Facile Synthesis of MnO2/CNTs Composite for Supercapacitor ...
Supplementary Information
Facile Synthesis of MnO2/CNTs Composite for Supercapacitor Electrodes with Long Cycle Stability Li Li,1,2 Zhong A. Hu,*1 Ning An,1 1
Yu Y. Yang,1 Zhi M. Li,1 and Hong Y. Wu1
Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of
Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, China. 2
College of Chemical Engineering, Northwest University for Nationalities, Lanzhou,
Gansu 730030, China.
XPS analysis
0
200
400
600
800
Mn 2p3/2
Intensity (a.u.)
O 1s Mn 2p3/2
11.6eV
C 1s
Mn 3p Mn 3s
Intensity (a.u.)
a
Mn 2p1/2
1.
1000
635
Binding energy (eV)
4.96eV
Mn 2p1/2
640 645 650 655 Binding energy (eV)
660
Mn 3s
Intensity (a.u.)
c
b
80
85 90 Binding energy (eV)
95
Figure S1 (a) XPS, (b) Mn 2p XPS and (c) Mn 3s XPS spectra of MnO2/CNTs composite. Figure S1a shows a typical overall XPS spectrum of the composite, which suggested that the composite is composed of Mn, O and C elements. In the Mn 2p region (Figure S1b), the Mn 2p3/2 peak is centered at 643.01 eV and the Mn 2p1/2 peak at 654.61 eV, with an energy separation of 11.6 eV, which matches with the reported data for MnO2.1,2 2.
Raman analysis
ID:IG=0.45
2D D
500 1000 1500 2000 2500 -1 Raman shift (cm )
571 648
b
G Intensity (a.u.)
Intensity (a.u.)
a
D ID:IG=1.21 G 2D D'
500 1000 1500 2000 2500 -1 Raman shift (cm )
Figure S2 Raman spectrum of (a) the pristine CNTs and (b) MnO2/CNTs composite. Figure S2b shows a typical spectrum of the MnO2/CNTs composite over the measured spectral range. Four characteristic peaks of CNTs at 1329 (D band), 1580 (G band), 1615 (D′ band) and 2663 cm-1 (2D band) are clearly observed from this figure, as reported previously.3-6 Among them, the D band is attributed to the defects in the curved graphene sheet on the nanotubes and the G band represents the crystalline structure of the nanotubes. Usually, the intensity ratio of D to G band (ID/IG) is an important yardstick to measure the degree of defects of carbon materials.7 Compared with the ID/IG value of the pristine CNTs (Figure S2a), the ID/IG value of the composite increased greatly. Near the G band, the D′ vibrational mode, which does not exist in pure graphite, is observed with high intensity in intercalated graphite compounds.8-10 In addition, two sharp, low frequency bands at about 571 and 648 cm-1 for the composite are in good agreement with the birnessite-type MnO2 compounds previously reported.11, 12 3.
TG analysis
Figure S3 TG curves of MnO2/CNTs composite. 4.
Wettability test
Figure S4 Contact angle measurement of (a) the pristine CNTs and (b) MnO2/CNTs composite. 5.
BET test
100
pristine CNTs 2 -1 surface area: 51m g Adsorption Desorption
60 40 20 0
120
3
Quantity Adsorbed (cm /g)
0.0
200 160
MnO2/CNTs composite 2 -1
80
surface area: 71m g
60
Adsorption Desorption
40 20 0 0.0
0.2 0.4 0.6 0.8 1.0 Relative Pressure (p/p0)
2 -1
surface area: 317m g
120 Adsorption Desorption
80 40 0.0
c
100
b pure MnO2
0.2 0.4 0.6 0.8 1.0 Relative Pressure (p/p0)
3
80
3
a
Quantity Adsorbed (cm /g)
120
dV/dlog(D) (cm /g)
3
Quantity Adsorbed (cm /g)
140
0.2 0.4 0.6 0.8 1.0 Relative Pressure (p/p0)
0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00
d MnO2/CNTs MnO2 CNTs
0
10
20
30
40
Pore Diameter (nm)
Figure S5 Nitrogen adsorption-desorption isotherms of (a) the pristine CNTs, (b) the pure MnO2, and (c) the MnO2/CNTs composite. (d) BJH pore size distributions plot.
REFERENCES
1.
Li, Z.; Wang, J.; Liu, S.; Liu, X.; Yang, S., Synthesis of Hydrothermally Reduced
Graphene/MnO2 Composites and Their Electrochemical Properties as Supercapacitors. J. Power Sources 2011, 196, 8160-8165. 2.
Xia, H.; Lai, M.; Lu, L., Nanoflaky MnO2/Carbon Nanotube Nanocomposites as
Anode Materials for Lithium-ion Batteries. J. Mater. Chem. 2010, 20, 6896-6902. 3.
Yan, X.; Itoh, T.; Kitahama, Y.; Suzuki, T.; Sato, H.; Miyake, T.; Ozaki, Y., A
Raman Spectroscopy Study on Single-Wall Carbon Nanotube/Polystyrene Nanocomposites: Mechanical Compression Transferred from the Polymer to Single-Wall Carbon Nanotubes. J. Phys. Chem. C 2012, 116, 17897-17903. 4.
