Supplementary material
Exceptional Adsorption and Catalysis Effects of Hollow Polyhedra/Carbon
Nanotube Confined CoP Nanoparticles Superstructures for Enhanced Lithium-
Sulfur Batteries
Zhengqing Yea, Ying Jianga, Ji Qiana, Wanlong Lia, Tao Fenga, Li Lia,b, Feng Wua,b, and
Renjie Chena,b,*
aBeijing Key Laboratory of Environmental Science and Engineering, School of
Material Science and Engineering, Beijing Institute of Technology, Beijing 100081,
China.
bCollaborative Innovation Center of Electric Vehicles in Beijing, Beijing 100081,
China.
E-mail: [email protected]
1
Fig. S1 SEM images of (a) ZIF-8, (b) ZIF-8/ZIF-67, and (c) Co@HPCN. (d) TEM
images of the as-prepared Co@HPCN.
2
Fig. S2 XRD patterns of the (a) ZIF8 and ZIF-8/ZIF-67, (b) Co@HPCN and (c) Co3O4@HPCN.
3
Fig. S3 TEM and HRTEM images of CoP@HPCN.
4
Fig. S4 HRTEM images of CoP@HPCN.
5
Fig. S5 TGA curves of CoP@HPCN samples treated in air.
6
Fig. S6 TGA curve of the CoP@HPCN/S composite.
7
Fig. S7 (a,b) HRTEM images, (c) Nitrogen adsorption–desorption isotherms, and (d) DFT pore size distributions of the CoP@HPCN/S material.
The nitrogen isotherm of CoP@HPCN/S shows a significant rise at a high relative pressure, indicating the macropore structure derived from the hollow interior. (Fig. S7c). A pore size distribution of CoP@HPCN/S exhibits some mesopores and macropores (Figure S7d, Supporting Information). Therefore, hollow polyhedra with interior cavities and mesoporous shell can relieve volumetric expansion during lithiation.
8
Fig. S8 Results of (a) Li2S6 and (b) Li2S8 adsorption experiments with MWCNT and CoP@HPCN.
9
Fig. S9 CV curves of the symmetric cell employing CoP@HPCN-MWCNT at various scan rates.
10
Fig. S10 Discharge–charge curves of CoP@HPCN-MWCNT/S and MWCNT/S
electrodes at 0.2 C.
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Fig. S11 CV curves of (a) CoP@HPCN-MWCNT/S and (b) MWCNT/S composite
cathode at a scan rate of 0.1 mV s−1.
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Fig. S12 Cyclic performance of CoP@HPCN/S electrode at 0.2 C.
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Fig. S13 (a) voltage profiles of the MWCNT/S at 1st and 300th cycles. (b) The
comparison of high and low plateau of the CoP@HPCN-MWCNT/S and MWCNT/S
cathodes at 1st and 300th cycles.
14
Fig. S14 Cycling stability of CoP@HPCN-MWCNT/S cathode at 2 and 3 C.
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Fig. S15 Galvanostatic discharge/charge profiles of (a) CoP@HPCN-MWCNT/S and (b) MWCNT/S at various current rates (0.1, 0.2, 1, 2, and 3 C).
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Fig. S16 (a) CV curves of CoP@HPCN-MWCNT/S cathode at various scan rates.
The calculated b values with plots of log(current) versus log(scan rate) for (b) peak 1,
(c) peak 2, (d) peak 3, and (e) peak 4.
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Fig. S17 (a) The discharge capacity of CoP@HPCN-MWCNT/S electrodes with (a)
2.3 mg cm−2 and (b) 3.7 mg cm−2 before (rhombus) and after (sphere) 60 days of rest
at room temperature.
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Fig. S18 Self-discharge performance comparison of the CoP@HPCN-MWCNT/S
electrode with other sulfur cathodes reported in literature.
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Fig. S19 The calculated lithium diffusion coefficient D (cm2 s−1) of CoP@HPCN-
MWCNT/S and MWCNT/S electrodes before and after 200 cycles at 0.2 C.
