4, K 2 Cl 4, Cl 3 H 2 O, NiCl 2 6H 2 O, H 2 SO 4 È Ã (CH 3 OH). ÇÓ ((20± 1), ph=7, ÔË ρ=18.3 MΩ cm) ÅÓ Å. Æ Å Đ (GC) ÔØ È Ö, 0.5 h, ± N 2. Å 1 mg MWCNTs «10 ml Ì, 30 min 0.1 mg/ml ÉÅÕ. Å 15 µl ÉÅÕ GC Ô Ø ¹, MWCNTs/GC ÔØ. Ô Ï ² Ni/MWCNTs: (1) 0.5 mol/l K 2 SO 4 Õ, Ò V, ÒÛ 200 mv/s, Ò 10 min, Æ MWCNTs ÈÂÐ ±¾À Á O ÞÆ (C=O, OH È COOH ); (2) 2.0 mol/l K 2 Cl mol/l Cl mol/l NiCl mol/l K 2 SO 4 (ph=4) Õ ÁÔ (PS), V, s, È PS ¼À Ø Ô, Æ Cl 2 4, 3+ È Ni 2+ MWCNTs À (IV), (IV) È Ni(III) Ì ; (3) 0.1 mol/l H 2 SO 4 Õ, Ò V, CV Ò Ð, Æ MWCNTs (IV), (IV) È Ni(III) Ì Á Ni Ì Ù É. /MWCNTs ÆÅ² (2) Õ 2.0 mol/l K 2 Cl mol/l Cl mol/l K 2 SO 4 Õ, Ni/MWCNTs ÆÅ² (2) Õ 2.0 mol/l K 2 Cl mol/l NiCl mol/l K 2 SO 4 Õ, /MWCNTs ÆÅ² (2) Õ 2.0 mol/l K 2 Cl mol/l K 2 SO 4 Õ. Æ ÔØ ÁÔ Ï ÈÔÌ ÄÞ». Á Ù ÉÔ Õ, MWCNTs/GC Ô Ø Á. Ô Ï Ã, MWCNTs/GC ÔØ» ÔØ. Æ ÔØ, Ag/AgCl ÔØ ÔØ. ÁÔÌ ÄÞ» Ã, Ù ÌµÈÔØ» ÔØ, ÔØ, Ag/AgCl ÔØ ÔØ. Ô Ï» CHI710a Ô Ï ²Ú.

3 6 Å ± : Ò Ô /MWCNTs Æ Ni/MWCNTs Û ½ ÁµÆÒ ÂÜ 701 Hitachi 600 TEM /MWCNTs È Ni/MWCNTs, ĐÛÔ 200 kv. X Pert PRO MPD XRD(X CuK α, º Ô ÈÔ 45 kv È 100 ma) È ESCALab220i XL XPS(ÔÉ Ð 300 W AlK α, Ñ Pa, ÌÞÜ ev C1s Ñ Ã) Á ². 2 Û 2.1 Ð Ô Ï ² /MWCNTs È Ni/MWCNTs Ù ÌµÈ «1 ßÊ. Ô Ï MWCNTs/GC ÔØ 2.0 mol/l K 2 Cl mol/l Cl mol/l K 2 SO 4 Õ È 2.0 mol/l K 2 Cl mol/l Cl mol/l NiCl mol/l K 2 SO 4 Õ CV «2 ßÊ. ÅË, Ni [22], Ò ÈÔ 0.3 V. Å O 2 [23], ÑÔ 1.1 V. ß, Ô Ï, MWCNTs À Á O ÞÆ, C=O, OH È COOH. Á O ÞÆ O É Ò Ñ, 1.05 V Å Cl 2 4 (IV) Ì, 0.87 V Å Ni 2+ Ni(III) Ì [24] («2b). «2a È b, 1.01 V Ø Ä 3+ (IV) Ì [25]. Ü», MWCNTs (IV), (IV) È Ni(III) Ì Î È Ni Ù É. ¼, 0.1 mol/l H 2 SO 4 Õ Ò Ð, Ò V, Æ MWCNTs (IV), (IV) È Ni(III) Ì Á È Ni Ù É. 1 ± Ni/MWCNTs( Ø ) Ø Ë Ç ÉÞÅ Fig.1 Schematic illustration of three step process for electrochemical synthesis of Ni/MWCNTs(multi walled carbon nanotubes) (a) 4.0 (b) I, A V 1.01 