Yu, K.; Lu, G.; Bo, Z.; Mao, S.; Chen, J., Carbon Nanotube with Chemically
Bonded Graphene Leaves for Electronic and Optoelectronic Applications. J. Phys.
Chem. Lett. 2011, 2, 1556-1562. 5.
Jorio, A.; Pimenta, M. A.; Souza Filho, A. G.; Saito, R.; Dresselhaus, G.;
Dresselhaus, M. S., Characterizing Carbon Nanotube Samples with Resonance Raman Scattering. New J. Phys. 2003, 5, 139. 6.
Lu, P.; Hsieh, Y., Multiwalled Carbon Nanotube (MWCNT) Reinforced
Cellulose Fibers by Electrospinning. ACS Appl. Mater. Interfaces 2010, 2, 2413-2420. 7.
Wang, H. J.; Peng, C.; Zheng, J. D.; Peng, F.; Yu, H., Design, Synthesis and the
Electrochemical Performance of MnO2/C@CNT as Supercapacitor Material. Mater.
Res. Bull. 2013, 48, 3389-3393. 8.
Osswald, S.; Havel, M.; Gogotsi, Y., Monitoring Oxidation of Multiwalled
Carbon Nanotubes by Raman Spectroscopy. J. Raman Spectrosc. 2007, 38, 728-736. 9.
Masarapu, C.; Subramanian, V.; Zhu, H.; Wei, B., Long‐Cycle Electrochemical
Behavior of Multiwall Carbon Nanotubes Synthesized on Stainless Steel in Li Ion Batteries. Adv. Funct. Mater. 2009, 19, 1008-1014. 10. Costa, S.; Borowiak-Palen, E.; Kruszynska, M.; Bachmatiuk, A.; Kalenczuk, R. J., Characterization of Carbon Nanotubes by Raman Spectroscopy. Mater. Sci. Poland.
2008, 26, 433-441. 11. Chen, Y.; Zhang, Y.; Geng, D.; Li, R.; Hong, H.; Chen, J.; Sun, X., One-pot
Synthesis of MnO2 Graphene Carbon Nanotube Hybrid by Chemical Method. Carbon
2011, 49, 4434-4442. 12. Xia, H.; Wang, Y.; Lin, J.; Lu, L., Hydrothermal Synthesis of MnO2/CNT Nanocomposite with a CNT Core/Porous MnO2 Sheath Hierarchy Architecture for Supercapacitors. Nanoscale res. lett. 2012, 7, 1-10.
Facile Synthesis of MnO2/CNTs Composite for Supercapacitor Electrodes with Long Cycle Stability Li Li,1,2 Zhong A. Hu,*1 Ning An,1 1
Yu Y. Yang,1 Zhi M. Li,1 and Hong Y. Wu1
Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of
Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, China. 2
College of Chemical Engineering, Northwest University for Nationalities, Lanzhou,
Gansu 730030, China.
XPS analysis
0
200
400
600
800
Mn 2p3/2
Intensity (a.u.)
O 1s Mn 2p3/2
11.6eV
C 1s
Mn 3p Mn 3s
Intensity (a.u.)
a
Mn 2p1/2
1.
1000
635
Binding energy (eV)
4.96eV
Mn 2p1/2
640 645 650 655 Binding energy (eV)
660
Mn 3s
Intensity (a.u.)
c
b
80
85 90 Binding energy (eV)
95
Figure S1 (a) XPS, (b) Mn 2p XPS and (c) Mn 3s XPS spectra of MnO2/CNTs composite. Figure S1a shows a typical overall XPS spectrum of the composite, which suggested that the composite is composed of Mn, O and C elements. In the Mn 2p region (Figure S1b), the Mn 2p3/2 peak is centered at 643.01 eV and the Mn 2p1/2 peak at 654.61 eV, with an energy separation of 11.6 eV, which matches with the reported data for MnO2.1,2 2.
Raman analysis
ID:IG=0.45
2D D
500 1000 1500 2000 2500 -1 Raman shift (cm )
571 648
b
G Intensity (a.u.)
Intensity (a.u.)
a
D ID:IG=1.21 G 2D D'
500 1000 1500 2000 2500 -1 Raman shift (cm )
Figure S2 Raman spectrum of (a) the pristine CNTs and (b) MnO2/CNTs composite. Figure S2b shows a typical spectrum of the MnO2/CNTs composite over the measured spectral range. Four characteristic peaks of CNTs at 1329 (D band), 1580 (G band), 1615 (D′ band) and 2663 cm-1 (2D band) are clearly observed from this figure, as reported previously.3-6 Among them, the D band is attributed to the defects in the curved graphene sheet on the nanotubes and the G band represents the crystalline structure of the nanotubes. Usually, the intensity ratio of D to G band (ID/IG) is an important yardstick to measure the degree of defects of carbon materials.7 Compared with the ID/IG value of the pristine CNTs (Figure S2a), the ID/IG value of the composite increased greatly. Near the G band, the D′ vibrational mode, which does not exist in pure graphite, is observed with high intensity in intercalated graphite compounds.8-10 In addition, two sharp, low frequency bands at about 571 and 648 cm-1 for the composite are in good agreement with the birnessite-type MnO2 compounds previously reported.11, 12 3.