The lithium ion diffusion coefficient from EIS can be calculated from the
formula as following: D=R2T2/(2A2n4F4C2σ2). where R is the gas constant (R= 8.314 J
K−1 mol−1), T is the room temperature in our experiment (T=298K), A is the electrode
area, n is the electron charge number (n=2), F is the Faraday constant, C is the
concentration of lithium ion (0.001 mol cm−3), σ is the slope of the line Z’∼ω−1/2,
which can be obtained from the fitted line of Z’∼ ω−1/2.
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Table S1. The comparisons of electrochemical properties of present work with
various cathode materials for Li-S batteries.
Cathode materials
S content (wt.%)
S loading(mg m-
2)
Initial capacity(mAh g-
1/C)
Reversible capacity
(mAh g-1)/Cycle
number
Decay rate
(%per cycle)
Rate properties
(mAh g-1/C)S loading(mg cm-2)
VO2 hollow spheres [S1] 71 -
930/0.1789/80 0.15
318/2-
TiO2/Co-carbon
polyhedras [S2]
66 1.5 -/1 466.3/300 - 383.8/31.5
Co3O4/ ACNT hybrid spheres
[S3]58.7 1.5
748.7/0.5496.5/550 0.064
589/21.1
Mn-Sn oxide nanocubes [S4] - 0.65–1.0
-/0.2390.7/300 -
107.5/10.65–1.0
C@TiN hollow nanosphere
[S5]70 -
1309/0.2884/100 0.3
591/21.1
NiCo2S4@CNTs
[S6]66 1.8
-/2310/100
470/30.4-0.79
ZnCo2O4@N-RGO [S7]
71 1.1–1.3905/1.6A
g−1 645/200 0.144 -
PANI@EDA-CNTs [S8]
72 2992/0.5
735/200 0.130462/3
2
Fe/Fe3C@N-CNT [S9]
- - 932/1 534/300 0.142464/2
p-CNT@Void@
MnO2 [S10]64.9 - 599/1 561/100 - 496.9/2
CoP@HPCN-MWCNT
(This work)70 2.2
887/0.2 753/200 0.076601/2
527.7/31.1
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References:
[S1] L. Zhou, L. Yao, S.X. Li, J.T. Zai, S.T. Li, Q.Q. He, K. He, X.M. Li, D.H.
Wang, X.F. Qian, The combination of intercalation and conversion reactions to
improve the volumetric capacity of the cathode in Li-S batteries, J. Mater. Chem. A 7
(2019) 3618-3623.
[S2] R. Liu, Z. Liu, W. Liu, Y. Liu, X. Lin, Y. Li, P. Li, Z. Huang, X. Feng, L. Yu, D.
Wang, Y. Ma, W. Huang, TiO2 and Co Nanoparticle-Decorated Carbon Polyhedra as
Efficient Sulfur Host for High-Performance Lithium-Sulfur Batteries, Small (2019)
1804533.
[S3] R. Liu, F. Guo, X. Zhang, J. Yang, M. Li, W. Miaomiao, H. Liu, M. Feng, L.
Zhang, Novel “Bird-Nest” Structured Co3O4/Acidified Multiwall Carbon Nanotube
(ACNT) Hosting Materials for Lithium–Sulfur Batteries, ACS Applied Energy
Materials 2 (2019) 1348-1356.
[S4] Y.Y. He, L.Q. Xu, C.C. Li, X.X. Chen, G. Xu, X.Y. Jiao, Mesoporous Mn-Sn
bimetallic oxide nanocubes as long cycle life anodes for Li-ion half/full cells and
sulfur hosts for Li-S batteries, Nano Research 11 (2018) 3555-3566.
[S5] Y. Wang, R. Zhang, Y.-c. Pang, X. Chen, J. Lang, J. Xu, C. Xiao, H. Li, K. Xi,
S. Ding, Carbon@titanium nitride dual shell nanospheres as multi-functional hosts for
lithium sulfur batteries, Energy Storage Mater. 16 (2019) 228-235.
