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Porous carbon matrix-encapsulated MnO in situ derived from metal-organic frameworks as advanced anode materials for Li-ion capacitors

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  • ReceivedMar 8, 2021
  • AcceptedJun 2, 2021
  • PublishedAug 6, 2021

Abstract


Funded by

the National Natural Science Foundation of China(21905148)

China Postdoctoral Science Foundation(2019T120567,2017M612184)

the 1000-Talents Plan

the World-Class Discipline Program

and the Taishan Scholars Advantageous and Distinctive Discipline Program of Shandong province for supporting the research team of energy storage materials.


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21905148), China Postdoctoral Science Foundation (2019T120567 and 2017M612184), the 1000-Talents Plan, the World-Class Discipline Program, and the Taishan Scholars Advantageous and Distinctive Discipline Program of Shandong province for supporting the research team of energy storage materials. The authors would like to express their gratitude to EasytoEdit for the expert linguistic services provided.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Jiang S and Chen H conceived the idea and wrote the manuscript. Jiang S, Yun S and Zhang Z performed the experiments. Cao H designed the schematic diagram. Feng H helped with the energy storage performance test. All authors contributed to the general discussion.


Author information

Sipeng Jiang received his BE degree in 2014 from the Central South University of Forestry and Technology. He is a master degree candidate at Qingdao University, China. His research interests mainly focus on lithium-ion batteries and lithium-ion hybrid capacitors.


Haichao Chen is currently an associate professor at the Institute of Materials for Energy and Environment/School of Materials Science and Engineering, Qingdao University. Prior to holding this position, he performed the research on preparation of high-performance active materials for supercapacitors at Huazhong University of Science and Technology, China. Now his main research interest focuses on the advanced electroactive materials for hybrid supercapacitors and Zn-ion batteries.


Supplement

Supplementary information

Experimental details are available in the online version of the paper.


References

[1] Ding J, Hu W, Paek E, et al. Review of hybrid ion capacitors: From aqueous to lithium to sodium. Chem Rev, 2018, 118: 6457-6498 CrossRef PubMed Google Scholar

[2] Sun B, Xiong P, Maitra U, et al. Design strategies to enable the efficient use of sodium metal anodes in high-energy batteries. Adv Mater, 2020, 32: 1903891 CrossRef PubMed Google Scholar

[3] Wang X, Kerr R, Chen F, et al. Toward high-energy-density lithium metal batteries: Opportunities and challenges for solid organic electrolytes. Adv Mater, 2020, 32: 1905219 CrossRef PubMed Google Scholar

[4] Wang T, Zhang S, Wang H. Binary NiCu layered double hydroxide nanosheets for enhanced energy storage performance as supercapacitor electrode. Sci China Mater, 2017, 61: 296-302 CrossRef Google Scholar

[5] Wang T, Chen HC, Yu F, et al. Boosting the cycling stability of transition metal compounds-based supercapacitors. Energy Storage Mater, 2019, 16: 545-573 CrossRef Google Scholar

[6] Cao J, Hu Y, Zhu Y, et al. Synthesis of mesoporous nickel-cobalt-manganese sulfides as electroactive materials for hybrid supercapacitors. Chem Eng J, 2021, 405: 126928 CrossRef Google Scholar

[7] Wang X, Tian L, Long X, et al. Cracked bark-inspired ternary metallic sulfide (NiCoMnS4) nanostructure on carbon cloth for high-performance aqueous asymmetric supercapacitors. Sci China Mater, 2021, 64: 1632-1641 CrossRef Google Scholar

[8] Li F, Yu L, Hu Q, et al. Fabricating low-temperature-tolerant and durable Zn-ion capacitors via modulation of co-solvent molecular interaction and cation solvation. Sci China Mater, 2021, 64: 1609-1620 CrossRef Google Scholar

[9] Dubal DP, Ayyad O, Ruiz V, et al. Hybrid energy storage: The merging of battery and supercapacitor chemistries. Chem Soc Rev, 2015, 44: 1777-1790 CrossRef PubMed Google Scholar

[10] Chen HC, Jiang S, Xu B, et al. Sea-urchin-like nickel-cobalt phosphide/phosphate composites as advanced battery materials for hybrid supercapacitors. J Mater Chem A, 2019, 7: 6241-6249 CrossRef Google Scholar

[11] Jia R, Jiang Y, Li R, et al. Nb2O5 nanotubes on carbon cloth for high performance sodium-ion capacitors. Sci China Mater, 2020, 63: 1171-1181 CrossRef Google Scholar

