MnO 2. : A : O 646; TM 911. (MEVVA ) ( ) ; LEO21530 ( ) ; Philip s PANalytical X Pert X. ( > 99. 9% ) ; KMnO 4, , (308 mah /g) Jahn2Teller

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1 ELECTROCHEM ISTRY Vol. 13 No. 4 Nov : (2007) , 2, 2, 2, 1, 23 (1., ; 2.,, ) : ( 2MnO 2 ),, ( 2MnO 2 2Ti). XRD SEM XPS,. :, MnO 2, Ti( )MnO 2. 2MnO 2, 2MnO 2 2Ti. : ; ; ; : O 646; TM 911 : A, L icoo 2. L icoo 2,,,.,, [ 122 ]., ( 2MnO 2 ),,,,,(308 mah /g),., Jahn2Teller,.,, [ 3 ].,, 2MnO 2 2 Ti, 2MnO 2, /, MnO 2, (MEVVA )( ) ; LEO21530 ( ) ; Philip s PANalytical X Pert X ( ) ; Quantum2000 XPS ( ) ; MBRAUN, LabMater100 ( )( ) ; LAND( ). ( > 99. 9% ) ; KMnO 4, ) 2MnO 2, [ 4 ] KMnO 4,,60 /h h,., h,, 2MnO 2. : , : , Tel: (862592) , E2mail: yyang@ xmu. edu. cn (: ), (2005H071),(20042L21)

2 4 : 437 2)( 2MnO 2 2Ti) 2MnO 2,, MEVVA, 60 kv, / cm 2, > 99. 9%, 250 nm, 150, 2 h [ 5 ]. 3) 2MnO 2, 2MnO 2 2Ti,. 2MnO 2 2MnO 2 2Ti,, ( PVDF)N2 (NMP) , 1. 5 cm,. 4) ( 2MnO 2 2Ti) [ 6 ] ; X, ; XPS A l K ev, W, < Pa. C1 s ( ev).,, 1mol/L L iclo 4 PC /DME (1 1, by Vol. ),,CR2025, 12 h V, 0. 2C (36 ma /g) XRD 1 2MnO 2 Ti 2MnO 2 2Ti XRD (30 ma,40 kv , 10 s, 5 80 )., 2MnO 2 ( a) ,,, C2 /m, nm. 2MnO 2 2Ti ( b), 2MnO 2, (001) (002), Ti 2MnO MnO 2 ( a) 2MnO 2 2Ti( b)xrd Fig. 1 XRD patterns of the 2MnO 2 ( a) and 2MnO 2 2Ti ( b) samp les 2. 2 SEM 2 2MnO 2 ( a) Ti 2MnO 2 2Ti( b) SEM., 2MnO 2, 2MnO 2 2Ti 2000, 5000, [ 3 ] MnO 2 2Ti EDS,, Ti, 1, ( 2MnO 2 2Ti) Ti/Mn MnO 2 2MnO 2 2TiSEM Fig. 2 SEM image of the 2MnO 2 ( a) and 2MnO 2 2Ti ( b) samp les

3 MnO 2 2TiEDS Fig. 3 EDS spectrum of the 2MnO 2 2Ti samp le 1 2MnO 2 2Ti EDS Tab. 1 Analytic result of EDS for the 2MnO 2 2Ti Element /% A tom ic /% O K Ti Mn Totals XPS 4 2MnO 2 2Ti Mn Ti XPS. Ti 260 nm, Ti 2p3 / ev, Ti 4 + ( ev ), Ti ( IV),Ti ( ev ) Ti( ) ( ev ),Ti ( ) ( ev ),. 4 2MnO 2 2Ti Mn ( a) Ti ( b) XPS ( ) Fig. 4 XPS p rofile spectra of Mn and Ti in the 2MnO 2 2Ti composite with different sputtering dep ths MnO 2 2MnO 2 2Ti, 0. 2 C 5 2MnO 2 2MnO 2 2Ti 0. 2C Fig. 5 D ischarge p rofiles of the 2MnO 2 ( a) and 2MnO 2 2Ti ( b) at 0. 2C ( V)

