Supporting Information Porous Nickel Hydroxide-Manganese Dioxide ...
Supporting Information Porous Nickel Hydroxide-Manganese Dioxide-Reduced Graphene Oxide Ternary Hybrid Spheres as Excellent Supercapacitor Electrode Materials Hao Chenab, Shuxue Zhou,a and Limin Wua* a
Department of Materials Science and Advanced Materials Laboratory, Fudan University,
Shanghai 20043, PR China; bSchool of Engineering, and National Engineering and Technology Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang Agriculture and Forestry Unversity, Hangzhou Lin’an 311300, PR China E-mail: [email protected]
1
Figure S1. EDX spectra of (a) entire area, (b) center area, and (c) edge region of hybrid sphere supported on Cu grid with a lacey film. (d) Full XPS spectra of Ni(OH)2-MnO2-RGO (A in
2
brackets denotes Auger electron peaks). (e) Full XPS and (g) C1s XPS spectra of GO and RGO. (f) Raman spectra of GO and RGO. (h) Photographs of as-obtained Ni(OH)2-MnO2 (left) and Ni(OH)2-MnO2-RGO hybrid spheres (right) powders.
3
Table S1. Comparison of maximum Cs of the reported nickel-manganese oxide/hydroxide-, manganese
dioxide-graphene-,
nickel
oxide/hydroxide-graphene-,
and
nickel-cobalt
oxide/hydroxide-graphene-based composite pseudocapacitive materials and the present work. Cs (F g–1)
Ref.
Binary Manganese-Nickel Oxides
160 (50 mV s–1)
1
Porous nickel manganite materials
180 (0.25 A g–1)
2
Nanosized Ni-Mn Oxides
195 (10 mV s–1)
3
Mn/Ni mixed oxides
210 (0.12 A g–1)
4
Nickel-manganese oxide
284 (5 mV s–1)
5
Ni(OH)2-MnO2 core-shell nanostructures
355 (0.5 A g–1)
6
Mesoporous Mn-Ni oxides
411 (2 mV s–1)
7
Nanostructured NiO-MnO2 composite
453 (10 mV s–1)
8
Ultra-fine Mn-Ni-Cu oxides
490 (2 mV s–1)
9
NiO-MnO2 core-shell nanocomposites
528 (1 mV s–1)
10
Microporous nickel-manganese oxide
685 (2 mA cm–2)
11
Nanostructured Mn-Ni-Co oxides
1260 (1 A g–1)
12
Ni(OH)2-MnO2 hybrid nanosheets
2628 (3 A g–1)
13*
Graphene-MnO2 nanowall
122 (10 mV s–1)
14
Graphene-MnO2-carbon nanotubes
193 (0.2 A g–1)
15
Graphene-honeycomb-like MnO2
210 (0.5 A g–1)
16
Hydrothermally reduced graphene-MnO2
212 (2 mV s–1)
17
Graphene Oxide-MnO2 nanowires
216 (0.15 A g–1)
18
Graphene nanosheets-MnO2
235 (20 mV s–1)
19
Flexible graphene-MnO2 composite papers
256 (0.5 A g–1)
20
Electrodes based on materials 1. Nickel-manganese oxide/hydroxide composites
2. Manganese dioxide-graphene composites
4
Graphene-needle-like MnO2
260 (0.2 A g–1)
21
Graphene sheet-MnO2 sheet mutilayers
263 (0.283 A g–1)
22
Graphene nanoplate-MnO2
309 (5 mV s–1)
23
Nanostructured graphene-MnO2
310 (2 mV s–1)
24
Graphene-MnO2 nanostructured textiles
315 (2 mV s–1)
25
Graphene-flower-like MnO2
328 (0.5 mA/cm2)
26
Graphene-MnO2 nanoparticles
365 (5 mV s–1)
27
Graphene-MnO2 film
400 (10 mV s–1)
28
Reduced graphene oxide-MnO2 hollow sphere
578 (0.5 A g–1)
29*
Graphene sheet-porous NiO hybrid film
400 (2 A g–1)
30
Graphene porous NiO nanocomposite
430 (0.2 A g–1)
31
Monolayer graphene-NiO nanosheets
525 (0.2 A g–1)
32
