Supporting information Polyaniline/Polyoxometalate Hybrid ...
Supporting information
Polyaniline/Polyoxometalate Hybrid Nanofibers as Cathode for Lithium Ion Batteries with Improved Lithium Storage Capacity Hongxun Yanga,c, Taeseup Songb, Li Liua, Anitha Devadossb, Fan Xiab, Hyungkyu Hanb, Hyunjung Parkb, Wolfgang Sigmunda,e, Kyungjung Kwond,*, and Ungyu Paika,b,* a
WCU Department of Energy Engineering, Hanyang University, Seoul 133-791,
Republic of Korea, b
Department of Materials Science Engineering, Hanyang University, Seoul 133-791,
Republic of Korea, c
School of Biology & Chemical Engineering, Jiangsu University of Science and
Technology, Zhenjiang 212003, China, d
Department of Energy & Mineral Resources Engineering, Sejong University, Seoul
143-747, Republic of Korea, e
Department of Materials Science and Engineering, University of Florida, Gainesville,
FL 32606, USA. *
Corresponding author: Ungyu Paik and Kyungjung Kwon
Prof. Ungyu Paik Tel: +82-2-2220-0502
Fax: +82-2-2281-0502
E-mail address: [email protected] Prof. Kyungjung Kwon Tel: +82-2-3408-3947 E-mail address: [email protected]
Materials: Phosphomolydic acid (H3PMo12O40, denoted as PMo12), Aniline, Dichloromethane, acetonitrile and other materials were received from Sigma-Aldrich Company. Ammonium peroxydisulfate (APS) was a radical initiator for the synthesis of polyaniline (PANI) hybrid nanofibers.
Table S1. The electrical conductivities of different materials. Material
σ (S/cm)
PANI/PMo12
1.37
PANI
0.85
bulk PANI/PMo12 ref. 27
0.5~1.0
Reference. (27) Lira-cantú M.; Gómez-Romero, P. Chem. Mater. 1998, 10, 698-704.
Figure S1. SEM of PANI nanofibers before charge-discharge.
Figure S2. Synthesis of nanofibrous PANI/PMo12 composite using an interfacial polymerization method.
Capacity retention (%)
100 80 60 40 20
PANI/PMo12 PANI
0 0
10
20
30
40
50
Cycle number Figure S3. Capacity retentions of PANI/PMo12 and PANI nanofibers at 0.1 C rates.
Figure S4. SEM of PANI/PMo12 nanofibers after 50 charge-discharge cycles at a constant rate of 0.1 C.
Figure S5. SEM of PANI nanofibers after 50 charge-discharge cycles at a constant rate of 0.1 C.
Intensity (a. u.)
(a) (b)
(c)
(d)
10
20
30
40
50
60
70
Figure S6. X-ray diffraction patterns of PMo12/PANI (a) and PANI/PMo12 after 50 charge-discharge cycles (b), PANI nanofibers before tested (c), and PANI nanofibers after 50 charge-discharge cycles (d).
(a)
T%
(b)
(c)
(d) (e)
1600 1400 1200 1000 800 Wavelength cm-1
600
Figure S7. FTIR spectra for PMo12/PANI (a), sPANI/PMo12 after 50 charge-discharge cycles (b), PANI nanofibers before tested (c), PANI nanofibers after 50 charge-discharge cycles (d), and H3PMo12O40 (e). Asterisks mark the peaks assigned to the [PMo12O40]3- anion (PMo12).
0.1 C
Ccapacity retention (%)
100
PANI/PMo12 PANI
0.2 C 0.5 C
80
1C
60
2C
40 20 0 0
5
10 15 Cycle number
20
25
Figure S8. Capacity retentions of PANI/PMo12 nanofibers and PANI nanofibers as cathode for lithium ion batteries at different charge-discharge rates.