[12] Wang H, Zhu C, Chao D, et al. Nonaqueous hybrid lithium-ion and sodium-ion capacitors. Adv Mater, 2017, 29: 1702093 CrossRef PubMed Google Scholar

[13] Ma Y, Chang H, Zhang M, et al. Graphene-based materials for lithium-ion hybrid supercapacitors. Adv Mater, 2015, 27: 5296-5308 CrossRef PubMed Google Scholar

[14] Lukatskaya MR, Dunn B, Gogotsi Y. Multidimensional materials and device architectures for future hybrid energy storage. Nat Commun, 2016, 7: 12647 CrossRef PubMed ADS Google Scholar

[15] Zhou J, Xu S, Kang Q, et al. Iron oxide encapsulated in nitrogen-rich carbon enabling high-performance lithium-ion capacitor. Sci China Mater, 2020, 63: 2289-2302 CrossRef Google Scholar

[16] Jiang C, Zhao J, Wu H, et al. Li4Ti5O12/activated-carbon hybrid anodes prepared by in situ copolymerization and post-CO2 activation for high power Li-ion capacitors. J Power Sources, 2018, 401: 135-141 CrossRef ADS Google Scholar

[17] Le Z, Liu F, Nie P, et al. Pseudocapacitive sodium storage in mesoporous single-crystal-like TiO2-graphene nanocomposite enables high-performance sodium-ion capacitors. ACS Nano, 2017, 11: 2952-2960 CrossRef PubMed Google Scholar

[18] Deng B, Lei T, Zhu W, et al. In-plane assembled orthorhombic Nb2O5 nanorod films with high-rate Li+ intercalation for high-performance flexible Li-ion capacitors. Adv Funct Mater, 2018, 28: 1704330 CrossRef Google Scholar

[19] Kong L, Zhang C, Zhang S, et al. High-power and high-energy asymmetric supercapacitors based on Li+-intercalation into a T-Nb2O5/graphene pseudocapacitive electrode. J Mater Chem A, 2014, 2: 17962-17970 CrossRef Google Scholar

[20] Kim HS, Cook JB, Lin H, et al. Oxygen vacancies enhance pseudocapacitive charge storage properties of MoO3−x. Nat Mater, 2017, 16: 454-460 CrossRef PubMed ADS Google Scholar

[21] Xiao YC, Xu CY, Wang PP, et al. Encapsulating MnO nanoparticles within foam-like carbon nanosheet matrix for fast and durable lithium storage. Nano Energy, 2018, 50: 675-684 CrossRef Google Scholar

[22] Liu S, Li F, Wang D, et al. 3D macroporous MoxC@N-C with incorporated Mo vacancies as anodes for high-performance lithium-ion batteries. Small Methods, 2018, 2: 1800040 CrossRef Google Scholar

[23] Huang C, Hu Y, Jiang S, et al. Amorphous nickel-based hydroxides with different cation substitutions for advanced hybrid supercapacitors. Electrochim Acta, 2019, 325: 134936 CrossRef Google Scholar

[24] Wang E, Chen M, Guo X, et al. Synthesis strategies and structural design of porous carbon-incorporated anodes for sodium-ion batteries. Small Methods, 2019, 4: 1900163 CrossRef Google Scholar

[25] Jiang H, Hu Y, Guo S, et al. Rational design of MnO/carbon nanopeapods with internal void space for high-rate and long-life Li-ion batteries. ACS Nano, 2014, 8: 6038-6046 CrossRef PubMed Google Scholar

[26] Liu Y, Xu X, Shao Z, et al. Metal-organic frameworks derived porous carbon, metal oxides and metal sulfides-based compounds for supercapacitors application. Energy Storage Mater, 2020, 26: 1-22 CrossRef Google Scholar

[27] Indra A, Song T, Paik U. Metal organic framework derived materials: Progress and prospects for the energy conversion and storage. Adv Mater, 2018, 30: 1705146 CrossRef PubMed Google Scholar

[28] Zheng F, Yin Z, Xia H, et al. Porous MnO@C nanocomposite derived from metal-organic frameworks as anode materials for long-life lithium-ion batteries. Chem Eng J, 2017, 327: 474-480 CrossRef Google Scholar

[29] Zhang Y, Chen P, Gao X, et al. Nitrogen-doped graphene ribbon assembled core-sheath MnO@graphene scrolls as hierarchically ordered 3D porous electrodes for fast and durable lithium storage. Adv Funct Mater, 2016, 26: 7754-7765 CrossRef Google Scholar

[30] Liu C, Fu H, Pei Y, et al. Understanding the electrochemical potential and diffusivity of MnO/C nanocomposites at various charge/discharge states. J Mater Chem A, 2019, 7: 7831-7842 CrossRef Google Scholar