NiO-attached graphene oxide nanosheets
569 (5 A g–1)
33
Reduced graphene oxide-nickel oxide composite
770 (2 mV s–1)
34
Ni(OH)2-graphene hybrid material
855 (5 mV s–1)
35
Graphene oxide-nickel oxide
890 (5 mV s–1)
36
Graphene-nickel hydroxide nanosheet hybrid
1163 (5 mV s–1)
37
Reduced graphene oxide-α-Ni(OH)2 hybrid composites
1215 (5 mV s–1)
38
Ni(OH)2 nanoplates grown on graphene
1335 (2.8 A g–1)
39
Ni(OH)2-graphene
1735 (1 mV s–1)
40
Spherical α-Ni(OH)2 grown on graphene
1761 (5 mV s–1)
41
Nanocomposites of Ni(OH)2-reduced graphene oxides
1804 (1 A g–1)
42
Ni(OH)2 nanoflakes on reduced graphene oxide
1828 (1 A g–1)
43
3. Nickel oxide/hydroxide-graphene composites
4. Nickel-cobalt binary oxide/hydroxide-graphene composites Cobalt-nickel oxides-carbon nanotube composites
569 (10 mA cm–2)
44
Graphene-nickel cobaltite nanocomposite
618 (5 mV s–1)
45
5
Co0.45Ni0.55O nanorods on reduced graphene oxide sheets
823 (1 A g–1)
46
NiCo2O4-reduced graphene oxide composites
835 (1 A g–1)
47
Nickel cobalt oxide-reduced graphite oxide composite
1222 (0.5 A g–1)
48
Ni(OH)2-CoO-reduced graphene oxide composites
1317 (2 A g–1)
49
Ni(OH)2-MnO2-RGO hybrid spheres
1985 (2 A g–1)
This work
* our previously reported work.
Table S2. Comparison of maximum densities and corresponding average power densities of some reported nickel-manganese oxide/hydroxide-, manganese dioxide-graphene-, nickel oxide/hydroxide-graphene-, and nickel-cobalt oxide/hydroxide-graphene-based composite pseudocapacitive materials and the present work Energy density
Power density
(Wh⋅⋅kg−1)
(kW⋅⋅kg−1)
Ni(OH)2/MnO2 core/shell nanostructures
41.2
0.50
6
Mn/Ni mixed oxides
3.12
1.00
4
Graphene-MnO2 nanoparticles
50.2
0.22
27
Graphene-flower-like MnO2
11.4
25.8 (Pmax)
26
Graphene-MnO2 nanostructured textiles
12.5
110 (Pmax)
25
Graphene nanosheets-MnO2
33.1
20.4 (Pmax)
19
Graphene-Ni(OH)2 nanoplates
37.0
10.0
39
Graphene Sheet/Porous NiO Hybrid Film
16.8
-
30
Ni(OH)2-MnO2-RGO hybrid spheres
54.0
0.39
This work
Electrodes based on materials
Ref.
Pmax: maximum power density.
6
Table S3. Comparison of the maximum energy densities, corresponding average power densities and voltage range of some reported nickel or manganese oxide/hydroxide based asymmetric supercapacitors, and the present work Energy density (Wh⋅⋅kg−1)
Power density (kW⋅⋅kg−1)
Voltage range (V)
Ref.
Graphitic hollow carbon spheres-MnO2 nanofibers//graphitic hollow carbon spheres
22.1
0.10
0-2
50
Graphite oxide-MnO2//graphite oxide
24.3
24.5 (Pmax)
0-2
51
Ni(OH)2//AC
25.0
-
0.6-1.3
52
MnO2//graphene
25.2
0.10
0-2
53
K0.27MnO2·0.6H2O//AC
25.3
0.14
0-1.8
54
MnO2 nanowire-SWCNT//In2O3 nanowireSWCNT
25.5
50.3 (Pmax)
0-2
55
RGO-MnO2-CNTs//AC-WCNT
27.0
0.13
0-2
56
Ni(OH)2//graphene
30.0
1.00
0-1.6
57
Poly(3,4-ethylenedioxythiophene)-MnO2//AC
30.2
0.18
0-1.8
58
Ni(OH)2-MnO2-RGO hybrid spheres// FRGO
32.6
0.31
0-1.6
This work
Positive materials//negative materials
AC: activated carbon, CNT: carbon nanotube, Pmax: maximum power density.