V I, A V 1.01V 0.87V E, V (vs Ag/AgCl) E, V (vs Ag/AgCl) 2 MWCNTs/GC Ó 2.0 mol/l K 2 Cl mol/l Cl mol/l K 2 SO 4 Ç 2.0 mol/l K 2 Cl mol/l Cl mol/l NiCl mol/l K 2 SO 4 Ô CV Å Fig.2 Cyclic voltammograms of MWCNTs/GC electrodes in 2.0 mol/l K 2 Cl mol/l Cl mol/l K 2 SO 4 (a) and 2.0 mol/l K 2 Cl mol/l Cl mol/l NiCl mol/l K 2 SO 4 (b) solution (GC glassy carbon, I current, E potential)

702 Ì 49 ¾ 2.2 Ù «3 /MWCNTs È Ni/MWCNTs TEM. Ü, Î 2 nm Ù Å º 3D ÆÉ. Ì Ù ÆÉ Ó ¹: Ð 2 ²Å, MWCNTs Ð ± Ì, Å º À MWCNTs ±¾, Á O ÞÆ. Å, ÞÆ Ü («1). È, Æ Ì º Ä ÛÀ Ì, ÛÀ Ì Å. Í, 0.1 mol/l H 2 SO 4 Õ, Ò 1.0 0.

4 702 Ì 49 ¾ 2.2 Ù «3 /MWCNTs È Ni/MWCNTs TEM. Ü, Î 2 nm Ù Å º 3D ÆÉ. Ì Ù ÆÉ Ó ¹: Ð 2 ²Å, MWCNTs Ð ± Ì, Å º À MWCNTs ±¾, Á O ÞÆ. Å, ÞÆ Ü («1). È, Æ Ì º Ä ÛÀ Ì, ÛÀ Ì Å. Í, 0.1 mol/l H 2 SO 4 Õ, Ò V, Å Ò Ô Ø, Ì Ù ÆÉ. /MWCNTs Ù ÆÉ 20 nm, Ni/MWCNTs Ù ÆÉ 5 8nm. ½ ± ÐÕÈÔ Ï Ä ÐÕ, ÔÌ Å Ê [21]. Å MWC- NTs Ù É µ, EDS Á ², «4 ßÊ. «4a, È ÐÆÚ, É 8 2. «4b,, È Ni ÐÆÚ, É 8 1 1(«4b)., È Ni ½ Õ MWCNTs. «5 /MWCNTs È Ni/MWCNTs XRD. Å, «5 Å /MWCNTs È Ni/MWCNTs XRD MWC- NTs. Î 4 (39.83, 46.52, È ) fcc, Ä (111), (200), (220) È (311) Ð. «/MWCNTs, Ni/MWCNTs, /MWCNTs È Ni/ MWCNTs (111) ±, ÀºÙ. /MWCNTs, Ni/MWCNTs, /MWCNTs È Ni/MWCNTs (111) 2θ 39.83, 40.19, È ÙÛÕÔ ³½. «5 ½ hcp È Ni fcc, ÕÔ È Ni fcc ³, «Ì Ì Ù Ì ß. 3 /MWCNTs Ç Ni/MWCNTs TEM Fig.3 TEM images of /MWCNTs (a) and Ni/MWCNTs (b) (a) (b) Energy, kev Intensity, a. u. Ni Ni Ni Energy, kev 4 Ç Ni Ø È EDS Å Fig.4 EDS spectra of (a) and Ni (b) nanoparticles

5 6 Å ± : Ò Ô /MWCNTs Æ Ni/MWCNTs Û ½ ÁµÆÒ ÂÜ 703 XPS ² /MWCNTs È Ni/ MWCNTs ÐÂÐ, «6 È 7 ßÊ. 3d ÔÉ ÌÞ C1s ÔÉ ÌÞ, ßÜ ¹ 3p. «6 ½ 2+ È 4+ ÔÉ ÌÞ (73.81 È ev), ÕÔ. /MWCNTs 4f 7/2 È 4f 5/2 ½ È ev, /MWCNTs 4f 7/2 È 4f 5/2 (71.20 È 74.53eV) ÙÛÅ 0.07 È 0.19eV, MWCNTs (111) (200) (220) (311) a b c ÕÔ «ÅÌ. È O 2 3p 3/2 ÔÉ ÌÞ È ev. Ü, Å ², O 2 ÄÍ. Ni/MWCNTs 4f, 3p È Ni2p Ô É ÌÞ «7 ßÊ. «/MWCNTs(71.20 È ev) È /MWCNTs(71.13 È ev), Ni/MWCNTs 4f 7/2 È 4f 5/2 ÔÉ ÌÞ À Ù, ½ È ev, ÐÕ¼ 4 3. ÔÉ ÌÞ ² Ü, Ì Ì Ð. Ni/MWCNTs È O 2 3p 3/2 ÔÉ ÌÞ È ev, /MWCNTs ² À Ù. Ni2p «, Ë ±Þ Ú Ä (µû (a) 4f 5/2 4f 7/ , deg d 5 /MWCNTs, Ni/MWCNTs, /MWCNTs Ç Ni/MWCNTs XRD Fig.5 XRD spectra of /MWCNTs (a), Ni/MWCNTs (b), /MWCNTs (c) and Ni/MWCNTs (d) (a) 4f5/2 4f 7/2 (b) O (b) (c) 2p 1/2 Shake-up 2p 3/2 Ni(OH) 2 Ni NiOOH NiO O /MWCNTs 4f Ç 3p XPS Fig.6 XPS spectra of 4f (a) and 3p (b) of /MWCNTs Ni/MWCNTs 4f, 3p Ç Ni2p XPS Fig.7 XPS spectra of 4f (a), 3p (b) and Ni2p (c) of Ni/MWCNTs

6 704 Ì 49 ¾ ), À ÔÉÖ. Ni2p 3/2 ßÈ ÕÔÌ Ni ½ Ð. Ni2p 3/2 XPS ½ , , È ev, Ni, NiO, Ni(OH) 2 È NiOOH. Æ, Ni/MWCNTs,, È Ni ÅÌ, MWCNTs Ä ³ È Ni. 2.3 Õ ÐÒ ßÐ «8 /MWCNTs, Ni/MWCNTs, / MWCNTs È Ni/MWCNTs ÔØ H 2 SO 4 Õ CV. Ü, µôø ORR ÔÌ Ä V, ½ ³ H., /MWCNTs 0.1 mol/l H 2 SO 4 Õ ORR ÈÔ 0.6 V(vs Ag/AgCl), Ni/MWCNTs, /MWCNTs È Ni/MWCNTs ORR È Ô 0.65, 0.70 È 0.75 V. /MWCNTs È Ni/MWCNTs ORR ÈÔ /MWCNT È Ni/MWCNTs ÀÔ¼ºÙ, Ô ±, Æ ORR Ì ÄÑ ±. Ni/MWCNTs ORR Ì Ä /MWCNTs ± ¹: /MWCNTs, ½ ÓÄ, ORR Å Û, Ni/MWCNTs, «È Ni Ì, Æ ORR Ô ºÙ. Ni ¾ ÙÛ O Ñ Å Ni/MWCNTs ORR Ì ÄÞ. 2.4 ßÕ ÐÒ ßÐ ÔØ ÔÌ Ä Ã Å ½»Ø. «9 Î /MWCNTs, Ni/MWCNTs, /MWCNTs È Ni/MWCNTs Ô Ø 2.0 mol/l CH 3 OH mol/l H 2 SO 4 Õ CV. 1 É Å 4 ÔØ Ã Å ÈÔ (E 0 ), Ô (E pa ), º Ò Ô (I f ), Ò Ô (I b ) ÜÜ I f /I b., Ni/MWCNTs ÔØ E 0 È E pa Ô¼ Ù, ÕÔ Ã Õ Ô ÏÌ Ä±, Ã Å Ý À. Ni/MWCNTs ÔØ I f /I b 2.73, 3 ÔØ ÝÐ±, ÕÔ º Ò, Á C ¼ Ý CO 2. Å Ã Ì ß Ì Ä Þ, º Ò Ã CV Ð Ý, Ni/MWCNTs Ô Ï Ä ÐÕ 215.0m 2 /g, ± /MWCNTs, Ni/MWCNTs È / MWCNTs 90.9, 56.0, m 2 /g. 8.0 I, ma/mg b a c d E, V(vs Ag/AgCl) 8 /MWCNTs, Ni/MWCNTs, /MWCNTs Ç Ni/MWCNTs Ó 0.1 mol/l H 2 SO 4 Ô CV Fig.8 Cyclic voltammograms of /MWCNTs (a), I, ma/mg Ni/MWCNTs (b), /MWCNTs (c) and