4 1 1998 2 EL ECTROCH EM ISTR Y V o l 4 N o 1 Feb 1998 3 ( 100080) (PAN ) 2 2L ic lo 4, R am an, ( IR ), X (XPS) (NM R ) L i + L i +, PAN C N N C = O S= O PAN C N L i +, L i + L i + PAN R am an,, X,,,,, (PEO ) (PPO ),, (10-7 10-8 Sgcm ),,, (PAN ) (> 10-3 Sgcm ) [ 1 ], [ 2,, ], 2 5 10-3 Sgcm, PAN, (EC) (PC) (DM F) (DM SO ), O = C<, O = S< PAN N C2, L i +,,,,, L i +, R am an ( IR ) X (XPS) (NM R ), 1997211224 ; (N SFC), (59672927); (1997) 3
80 1998 PAN, L ic lo 4, EC PC DM F DM SO, PAN 2EC2L i2 C lo 4, 1, L ic lo 4, 50 PAN PAN ( L ic lo 4), 120 10 h IFS66+ FRA 106 Fou rier IR 2R am an R am an 1 064 Λm, 200 mw, R am an, 0 1 mm IR KB r O Sg2 2 2 1 1 EC 2L ic lo 4 R am an, EC (713 cm - 1 ) [ 3 ] R am an EC2L ic lo 4, 713 cm - 1,,, (727 cm - 1 ) L ic lo 4 EC R am an EC C= O (893 cm - 1 ) IR C lo - 4 [ 4 ], EC R am an IR, L ic lo 4 L i + EC C= O O 1 EC2L ic lo 4, EC (L ic lo 4 DM F DM SO EC) R am an L i + F ig 1 T he R am an spectra of ring bending DM F O = C- N < O N mode of EC at different mo lar ratio s DM SO 2L ic lo of L ic lo 4gEC 4, a) 0; b) 0 13; c) 0 65; d) 1 38; L i + DM SO e) 3 11; f) 5 33, DM SO,
1 : 81 2 L ic lo 4gEC EC 713 cm - 1 ( EC 1 230 cm - 1 ), L i + EC, EC n s 6, (C f) (C b) (C) 2, C lo - 4 L ic lo 4, L i + 2 2C lo - 4 {L i + C lo - 4 }n (n 1), 2 2 PAN EC PAN PAN 2EC R am an, PAN EC ( 3) EC C= O PAN C N, 4 DM SO 2PAN, PAN, PAN C N, R am an, DM SO PAN C N 2 3 L iclo 4 PAN PAN C N N, L i +, ( 5% ), 2 EC2L ic lo 4 (C f) (C b) F ig 3 T he R am an spectra of the C= O stretch2 F ig 2 D ependences of the free and bound L i + ion concentrations (C r and C b) on the so lution concen tration C 3 EC R am an C = O (1 762 cm - 1 ) EC PAN ing mode (at 1 762 cm - 1 ) of EC at differ2 ent EC PAN mo lar ratio s, a) o ; b) 1 3; c) 3 2
82 1998 PAN 2EC2L ic lo 4, 5 PAN EC L ic lo 4 20 60 20, (2 270 cm - 1 ) PAN C N (2 240 cm - 1 ) [ 5 ], EC PAN ( 120 12 h ) EC2L ic lo 4 EC2PAN, L i + PAN C N N, (2 240 cm - 1 ) IR, L ic lo 4gPAN PAN gpcgl ic lo 4, DM F DM SO, L ic lo 4gPAN, L i + PAN C N PAN 4 PAN DM SO 5 R am an L i + PAN R am an DM SO PAN ( 303 cm - 1 CSC a) ECgPAN = 3 2 (, ); ; 670 cm - 1 b) ECgL ic lo 4= 7 3; CSC ; c) ECgPAN gl ic lo 4= 49 25 26 700 cm - 1 CSC ) F ig 4 T he mo lar ratio dependences of the relative R am an in ten sity of the n itrile stretch ing mode to different modes of DM SO CSC bending mode at 303 cm - 1 ; symm etric CSC stretch ing mode at 670 cm - 1 and CSC asymm etric stretch ing mode at 700 cm - 1 F ig 5 Identification of the interaction be2 tw een L i + ion and the nitrile group of PAN : a) R am an spectrum of ECg PAN w ith a m ass ratio of 3 2, b) R am an spectrum of ECgL ic lo 4 w ith a m ass ratio of 7 3, and c) R am an spectrum of po lym er electro lyte ECg PAN gl ic lo 4 w ith a m ass ratio of 49 25 26
1 : 83 L i +, PAN L i + DM SO DM F, DM F DM SO L i + PAN 2 4 ClO - 4 6 PAN gpcgl ic lo 4, PAN C N (2 240 cm - 1 ) L ic lo 4 PAN R am an, PC, L ic lo 4gPAN (1 2) PAN L i + (, 120 12 h, 7 ) (PC), L ic lo 4gPAN (1 7) IR ( 7) X, PAN 4 C N C lo - 4 8 R am an L ic lo 4g R am an, 6 PC ( : PC L ic lo 4 PAN 0; 7 2 1; 7 1 1; 7 1 2; 7 1 3), ( : L ic lo 4 PAN 0; 1 7; 1 4; 1 1) PAN 2PC2L ic lo 4 C N R am an F ig 6 R am an spectra of the nitrile stretch ing mode of PAN in po lym er clectro lytes PC L ic lo 4 PAN at mo lar ratio s of 0; 7 2 1, 7 1 1, 7 1 2 and 7 1 3 (from the bo ttom to the top) befo re ( left) and after (righ t) the p lasticizer is rem oved (from the bo ttom to the top: L ic lo 4 PAN = 0, 1 7, 1 4, and 1 1)
84 1998 7 PAN 8 L ic lo 4 L ic lo 4 PAN ( : 0 ( PAN ); 1 PAN C lo - 4 10; 1 8; 1 3; 1 1) R am an : 1 7; 1 4; 1 1 F ig 7 T he IR spectra of the nitrle group of PAN at PAN at different mo lar ratio s ( ) of L ic lo 4 PAN after the p lasticizer is rem oved from the po lym er electro lyte (from the bo ttom to the top: 0 (pu re F ig 8 T he R am an spectra of the v 1 mode of C lo - 4 anion at different mo lar ratio s of L ic lo 4 PAN ), 1 10, 1 8, 1 3 and 1 1) PAN in p lasticizer2rem oved po lym er elec2 tro lytes 1 7; 1 4; and 1 1 (from the bo t2 tom to top), C lo - 4 Rm an L ic lo 4gPAN L ic lo 4g ( ) L ic lo 4g,, 935 945 955 cm - 1 [ 6 ], L i + 2 2C lo - 4 L i + C lo - 4 {L i + C lo - 4 }n (n 2), 955 cm - 1 C lo - 4 C lo - 4 C lo - 4 PAN, PAN L i + 2PAN 2, {L i + C lo - 4 }n (n 1),, PAN 2 5 9 PAN ( 1 5 10-3 Sgcm ) 7 L i (NM R ), PAN,L i + NM R, ( ) ), ( ) ( )