7
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(27) Chen, C.-Y.; Fan, C.-Y.; Lee, M.-T.; Chang, J.-K. Tightly Connected MnO2-Graphene with Tunable Energy Density and Power Density for Supercapacitor Applications. J. Mater. Chem. 2012, 22, 7697-7700. (28) Lee, H.; Kang, J.; Cho, M. S.; Choi, J.-B.; Lee, Y. MnO2/Graphene Composite Electrodes for Supercapacitors: the Effect of Graphene Intercalation on Capacitance. J. Mater. Chem. 2011, 21, 18215-18219. (29) Chen, H.; Zhou, S.; Chen, M.; Wu, L. Reduced Graphene Oxide-MnO2 Hollow Sphere Hybrid Nanostructures as High-Performance Electrochemical Capacitors. J. Mater. Chem. 2012, 22, 25207-25216. (30) Xia, X.; Tu, J.; Mai, Y.; Chen, R.; Wang, X.; Gu, C.; Zhao, X. Graphene Sheet/Porous NiO Hybrid Film for Supercapacitor Applications. Chem. -Eur. J. 2011, 17, 10898-10905. (31) Jiang, Y.; Chen, D.; Song, J.; Jiao, Z.; Ma, Q.; Zhang, H.; Cheng, L.; Zhao, B.; Chu, Y. A Facile Hydrothermal Synthesis of Graphene Porous NiO Nanocomposite and its Application in Electrochemical Capacitors. Electrochim. Acta 2013, 91, 173-178. (32) Zhao, B.; Song, J.; Liu, P.; Xu, W.; Fang, T.; Jiao, Z.; Zhang, H.; Jiang, Y. Monolayer Graphene/NiO Nanosheets with Two-Dimension Structure for Supercapacitors. J. Mater. Chem. 2011, 21, 18792-18798. (33) Wu, M.-S.; Lin, Y.-P.; Lin, C.-H.; Lee, J.-T. Formation of Nano-Scaled Crevices and Spacers in NiO-Attached Graphene Oxide Nanosheets for Supercapacitors. J. Mater. Chem. 2012, 22, 2442-2448. (34) Zhu, X.; Dai, H.; Hu, J.; Ding, L.; Jiang, L. Reduced Graphene Oxide-Nickel Oxide Composite as High Performance Electrode Materials for Supercapacitors. J. Power Sources 2012, 203, 243-249.
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(35) Wang, H.; Liang, Y.; Mirfakhrai, T.; Chen, Z.; Casalongue, H.; Dai, H. Advanced Asymmetrical Supercapacitors Based on Graphene Hybrid Materials. Nano Res. 2011, 4, 729-736. (36) Yuan, B.; Xu, C.; Deng, D.; Xing, Y.; Liu, L.; Pang, H.; Zhang, D. Graphene Oxide/Nickel Oxide Modified Glassy Carbon Electrode for Supercapacitor and Nonenzymatic Glucose Sensor. Electrochim. Acta 2013, 88, 708-712. (37) Zhu, J.; Chen, S.; Zhou, H.; Wang, X. Fabrication of a Low Defect Density GrapheneNickel Hydroxide Nanosheet Hybrid with Enhanced Electrochemical Performance. Nano Res. 2012, 5, 11-19. (38) Lee, J. W.; Ahn, T.; Soundararajan, D.; Ko, J. M.; Kim, J.-D. Non-Aqueous Approach to the Preparation of Reduced Graphene Oxide/α-Ni(OH)2 Hybrid Composites and Their High Capacitance Behavior. Chem. Commun. 2011, 47, 6305-6307. (39) Wang, H.; Casalongue, H. S.; Liang, Y.; Dai, H. Ni(OH)2 Nanoplates Grown on Graphene as Advanced Electrochemical Pseudocapacitor Materials. J. Am. Chem. Soc. 2010, 132, 7472-7477. (40) Yan, J.; Fan, Z.; Sun, W.; Ning, G.; Wei, T.; Zhang, Q.; Zhang, R.; Zhi, L.; Wei, F. Advanced Asymmetric Supercapacitors Based on Ni(OH)2/Graphene and Porous Graphene Electrodes with High Energy Density. Adv. Funct. Mater. 2012, 22, 2632-2641. (41) Yang, S.; Wu, X.; Chen, C.; Dong, H.; Hu, W.; Wang, X. Spherical α-Ni(OH)2 Nanoarchitecture Grown on Graphene as Advanced Electrochemical Pseudocapacitor Materials. Chem. Commun. 2012, 48, 2773-2775.