[S6] X. Lu, Q. Zhang, J. Wang, S. Chen, J. Ge, Z. Liu, L. Wang, H. Ding, D. Gong,
H. Yang, X. Yu, J. Zhu, B. Lu, High performance bimetal sulfides for lithium-sulfur
batteries, Chem. Eng. J. 358 (2019) 955-961.22
[S7] Q. Sun, B. Xi, J.-Y. Li, H. Mao, X. Ma, J. Liang, J. Feng, S. Xiong, Nitrogen-
Doped Graphene-Supported Mixed Transition-Metal Oxide Porous Particles to
Confine Polysulfides for Lithium-Sulfur Batteries, Adv. Energy Mater. 8 (2018)
1800595.
[S8] M. Yan, H. Chen, Y. Yu, H. Zhao, C.-F. Li, Z.-Y. Hu, P. Wu, L. Chen, H. Wang,
D. Peng, H. Gao, T. Hasan, Y. Li, B.-L. Su, 3D Ferroconcrete-Like Aminated Carbon
Nanotubes Network Anchoring Sulfur for Advanced Lithium-Sulfur Battery, Adv.
Energy Mater. 8 (2018) 1801066.
[S9] Y.-S. Liu, C. Ma, Y.-L. Bai, X.-Y. Wu, Q.-C. Zhu, X. Liu, X.-H. Liang, X. Wei,
K.-X. Wang, J.-S. Chen, Nitrogen-doped carbon nanotube sponge with embedded
Fe/Fe3C nanoparticles as binder-free cathodes for high capacity lithium–sulfur
batteries, J. Mater. Chem. A 6 (2018) 17473-17480.
[S10] Q. Liu, J. Zhang, S.A. He, R. Zou, C. Xu, Z. Cui, X. Huang, G. Guan, W.
Zhang, K. Xu, J. Hu, Stabilizing Lithium-Sulfur Batteries through Control of Sulfur
Aggregation and Polysulfide Dissolution, Small 14 (2018) 1703816.
[S11] M. Kazazi, M.R. Vaezi, A. Kazemzadeh, Improving the self-discharge behavior
of sulfur-polypyrrole cathode material by LiNO3 electrolyte additive, Ionics 20 (2014)
1291-1300.
[S12] T. Takahashi, M. Yamagata, M. Ishikawa, A sulfur–microporous carbon
composite positive electrode for lithium/sulfur and silicon/sulfur rechargeble
batteries, Progress in Natural Science: Materials International 25 (2015) 612-621.
23
[S13] H. Wang, W. Zhang, H. Liu, Z. Guo, A Strategy for Configuration of an
Integrated Flexible Sulfur Cathode for High-Performance Lithium–Sulfur Batteries,
Angew. Chem. Int. Ed. 55 (2016) 3992-3996.
[S14] Y. Ansari, S. Zhang, B. Wen, F. Fan, Y.-M. Chiang, Stabilizing Li–S Battery
Through Multilayer Encapsulation of Sulfur, Adv. Energy Mater. 9 (2018) 1802213.
[S15] G. Li, W. Lei, D. Luo, Y.-P. Deng, D. Wang, Z. Chen, 3D Porous Carbon
Sheets with Multidirectional Ion Pathways for Fast and Durable Lithium-Sulfur
Batteries, Adv. Energy Mater. 8 (2018) 1702381.
[S16] S. Majumder, M. Shao, Y. Deng, G. Chen, Ultrathin sheets of MoS2/g-C3N4
composite as a good hosting material of sulfur for lithium–sulfur batteries, J. Power
Sources 431 (2019) 93-104.
[S17] R. Yu, S.-H. Chung, C.-H. Chen, A. Manthiram, An ant-nest-like cathode
substrate for lithium-sulfur batteries with practical cell fabrication parameters, Energy
Storage Mater. 18 (2019) 491-499.
[S18] M. Wang, L. Fan, X. Wu, Y. Qiu, B. Guan, Y. Wang, N. Zhang, K. Sun,
Metallic NiSe2 Nanoarray Towards Ultralong life and Fast Li2S Oxidation Kinetic of
Li-S Batteries, J. Mater. Chem. A 7 (2019) 15302-15308.
24