1 : 85 ( ), (0 28 ev ), PAN L i +, L i +,,, ( ( ) ) 3 3 1, PAN 9 PAN 7 L i NM R (PAN 2PC2DM SO 2L ic lo 4, 25 35 35 5) F ig 9 A typ ical 7 L inm R spectrum of the p las2,, ticized po lym er electro lyte (PAN 2PC2DM 2, L i + SO 2L ic lo 4 at a m ass ratio of 25 35 35 5) 6 EC, L i + L i + 2 2C lo - 4, L i +,, L i +,, L i + PAN 4 C N L i + PAN L i + PAN,, L i + C lo - 4 PAN PAN, ( ) PAN PAN 2L i + ( 10a, b, c), L i +, ( L i + ), 3 2,, L i +,, L i + 2 2C lo - 4 ( 10d) L i + ( ) L i + PAN, PAN
86 1998, 10 L ic lo 4gPAN a L i +, L i + 2PAN, ; b c, L i + 2PAN, ; d, L i + 2PAN L i +,, F ig 10 A ssociation of ionic species in a p lasticized L ic lo 4gPAN system a T he L i + 2PAN associates and the ion pairs are decoup led due to the so lvation and strong com 2 petition effects of the p lasticizer fo r the L i + ions w hen p lasticizer is added to a L ic lo 4gPAN sys2 tem ; a repulsion exists betw een the po lym er and the p lasticizeṙ b and c M o re and mo re ion as2 sociates are decoup led and the content of the so lvent (p lasticizer) 2separated ion pairs is low ; a gel po lym er electro lyte w ith h igh ionic conductivity is obtained w hen mo re p lasticizer is added d If a p lasticizer w ith very strong competitive capability is added to the L ic lo 4gPAN system, the L i + 2PAN associates w ill be decoup led and the L i + ions turn to fo rm so lvent separated ion pairs w ith the p lasticizeṙ free charge carrierṡ T he appearance of the ion pairs w ill reduce the concentration of the
1 : 87 Spectro scop ic Investigation of Ion T ran spo rt M echan ism s in Po lyacrylon itrile Based E lectro lytes W ang Zhaox iang H uang B iying Xue Rongjian H uang Xuejie Chen L iquan 3 (L ab f or S olid S ta te Ion, Insṫ of P hy, Ch inese A cad em y of S ciences, B eij ing 100080) A bs tra c t R am an, IR, X2ray pho toelectron (XPS), and NM R spectra of com po2 nen ts in po lyacrylon itrile2based electro lytes have been studied It is found that there are strong in teraction s am ong the com ponen ts though differen t system s show differen t in terac2 tion characteristicṡ A concep t of com petition is p ropo sed betw een the po lym er m atrix and the p lasticizer on associating w ith the L i + ion ṡ By analyzing the im po rtan t function s of the p lasticizer, a po ssib le m echan ism of the ion s tran spo rt in the po lym er electro lyte is suggest2 ed Ke y w o rds R am an, IR, XPS, NM R, Po lym er electro lyte, L ic lo 4, PAN, P las2 ticiizer (so lven t) Re fe re nce s 1 A braham K M, A lam gir M L i + 2conductive so lid po lym er electro lytes w ith liquid2like conductivity J E lectrochem Soc, 1990, 137: 1 657 2 H uang H, Chen L Q, Xue R J M aterials and app licationṡ In So lid State Ionicṡ Edṡ Chow darib V R, Chandra S, Singh S and Srivastava P C Singapo re: W o rld Scientific, 1992: 199 3 H yodo S, O kabayash i K R am an intensity study of local structure in non2aqueous electro lyte so lutiong cation2so lven t in teraction in L ic lo 4gethylene carbonate E lectroch im A cta, 1989, 34: 1 551 4 Yeager H L, Fedyk J D, Parker R J Spectro scop ic studies of ionic so lvation in p ropylene carbonate J Phyṡ Chem, 1973, 77: 2 407 5 K laboe P, Grundnes J T he vibrational spectra of p rop ionitrile, 22ch lo ro and 22bromo p rop initrile Spec2 troch im A cta, 1968, 24A : 1 905 6 F ro st R L, Jam es D W, A pp leby R, M ayes R E Ion2pair fo rm ation and anion relaxation in aqueous so lu2 tions of group 1 perch lo rateṡ a R am an spectral study J Phyṡ Chem, 1992, 86: 3 840