TG analysis
Figure S3 TG curves of MnO2/CNTs composite. 4.
Wettability test
Figure S4 Contact angle measurement of (a) the pristine CNTs and (b) MnO2/CNTs composite. 5.
BET test
100
pristine CNTs 2 -1 surface area: 51m g Adsorption Desorption
60 40 20 0
120
3
Quantity Adsorbed (cm /g)
0.0
200 160
MnO2/CNTs composite 2 -1
80
surface area: 71m g
60
Adsorption Desorption
40 20 0 0.0
0.2 0.4 0.6 0.8 1.0 Relative Pressure (p/p0)
2 -1
surface area: 317m g
120 Adsorption Desorption
80 40 0.0
c
100
b pure MnO2
0.2 0.4 0.6 0.8 1.0 Relative Pressure (p/p0)
3
80
3
a
Quantity Adsorbed (cm /g)
120
dV/dlog(D) (cm /g)
3
Quantity Adsorbed (cm /g)
140
0.2 0.4 0.6 0.8 1.0 Relative Pressure (p/p0)
0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00
d MnO2/CNTs MnO2 CNTs
0
10
20
30
40
Pore Diameter (nm)
Figure S5 Nitrogen adsorption-desorption isotherms of (a) the pristine CNTs, (b) the pure MnO2, and (c) the MnO2/CNTs composite. (d) BJH pore size distributions plot.
REFERENCES
1.
Li, Z.; Wang, J.; Liu, S.; Liu, X.; Yang, S., Synthesis of Hydrothermally Reduced
Graphene/MnO2 Composites and Their Electrochemical Properties as Supercapacitors. J. Power Sources 2011, 196, 8160-8165. 2.
Xia, H.; Lai, M.; Lu, L., Nanoflaky MnO2/Carbon Nanotube Nanocomposites as
Anode Materials for Lithium-ion Batteries. J. Mater. Chem. 2010, 20, 6896-6902. 3.
Yan, X.; Itoh, T.; Kitahama, Y.; Suzuki, T.; Sato, H.; Miyake, T.; Ozaki, Y., A
Raman Spectroscopy Study on Single-Wall Carbon Nanotube/Polystyrene Nanocomposites: Mechanical Compression Transferred from the Polymer to Single-Wall Carbon Nanotubes. J. Phys. Chem. C 2012, 116, 17897-17903. 4.
Yu, K.; Lu, G.; Bo, Z.; Mao, S.; Chen, J., Carbon Nanotube with Chemically
Bonded Graphene Leaves for Electronic and Optoelectronic Applications. J. Phys.
Chem. Lett. 2011, 2, 1556-1562. 5.
Jorio, A.; Pimenta, M. A.; Souza Filho, A. G.; Saito, R.; Dresselhaus, G.;
Dresselhaus, M. S., Characterizing Carbon Nanotube Samples with Resonance Raman Scattering. New J. Phys. 2003, 5, 139. 6.
Lu, P.; Hsieh, Y., Multiwalled Carbon Nanotube (MWCNT) Reinforced
Cellulose Fibers by Electrospinning. ACS Appl. Mater. Interfaces 2010, 2, 2413-2420. 7.
Wang, H. J.; Peng, C.; Zheng, J. D.; Peng, F.; Yu, H., Design, Synthesis and the
Electrochemical Performance of MnO2/C@CNT as Supercapacitor Material. Mater.
Res. Bull. 2013, 48, 3389-3393. 8.
Osswald, S.; Havel, M.; Gogotsi, Y., Monitoring Oxidation of Multiwalled
Carbon Nanotubes by Raman Spectroscopy. J. Raman Spectrosc. 2007, 38, 728-736. 9.
Masarapu, C.; Subramanian, V.; Zhu, H.; Wei, B., Long‐Cycle Electrochemical
Behavior of Multiwall Carbon Nanotubes Synthesized on Stainless Steel in Li Ion Batteries. Adv. Funct. Mater. 2009, 19, 1008-1014. 10. Costa, S.; Borowiak-Palen, E.; Kruszynska, M.; Bachmatiuk, A.; Kalenczuk, R. J., Characterization of Carbon Nanotubes by Raman Spectroscopy. Mater. Sci. Poland.
2008, 26, 433-441. 11. Chen, Y.; Zhang, Y.; Geng, D.; Li, R.; Hong, H.; Chen, J.; Sun, X., One-pot
Synthesis of MnO2 Graphene Carbon Nanotube Hybrid by Chemical Method. Carbon
2011, 49, 4434-4442. 12. Xia, H.; Wang, Y.; Lin, J.; Lu, L., Hydrothermal Synthesis of MnO2/CNT Nanocomposite with a CNT Core/Porous MnO2 Sheath Hierarchy Architecture for Supercapacitors. Nanoscale res. lett. 2012, 7, 1-10.