Table S2. Impedance parameters for PANI/PMo12 and PANI. Samples
Rs (Ω)
Rct (Ω)
PANI/PMo12 0.5217 93.6 PANI
1.088
203.8
Polyaniline/Polyoxometalate Hybrid Nanofibers as Cathode for Lithium Ion Batteries with Improved Lithium Storage Capacity Hongxun Yanga,c, Taeseup Songb, Li Liua, Anitha Devadossb, Fan Xiab, Hyungkyu Hanb, Hyunjung Parkb, Wolfgang Sigmunda,e, Kyungjung Kwond,*, and Ungyu Paika,b,* a
WCU Department of Energy Engineering, Hanyang University, Seoul 133-791,
Republic of Korea, b
Department of Materials Science Engineering, Hanyang University, Seoul 133-791,
Republic of Korea, c
School of Biology & Chemical Engineering, Jiangsu University of Science and
Technology, Zhenjiang 212003, China, d
Department of Energy & Mineral Resources Engineering, Sejong University, Seoul
143-747, Republic of Korea, e
Department of Materials Science and Engineering, University of Florida, Gainesville,
FL 32606, USA. *
Corresponding author: Ungyu Paik and Kyungjung Kwon
Prof. Ungyu Paik Tel: +82-2-2220-0502
Fax: +82-2-2281-0502
E-mail address: [email protected] Prof. Kyungjung Kwon Tel: +82-2-3408-3947 E-mail address: [email protected]
Materials: Phosphomolydic acid (H3PMo12O40, denoted as PMo12), Aniline, Dichloromethane, acetonitrile and other materials were received from Sigma-Aldrich Company. Ammonium peroxydisulfate (APS) was a radical initiator for the synthesis of polyaniline (PANI) hybrid nanofibers.
Table S1. The electrical conductivities of different materials. Material
σ (S/cm)
PANI/PMo12
1.37
PANI
0.85
bulk PANI/PMo12 ref. 27
0.5~1.0
Reference. (27) Lira-cantú M.; Gómez-Romero, P. Chem. Mater. 1998, 10, 698-704.
Figure S1. SEM of PANI nanofibers before charge-discharge.
Figure S2. Synthesis of nanofibrous PANI/PMo12 composite using an interfacial polymerization method.
Capacity retention (%)
100 80 60 40 20
PANI/PMo12 PANI
0 0
10
20
30
40
50
Cycle number Figure S3. Capacity retentions of PANI/PMo12 and PANI nanofibers at 0.1 C rates.
Figure S4. SEM of PANI/PMo12 nanofibers after 50 charge-discharge cycles at a constant rate of 0.1 C.
Figure S5. SEM of PANI nanofibers after 50 charge-discharge cycles at a constant rate of 0.1 C.
Intensity (a. u.)
(a) (b)
(c)
(d)
10
20
30
40
50
60
70
Figure S6. X-ray diffraction patterns of PMo12/PANI (a) and PANI/PMo12 after 50 charge-discharge cycles (b), PANI nanofibers before tested (c), and PANI nanofibers after 50 charge-discharge cycles (d).
(a)
T%
(b)
(c)
(d) (e)
1600 1400 1200 1000 800 Wavelength cm-1
600
Figure S7. FTIR spectra for PMo12/PANI (a), sPANI/PMo12 after 50 charge-discharge cycles (b), PANI nanofibers before tested (c), PANI nanofibers after 50 charge-discharge cycles (d), and H3PMo12O40 (e). Asterisks mark the peaks assigned to the [PMo12O40]3- anion (PMo12).
0.1 C
Ccapacity retention (%)
100
PANI/PMo12 PANI
0.2 C 0.5 C
80
1C
60
2C
40 20 0 0
5
10 15 Cycle number
20
25
Figure S8. Capacity retentions of PANI/PMo12 nanofibers and PANI nanofibers as cathode for lithium ion batteries at different charge-discharge rates.
Table S2. Impedance parameters for PANI/PMo12 and PANI. Samples
Rs (Ω)
Rct (Ω)
PANI/PMo12 0.5217 93.6 PANI
1.088
203.8