4 4 : 439 5,Ti 2 MnO 2 ( a) mah / g, mah /g;ti 2MnO 2 2Ti ( b), mah /g, mah /g, 2MnO 2., 2MnO 2 2 MnO 2 2Ti, 2, 2MnO 2, Mn 3. 7 [ 7 ],,, Mn, 2,., 2 MnO 2, 2MnO 2 2Ti 2,,, [ 8 ], MnO 2 ( /cm 2 ), Ti, Ti, [ 9 ], /,., 2MnO 2,, MnO 2 B i Pb [ ],. 3, 2MnO 2 2MnO 2 2Ti. Ti 2MnO 2, 2MnO 2,. ( Reference) : [ 1 ] GUO Xiao2jian (), L I J ie ( ), L I Yi2xiao (), et al. Studies on synthesis and electrochem2 ical performance of L i x N i 1 /3 Mn 1 /3 Co 1 /3 O 2 as cathode ma2 terial for lithium ion batteries[ J ]. Chinese), 2006, ( 3), Electrochem istry ( in [ 2 ] Ammundsen B, Paulsen J. Novel lithium 2 ion cathode materials based on layered manganese oxides [ J ]. Adv Maler, 2001, 13: [ 3 ] SHAO Na ( ), HUANG He2ning (), HU J ing2bo (), et al. Electrochem ical behavior of estazolam at a Pt/ glassy carbon ion imp lantation modi2 fied electrode [ J ]. Chinese J Anal Chem ( in Chinese), 2003, 31 ( 5) : [ 4 ] Komaba S, Kumagai N, Chiba S. Synthesis of layered MnO 2 by calcinations of KMnO 4 for rechargeable lithium cathode [ J ]. Electrochim Acta, 2000, 46, ( 1) : [ 5 ] HU J ing2bo (), L IQ i2long (). Studies on the voltammetric behavior of m itoxantrone and its ap2 p lication at the N i/gc modified electrode [ J ]. Chem J Chin Univ( in Chinese), 2001, 22 ( 3) : [ 6 ] HUANG Xing 2 kang. Preparation characterization and electrochem ical performances of MnO 2 [ D ]. Xiamen: Xiamen University, [ 7 ] Bach S, Pereira2Ramos J P, Baffier N. Rechargeable 3V L i cell using hydrated lamellar manganese oxide [ J ]. J Electrochem Soc, 1996, 143, ( 11 ) : [ 8 ] Department of Inorganic Chem istry in Dalian Technology University. Inorganic chem istry[m ]. Beijing : H igher Education Press, [ 9 ] TONGQ ing 2song ( ), YANG Yong ( ). Storage performance of the doped L i2mn2o sp inels[ J ]. J Funct Mater ( in Chinese), 2005, 36 ( 11 ) : [ 10 ] L I Juan ( ), GONG L iang2yu (), X IA Xi ( ). Synthesis of nanophase 2PbO by solid state reaction and its influence on MnO 2 electrode [ J ]. Chi2 nese J App l Chem ( in Chinese), 2001, 18 ( 4) : [ 11 ] TONGQ ing 2song ( ), GAN Hui ( ), L IAN J in2m ing (), et al. Research on the re2 chargeability of bismuth ( ) doped electrolytic man2 ganese dioxide [ J ]. Battery B imonthly ( in Chinese), 1997, 27 ( 1) : [ 12 ] D ING Shu 2rong ( ), L IXin 2hai ( ), WANG Zhi2xing(), et al. Modification of elec2 trolytic manganese dioxide [ J ]. Electrochem istry ( in Chinese), 2007, ( 2) :

5 Ion2implanting M odification of Layered Manganese D ioxide and Its Electrochem ica l Performance HUANG He2ning 1, 2, LΒ Dong2p ing 2, HUANG Xing2kang 2, ZHANG Q i2wei 1, YANG Yong 23 (1. D epa rtm en t of Chem ical and B iological Engineering, Collage of Sanm ing, S anm ing , Fu jian, Ch ina, 2. S tate Key L ab for Physical Chem istry of solid Surface, D epartm ent of Chem istry, X iam en U niversity, X iam en , Fujian, China ) Abstract: Layered MnO 2 ( 2MnO 2 ) was p repared by thermal decomposition of potassium permanganate. Tiwas ion2imp lanted into such 2MnO 2 by physical techniques, form ing a composite ( 2MnO 2 2Ti). These materials were characterized by XRD, SEM, XPS techniques and their electrochem ical p rop rieties were investigated. The results showed that the layered structure of 2MnO 2 did not been destroyed after Ti ion imp lantation, and the im2 p lanted Ti element was mainly Ti 4 + as indicated by XPS. Both of the first and the highest discharge specific ca2 pacities of the ion2imp lanted layered MnO 2 ( 2MnO 2 2Ti), compared to those of 2MnO 2, were imp roved signifi2 cantly. Key words: layered MnO 2 ; ion imp lantation; surface structure; electrochem ical performance