16 2 Vol 16 No 2 2010 5 ELECTROCHEMISTRY May 2010 1006-3471 2010 02-0161-07 Sn-Co 1 1* 1 2* 1 2 361005 Sn-Co X- XRD SEM SnCo CoSn 2 Sn SnCo SnCo 636 3 mah /g 528 7 mah /g 83 1% 70 529 5 mah g - 1 82 6% Sn-Co Sn-Co O646 TM911 A 15 9 Sn-Co 372 mah g - 1 10 PS PS PS 1 11 Sn Sn-Co Sn-Co Sn Sb Co Cu Ni Sn-Sb 2 Sn-Co 3 Sn-Cu 4 Sn-Ni 5 Sn Tamura 6-8 Sn-Co Sn-Co 2009-09-02 2010-02-20 xmu edu cn * Tel 86-592 5343629 E-mail huangl@ xmu edu cn sgsun@ 20773102 20833005 973 2009CB220102
162 2010 Sn 1 3 Sn-Co Sn XRD X pert PRO X 1 Panalytical Cu Kα 1 1 40 kv 30 ma 20 ~ 80 0 016 15 s LEO1530 LEO SEM 1 4 Sn-Co 2025 Sn-Co 1 mol L - 1 20 min LiPF 6 / EC DMC DEC 1 1 1 + 2% VC 1 Celgard 2300 1 BTS 100 Tab 1 Chemical compositions of electroless porous Cu film ma g - 1 Component plating solution Compositions CuSO 4 5 0 g /L Na 3 C 6 H 5 O 7 4H 2 O 15 g /L NaH 2 PO 2 H 2 O 30 g /L H 3 BO 3 30 g /L NiSO 4 1 g /L C 14 H 26 O 2 0 8 g /L ph = 9 0 t = 70 1 2 Sn-Co SnCo XRD 1 Sn-Co Sn JCR No 00-001-0926 CoSn 2 2 2 Sn-Co a b Sn-Co Tab 2 Chemical compositions of Sn-Co alloy electrodeposition solution c d Sn-Co e f SEM Component Compositions Sn-Co Na 2 SnO 3 3H 2 O 75 g /L Sn-Co c d CoCl 2 6H 2 O 4 0 g /L C 4 H 4 O 6 KNa 4H 2 O 150 g /L K 3 C 6 H 5 O 7 4H 2 O 20 g /L SnCo ph = 7 ~ 8 t = 55 j = 10 A /cm 2 Ti supported Pt RE PARSTAT2263 PRIN- CETON Co SnCo 1 mol L - 1 LiPF 6 / EC DMC DEC 1 1 1 + 2% VC 10 5 ~ 10-2 Hz 5 mv 1 5 h 2 2 1 SnCo JCR No 03-065-2697 EDS Sn-Co Sn Co 73 27 2 e f
2 Sn-Co 163 1 Fig 1 Sn-Co XRD XRD pattern of the electrodeposited Sn-Co alloy 2 2 Sn-Co 3 Sn-Co Sn-Co 100 ma g - 1 SnCo SnCo 637 3 mah g - 1 486 5 mah g - 1 76 3% 60 230 mah g - 1 36 % SnCo 2 Fig 2 a b SnCo c d SnCo e f SEM SEM images of three-dimensional porous Cu film a b prepared by electroless plating the porous SnCo alloy electrode c d and planar SnCo alloy electrode e f prepared by electrodeposition
164 2010 3 Fig 3 a b SnCo Charge /discharge performances of the Sn-Co alloy electrode electrodeposited at planar Cu sheet a and porous Cu film b 4 Fig 4 Sn-Co a 1 b 2 c 20 d 50 e 70 f Selected discharge-charge curves a and the 1 st 2 nd 20 th 50 th 70 th cycle s differential capacity curves cycle s b 1 st c 2 nd d 20 th e 50 th f 70 th of the 3D porous Sn-Co alloy electrode 3b SEI 636 3 mah /g 12 1 5 V 528 7 mah /g 83 1% 70 82 6% 529 5 mah g - 1 0 4 ~ 0 02 V vs Li + /Li 0 05 V vs Li + / Li 0 4 ~ 0 6 V 4 Sn-Co Sn b ~ f 1 0 35 V
2 Sn-Co 165 5 Fig 5 SnCo Nyquist Electrochemical impedance spectra Nyquist plots of the 3-dementional structured SnCo alloy electrode at different potentials during initial lithiation at room temperature 2 0 34 V 0 41 V 0 5 V 13 4e 4f 1 3 V SEI Sn 14-16 0 3 V SEI 12 0 2 V SEI 4a SnCo 0 3 V 17 0 59 V 0 6 V 2 3 SnCo SnLi x 18 19-20 4 5 SnCo 2 7 V SnCo / 1 5 V SnCo
166 2010 SnCo 10 Ke F S Huang L Wei H B et al Fabrication and properties of macroporous tin-cobalt alloy film electrodes for lithium-ion batteries J J Power Souces 2007 170 450-455 11 Fan X Y Ke F S Wei G Z et al Sn-Co alloy anode u- sing porous Cu as current collector for lithium ion battery J J Alloys and Compounds 2009 476 70-73 References 1 Tarascon J M Armand M Issues and challenges facing rechargeable lithium batteries J Nature 2001 414 359-367 2 Yang J Takeda Y Imanishi N et al Ultrafine Sn and SnSb 0 14 powders for lithium storage matrices in lithiumion batteries J Journal of the Electrochemical Society 1999 146 4009-4013 3 Kim H Cho J Synthesis and electrochemical properties of Sn 87 Co 13 alloys by NaBH 4 and sodium naphthalenide reduction methods J Electrochim Acta 2007 52 4197-4201 4 Kepler K D Vaughey J T Thackray M M Copper-tin anodes for rechargeable lithium batteries an example of the matrix effect in an intermetallic system J