12
(42) Xiao, J.; Yang, S. Nanocomposites of Ni(OH)2/Reduced Graphene Oxides with Controllable
Composition,
Size,
and
Morphology:
Performance
Variations
as
Pseudocapacitor Electrodes. ChemPlusChem 2012, 77, 807-816. (43) Chang, J.; Xu, H.; Sun, J.; Gao, L. High Pseudocapacitance Material Prepared via in Situ Growth of Ni(OH)2 Nanoflakes on Reduced Graphene Oxide. J. Mater. Chem. 2012, 22, 11146-11150. (44) Fan, Z.; Chen, J.; Cui, K.; Sun, F.; Xu, Y.; Kuang, Y. Preparation and Capacitive Properties of Cobalt-Nickel Oxides/Carbon Nanotube Composites. Electrochim. Acta 2007, 52, 29592965. (45) Wang, H.; Holt, C. B.; Li, Z.; Tan, X.; Amirkhiz, B.; Xu, Z.; Olsen, B.; Stephenson, T.; Mitlin, D. Graphene-Nickel Cobaltite Nanocomposite Asymmetrical Supercapacitor with Commercial Level Mass Loading. Nano Res. 2012, 5, 605-617. (46) Xiao, J.; Yang, S. Bio-Inspired Synthesis of NaCl-type CoxNi1-xO (0
Department of Materials Science and Advanced Materials Laboratory, Fudan University,
Shanghai 20043, PR China; bSchool of Engineering, and National Engineering and Technology Research Center of Wood-based Resources Comprehensive Utilization, Zhejiang Agriculture and Forestry Unversity, Hangzhou Lin’an 311300, PR China E-mail: [email protected]
1
Figure S1. EDX spectra of (a) entire area, (b) center area, and (c) edge region of hybrid sphere supported on Cu grid with a lacey film. (d) Full XPS spectra of Ni(OH)2-MnO2-RGO (A in
2
brackets denotes Auger electron peaks). (e) Full XPS and (g) C1s XPS spectra of GO and RGO. (f) Raman spectra of GO and RGO. (h) Photographs of as-obtained Ni(OH)2-MnO2 (left) and Ni(OH)2-MnO2-RGO hybrid spheres (right) powders.
3
Table S1. Comparison of maximum Cs of the reported nickel-manganese oxide/hydroxide-, manganese
dioxide-graphene-,
nickel
oxide/hydroxide-graphene-,
and
nickel-cobalt
oxide/hydroxide-graphene-based composite pseudocapacitive materials and the present work. Cs (F g–1)
Ref.
Binary Manganese-Nickel Oxides
160 (50 mV s–1)
1
Porous nickel manganite materials
180 (0.25 A g–1)
2
Nanosized Ni-Mn Oxides
195 (10 mV s–1)
3
Mn/Ni mixed oxides
210 (0.12 A g–1)
4
Nickel-manganese oxide
284 (5 mV s–1)
5
Ni(OH)2-MnO2 core-shell nanostructures
355 (0.5 A g–1)
6
Mesoporous Mn-Ni oxides
411 (2 mV s–1)
7
Nanostructured NiO-MnO2 composite
453 (10 mV s–1)
8
Ultra-fine Mn-Ni-Cu oxides
490 (2 mV s–1)
9
NiO-MnO2 core-shell nanocomposites
528 (1 mV s–1)
10
Microporous nickel-manganese oxide
685 (2 mA cm–2)
11
Nanostructured Mn-Ni-Co oxides
1260 (1 A g–1)
12
Ni(OH)2-MnO2 hybrid nanosheets
2628 (3 A g–1)
13*
Graphene-MnO2 nanowall
122 (10 mV s–1)
14
Graphene-MnO2-carbon nanotubes
193 (0.2 A g–1)
15
Graphene-honeycomb-like MnO2
210 (0.5 A g–1)
16
Hydrothermally reduced graphene-MnO2
212 (2 mV s–1)
17
Graphene Oxide-MnO2 nanowires
216 (0.15 A g–1)
18
Graphene nanosheets-MnO2
235 (20 mV s–1)
19
Flexible graphene-MnO2 composite papers
256 (0.5 A g–1)
20
Electrodes based on materials 1. Nickel-manganese oxide/hydroxide composites
2. Manganese dioxide-graphene composites
4
Graphene-needle-like MnO2
260 (0.2 A g–1)
21
Graphene sheet-MnO2 sheet mutilayers
263 (0.283 A g–1)
22
Graphene nanoplate-MnO2
309 (5 mV s–1)
23
Nanostructured graphene-MnO2
310 (2 mV s–1)
24
Graphene-MnO2 nanostructured textiles
315 (2 mV s–1)
25
Graphene-flower-like MnO2
328 (0.5 mA/cm2)
26