Ni/MWCNTs (d) electrodes in 0.1 mol/l H 2 SO 4 solution E, V (vs Ag/AgCl) 9 /MWCNTs, Ni/MWCNTs, /MWCNTs Ç Ni/MWCNTs Ó 2.0 mol/l CH 3 OH+ 0.1 mol/l H 2 SO 4 Ô CV Fig.9 Cyclic voltammograms of /MWCNTs (a), d c a b Ni/MWCNTs (b), /MWCNTs (c) and Ni/MWCNTs (d) electrodes in 2.0 mol/l CH 3 OH mol/l H 2 SO 4 solution 1 /MWCNTs, Ni/MWCNTs, /MWCNTs É Ni/MWCNTs ÕÙ Ä «¹ Table 1 Methanol oxidation reaction parameters of /MWCNTs, Ni/MWCNTs, /MWCNTs and Ni/MWCNTs electrodes (E 0 onset potential, E pa anodic peak potential, I f forward anodic peak current, I b reverse anodic peak current) Catalyst E 0, V E pa, V I f, ma/mg I b, ma/mg I f /I b Ni/MWCNTs /MWCNTs Ni/MWCNTs

7 6 Å ± : Ò Ô /MWCNTs Æ Ni/MWCNTs Û ½ ÁµÆÒ ÂÜ 705 ÐÃÔ» Å /MWCNTs, Ni/ MWCNTs, /MWCNTs È Ni/MWCNTs 2.0 mol/l CH 3 OH+0.1 mol/l H 2 SO 4 Õ Ã Ô, Ô 0.66 V, Ã 3600 s. Å I f «Ð Ç º Ò Ô (I 0 f ), I f/i 0 f, Ã «, «10 ßÊ. I f /I 0 f ÞÃ Ð, ÔØ, Ð Ì. /MWCNTs ÔØ I f 10 min ÛÐ Å I 0 f 70%. /MWCNTs Normalized current I f /I 0 f a Time, s 10 /MWCNTs, Ni/MWCNTs, /MWCNTs Ç Ni/MWCNTs Ó 2.0 mol/l CH 3 OH+ 0.1 mol/l H 2 SO 4 Ô ÂÓ Fig.10 Normalized current time plots of /MWCNTs (a), Ni/MWCNTs (b), /MWCNTs (c) and Ni/MWCNTs (d) electrodes in 2.0 mol/l CH 3 OH mol/l H 2 SO 4 solution (I 0 f forward anodic peak current of the first time) d c b È Ni/MWCNTs Ð I 0 f 70% Æ 1 h, ÕÔ /MWCNTs È Ni/MWCNTs Ã Ô ÈÌ ØÄ /MWCNTs ±. Ü, Ã Ì ÄÈ ØÄÔÇ : Ni/ MWCNTs > /MWCNTs > Ni/MWCNTs > /MWCNTs, Ni/MWCNTs ÍÏÌÎ DMFCs ØÌ ß. Ni/MWCNTs Ã Ì Ä± ½ Ì Ù É, ÝÒ½Þ» È MWCNTs Ð± Ô Ï À Í Á O ÞÆ. Á O ÞÆ O É CO 2 Å Ä, ±ÅÅ Ä. Ni/MWCNTs Ò½Þ ¹: Ì Ð,, Ni È Ni(II)(«11a). Þ Ã, ¼À CO, Ô ¹ H 2 O, ¾ OH, ½ Í À O Þ [26].» d Ù È Ð ² ÐÝ [27], Ni «Ì, Ü ÔÉ ÌÞÊ Ã Å [28], Ni(II) È Ë Å ÑÝÞ ¾ ÙÛ O [29,30]. Ã ÏÌ ß Ð, È ÈÅ ÑÆ Ã C H Ê, Ni(II) È ¾ ÙÛ O(«11b), «È Ì CO À CO 2 («11c) [31]., È Ni( Á O