Journal of Power Sources 1999 81 /82 383-387 5 Mukaibo H Sumi T Yokoshima T et al Electrodeposited Sn-Ni alloy film as a high capacity anode material for lithium-ion secondary batteries J Electrochemical and Solid State Letters 2003 6 10 A218-A220 6 Tamura N Fujimoto M Kamino M et al Mechanic stability of Sn-Co alloy anodes for lithium secondary batteries J Electrochimica Acta 2004 49 1949-1956 7 Tamura N Y Kato A Mikami Kamino M et al Study on Sn-Co alloy anodes for lithium secondary batteries I A- morphous system J J Electrochem Soc 2006 153 8 A1626-A1632 8 Tamura N Kato Y Mikami A et al Study on Sn-Co alloy anodes for lithium secondary batteries II Nanocomposite system J J Electrochem Soc 2006 153 12 A2227-A2231 9 Huang L Jiang H H Ke F S et al Structure and performance of novel three-dimentional porous Sn-Co negative materials J Acta Phys-Chim Sin 2006 22 12 1537-1541 12 Pereira N Klein L C Amatucci G G Particle size and multiphase effects on cycling stability using tin-based materials J Solid State Ionics 2004 167 29-40 13 Tamura N Kato Y Mikami A et al Study on Sn-Co alloy anodes for lithium secondary batteries I Amorphous system J Journal of the Electrochemical Society 2006 153 8 A1626-A1632 14 Dokko K Fujita Y Mohamedi M et al Electrochemical impedance study of Li-ion insertion into mesocarbon microbead single particle electrode Part II Disordered carbon J Electrochimica Acta 2001 47 933-938 15 Umeda M Dokko K Fujita Y et al Electrochemical impedance study of Li-ion insertion into mesocarbon microbead single particle electrode Part I Graphitized carbon J Electrochimica Acta 2001 47 885-890 16 Fan X Y Zhuang Q C Sun S G et al Fabrication and performance of Cu 6 Sn 5 alloy anode using porous Cu as current collector J Acta Phys Chim Sin 2009 15 611-616 17 Barsoukov E Kim J H Kim D H et al Parametric a- nalysis using impedance spectroscopy relationship of between material properties and battery performance J Journal of New Materials for Electrochemical System 2000 3 301-308 18 Larcher D Beaulieu L Y Macneil D D et al In Situ X- Ray study of the electrochemical reaction of Li with η- Cu 6 Sn 5 J J Electrochem Soc 2000 147 1658-1662 19 Hong J Wang C S Kasavajjula U Kinetic behavior of LiFeMgPO 4 cathode material for Li-ion batteries J Journal of Power Sources 2006 162 1289-1296 20 Levi M D Aurbach D The application of electroanalytical methods to the analysis of phase transitions during intercalation of ions into electrodes J J Solid State Electrochem 2007 11 1031-1042
2 Sn-Co 167 Preparation and Electrochemical Performance of Three-Dimensional Porous SnCo Alloy Electrode XUE Lian-jie 1 HUANG Ling 1* KE Fu-sheng 1 2 WEI Guo-zhen 1 2 ZHENG Xiao-mei 1 2 LI Jun-tao 1 2 Fan Xiao-yong 1 2 SUN Shi-gang 1 2* 1 Department of Chemistry College of Chemistry and Chemical Engneering 2 State Key Lab for Physical Chemistry of Solid Surface Xiamen University Xiamen 361005 Fujian China Abstract Three-dimensional porous Cu film was prepared by electroless plating and used as a current collector for preparation of three-dimensional structured SnCo alloy electrode which was mainly prepared by an electrodeposition method and composed of pure Sn and CoSn 2 phases Electrochemical experimental results show that three-dimensional structured SnCo alloy electrode exhibits much better cycleability than planar SnCo alloy electrode with first discharge capacity and charge capacity of 636 3 and 528 7 mah g - 1 respectively After 70 th cycling capacity retention is 83 1% with 529 5 mah g - 1 The lithiation process during first discharge was investigated by electrochemical impedance spectroscopy Key words porous Cu lithium ion batteries SnCo alloy electrode anode electrochemical impedance spectroscopy