Graphene-MnO2 nanoparticles
365 (5 mV s–1)
27
Graphene-MnO2 film
400 (10 mV s–1)
28
Reduced graphene oxide-MnO2 hollow sphere
578 (0.5 A g–1)
29*
Graphene sheet-porous NiO hybrid film
400 (2 A g–1)
30
Graphene porous NiO nanocomposite
430 (0.2 A g–1)
31
Monolayer graphene-NiO nanosheets
525 (0.2 A g–1)
32
NiO-attached graphene oxide nanosheets
569 (5 A g–1)
33
Reduced graphene oxide-nickel oxide composite
770 (2 mV s–1)
34
Ni(OH)2-graphene hybrid material
855 (5 mV s–1)
35
Graphene oxide-nickel oxide
890 (5 mV s–1)
36
Graphene-nickel hydroxide nanosheet hybrid
1163 (5 mV s–1)
37
Reduced graphene oxide-α-Ni(OH)2 hybrid composites
1215 (5 mV s–1)
38
Ni(OH)2 nanoplates grown on graphene
1335 (2.8 A g–1)
39
Ni(OH)2-graphene
1735 (1 mV s–1)
40
Spherical α-Ni(OH)2 grown on graphene
1761 (5 mV s–1)
41
Nanocomposites of Ni(OH)2-reduced graphene oxides
1804 (1 A g–1)
42
Ni(OH)2 nanoflakes on reduced graphene oxide
1828 (1 A g–1)
43
3. Nickel oxide/hydroxide-graphene composites
4. Nickel-cobalt binary oxide/hydroxide-graphene composites Cobalt-nickel oxides-carbon nanotube composites
569 (10 mA cm–2)
44
Graphene-nickel cobaltite nanocomposite
618 (5 mV s–1)
45
5
Co0.45Ni0.55O nanorods on reduced graphene oxide sheets
823 (1 A g–1)
46
NiCo2O4-reduced graphene oxide composites
835 (1 A g–1)
47
Nickel cobalt oxide-reduced graphite oxide composite
1222 (0.5 A g–1)
48
Ni(OH)2-CoO-reduced graphene oxide composites
1317 (2 A g–1)
49
Ni(OH)2-MnO2-RGO hybrid spheres
1985 (2 A g–1)
This work
* our previously reported work.
Table S2. Comparison of maximum densities and corresponding average power densities of some reported nickel-manganese oxide/hydroxide-, manganese dioxide-graphene-, nickel oxide/hydroxide-graphene-, and nickel-cobalt oxide/hydroxide-graphene-based composite pseudocapacitive materials and the present work Energy density
Power density
(Wh⋅⋅kg−1)
(kW⋅⋅kg−1)
Ni(OH)2/MnO2 core/shell nanostructures
41.2
0.50
6
Mn/Ni mixed oxides
3.12
1.00
4
Graphene-MnO2 nanoparticles
50.2
0.22
27
Graphene-flower-like MnO2
11.4
25.8 (Pmax)
26
Graphene-MnO2 nanostructured textiles
12.5
110 (Pmax)
25
Graphene nanosheets-MnO2
33.1
20.4 (Pmax)
19
Graphene-Ni(OH)2 nanoplates
37.0
10.0
39
Graphene Sheet/Porous NiO Hybrid Film
16.8
-
30
Ni(OH)2-MnO2-RGO hybrid spheres
54.0
0.39
This work
Electrodes based on materials
Ref.
Pmax: maximum power density.
6
Table S3. Comparison of the maximum energy densities, corresponding average power densities and voltage range of some reported nickel or manganese oxide/hydroxide based asymmetric supercapacitors, and the present work Energy density (Wh⋅⋅kg−1)
Power density (kW⋅⋅kg−1)
Voltage range (V)
Ref.
Graphitic hollow carbon spheres-MnO2 nanofibers//graphitic hollow carbon spheres
22.1
0.10
0-2
50
Graphite oxide-MnO2//graphite oxide
24.3
24.5 (Pmax)
0-2
51
Ni(OH)2//AC
25.0
-
0.6-1.3
52
MnO2//graphene
25.2
0.10
0-2
53
K0.27MnO2·0.6H2O//AC
25.3
0.14
0-1.8
54
MnO2 nanowire-SWCNT//In2O3 nanowireSWCNT
25.5
50.3 (Pmax)
0-2
55
RGO-MnO2-CNTs//AC-WCNT
27.0
0.13
0-2
56
Ni(OH)2//graphene
30.0
1.00
0-1.6
57
Poly(3,4-ethylenedioxythiophene)-MnO2//AC
30.2
0.18
0-1.8
58
Ni(OH)2-MnO2-RGO hybrid spheres// FRGO
32.6
0.31
0-1.6
This work
Positive materials//negative materials
AC: activated carbon, CNT: carbon nanotube, Pmax: maximum power density.
7
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