ÞÆ) Æ È Ð Ä CO ¼ «Đ ¹ Å («11d). Æ,, È Ni Ð «Ã Ì Í 11 Ni/MWCNTs Ó Â Ô Ñ¼ÝÒ ÉÞÅ Fig.11 Schematic illustration of bifunction mechanism for Ni/MWCNTs electrode surface in methanol solution (a) electrodeposition of Ni nanoparticles on MWCNTs (b) oxidation of adsorbed H 2 O (c) oxidation of boned CO to form CO 2 on Ni(II) and sites (d) removal of adsorbed CO for next round of reaction

8 706 Ì 49 ¾ Ð, Ü Đ Ì ß CO ß Ú Ä ¾ Õ, Æ Ni/MWCNTs Ã Å ½ ± Ì Ä. 3 Å H 2 SO 4 Õ, Ni/MWCNTs (ORR) ÈÔ ÀºÙ, Ô ±, ORR Ì Ä±; Ã Å, ÈÔ (E 0 ) È Ô (E pa ) Ù, º «Ò Ô (I f /I b ) ±, º Ò Ô (I f /If 0 ) Ð Ì, ¼ÊÁ Ã Ô Ï ÄÜ ØÄ. Ni/MWCNTs ORR È Ã ÔÌ Ä±, ÎÒ½Þ» È MWCNTs Ð± Ô Ï À Á O ÞÆ Ú. Ni/MWCNTs ± Ø Ì Ã ¾Å Ë, ÎÏÌÎ DM- FCs ØÌ ß Ù µè. [1] Zhao X, Li W, Fu Y, Manthiram A. Int J Hydrogen Energy, 2012; 37: 9845 [2] Bennett B, Koraishy M B, Meyers P J. J Power Sources, 2012; 218: 268 [3] Zheng W, Suominen A, Tuominen A. Energy Procedia, 2012; 28: 78 [4] Umeda M, Ueda M, Shironita S. Energy Procedia, 2012; 28: 102 [5] Wang X D, Xie X F, Wang M, Liu G C, Miao R Y, Wang Y T, Yan Q. Prog Chem, 2011; 23: 509 ( Ù,,,, Ñ, Ö, ². Î, 2011; 23: 509) [6] Kakati N, Lee S H, Maiti J, Yoon Y S. Surf Sci, 2012; 606: 1633 [7] Escudero Cid R, Hernández Fernández P, Pérez Flores J C, Rojas S, Garcia Rodríguez S, Fatás E, Ocón P. Int J Hydrogen Energy, 2012; 37: 7119 [8] Kang S, Lim S, Peck D H, Kim S K, Jung D H, Hong S H, Jung H G, Shul Y. Int J Hydrogen Energy, 2012; 37: 4685 [9] Murthi V S, Urian R C, Mukerjee S. J Phys Chem, 2004; 108 B: [10] Wei Z D, Li L L, Luo Y H, Yan C, Sun C X, Yin G Z, Shen P K. J Phys Chem, 2006; 110B: [11] Basnayake R, Li Z, Katar S, Zhou W, Rivera H, Smotkin E S, Casadonte D J, Korzeniewski C. Langmuir, 2006; 22: [12] Ahn S H, Choi I, Kwon O J, Kim J J. Chem Eng J, 2012; : 276 [13] Li B, Higgins D C, Zhu S, Li H, Wang H, Ma J, Chen Z. Catal Commun, 2012; 18: 51 [14] Yang D S, Sim K S, Kwen H D, Choi S H. J Ind Eng Chem, 2012; 18: 538 [15] Li Q W, Wei Z D, Chen S G, Qi X Q, Liu X, Ding W, Ma Y. Acta Phys Chim Sin, 2011; 27: 2857 (, ÈÜ, Ø, Î,, Ö,. ÎÎ, 2011; 27: 2857) [16] Xiong L, Manthiram A. J Electrochem Soc, 2005; 152: 697 [17] Guillén Villafuerte O, Guil López R, Nieto E, García G, Rodríguez J L, Pastor E, Fierro J L G. Int J Hydrogen Energy, 2012; 37: 7171 [18] Dong S A, Liu F, Hou S Q, Pan Z F. Acta Chim Sin, 2010; 68: 1519 (Ú,, Î,. ÎÎ, 2010; 68: 1519) [19] Dillon A C, Jones K M, Bekkedahl T A, Kiang C H, Bethune D S, Heben M J. Nature, 1997; 386: 377 [20] Collins P G, Zettl A, Bando H, Thess A, Smalley R E. Science, 1997; 278: 100 [21] Zhao Y, Fan L Z, Zhong H Z, Li Y F, Yang S H. Adv Funct Mater, 2007; 17: 1537 [22] Zhang Y Y, Liu M L, Wang M L, Xie Q J, Yao S Z. Sensor Actuat, 2007; 123B: 444 [23] Fachinotti E, Guerrini E, Tavares A C, Trasatti S. J Electroanal Chem, 2007; 600: 103 [24] Hu C C, Cheng C Y. J Power Sources, 2002; 111: 137 [25] Vukovic M, Cukman D. J Electroanal Chem, 1999; 474: 167 [26] Park K W, Choi J H, Kwon B K, Lee S A, Sung Y E. J Phys Chem, 2002; 106B: 1869 [27] Demirci U B. J Power Sources, 2007; 173: 11 [28] Wang W, Wang R, Wang H, Ji S, Key J, Li X. J Power Sources, 2011; 196: 9346 [29] Liu F, Lee J Y, Zhou W. J Phys Chem, 2004; 108B: [30] Zhao Y, E Y F, Fan L Z, Qiu Y F, Yang S H. Electrochim Acta, 2007; 52: 5873 [31] Kardash D, Korzeniewski C, Markovic N. J Electroanal Chem, 2001; 500: 518 ( ¼: ¾ º)

» LiNi 0.5 x Co 2x Mn 0.5 x O 2 Æ º

«22 «5 Æ Ç Vol. 22, No. 5 2007 À 9 ³ Journal of Inorganic Materials Sep., 2007 Ç : 1000-324X(2007)05-0873-06» LiNi 0.5 x Co 2x Mn 0.5 x O 2 Æ º ÔÒ Ó Ð Ó Ñ ( Ï 410083) Æ Ã Ç ÊÉ É Ni 0.5 xco 2xMn 0.5 xco