[31] Gu X, Yue J, Chen L, et al. Coaxial MnO/N-doped carbon nanorods for advanced lithium-ion battery anodes. J Mater Chem A, 2015, 3: 1037-1041 CrossRef Google Scholar

[32] Zhu G, Wang L, Lin H, et al. Walnut-like multicore-shell MnO encapsulated nitrogen-rich carbon nanocapsules as anode material for long-cycling and soft-packed lithium-ion batteries. Adv Funct Mater, 2018, 28: 1800003 CrossRef Google Scholar

[33] Guo S, Lu G, Qiu S, et al. Carbon-coated MnO microparticulate porous nanocomposites serving as anode materials with enhanced electrochemical performances. Nano Energy, 2014, 9: 41-49 CrossRef Google Scholar

[34] Zhang L, Xia G, Huang Y, et al. MnO quantum dots embedded in carbon nanotubes as excellent anode for lithium-ion batteries. Energy Storage Mater, 2018, 10: 160-167 CrossRef Google Scholar

[35] Yang X, Liu X, Wang Y, et al. Spray-assisted synthesis of MnO@C/graphene composites as electrode materials for supercapacitors. Energy Technol, 2019, 7: 1800625 CrossRef Google Scholar

[36] Qin Y, Wang B, Jiang S, et al. Strongly anchored MnO nanoparticles on graphene as high-performance anode materials for lithium-ion batteries. Ionics, 2020, 26: 3315-3323 CrossRef Google Scholar

[37] Simon P, Gogotsi Y, Dunn B. Where do batteries end and supercapacitors begin?. Science, 2014, 343: 1210-1211 CrossRef PubMed ADS Google Scholar

[38] Fleischmann S, Mitchell JB, Wang R, et al. Pseudocapacitance: From fundamental understanding to high power energy storage materials. Chem Rev, 2020, 120: 6738-6782 CrossRef PubMed Google Scholar

[39] Brezesinski T, Wang J, Tolbert SH, et al. Ordered mesoporous α-MoO3 with iso-oriented nanocrystalline walls for thin-film pseudocapacitors. Nat Mater, 2010, 9: 146-151 CrossRef PubMed ADS Google Scholar

[40] Augustyn V, Simon P, Dunn B. Pseudocapacitive oxide materials for high-rate electrochemical energy storage. Energy Environ Sci, 2014, 7: 1597 CrossRef Google Scholar

[41] Chen HC, Qin Y, Cao H, et al. Synthesis of amorphous nickel-cobalt-manganese hydroxides for supercapacitor-battery hybrid energy storage system. Energy Storage Mater, 2019, 17: 194-203 CrossRef Google Scholar

[42] Sun Y, Hu X, Luo W, et al. Reconstruction of conformal nanoscale MnO on graphene as a high-capacity and long-life anode material for lithium ion batteries. Adv Funct Mater, 2013, 23: 2436-2444 CrossRef Google Scholar

[43] Liu DH, Lü HY, Wu XL, et al. Constructing the optimal conductive network in MnO-based nanohybrids as high-rate and long-life anode materials for lithium-ion batteries. J Mater Chem A, 2015, 3: 19738-19746 CrossRef Google Scholar

[44] Yang M, Zhong Y, Ren J, et al. Fabrication of high-power Li-ion hybrid supercapacitors by enhancing the exterior surface charge storage. Adv Energy Mater, 2015, 5: 1500550 CrossRef Google Scholar

[45] Ding R, Qi L, Wang H. Porous NiCo2O4 as an anode material for 4.5 V hybrid Li-ion capacitors. RSC Adv, 2013, 3: 12581 CrossRef ADS Google Scholar

[46] Liu C, Zhang C, Fu H, et al. Exploiting high-performance anode through tuning the character of chemical bonds for Li-ion batteries and capacitors. Adv Energy Mater, 2017, 7: 1601127 CrossRef Google Scholar

[47] Liu C, Zhang C, Song H, et al. MnO nanoparticles with cationic vacancies and discrepant crystallinity dispersed into porous carbon for Li-ion capacitors. J Mater Chem A, 2016, 4: 3362-3370 CrossRef Google Scholar

[48] Ulaganathan M, Aravindan V, Ling WC, et al. High energy Li-ion capacitors with conversion type Mn3O4 particulates anchored to few layer graphene as the negative electrode. J Mater Chem A, 2016, 4: 15134-15139 CrossRef Google Scholar

[49] Liu C, Ren QQ, Zhang SW, et al. High energy and power lithium-ion capacitors based on Mn3O4/3D-graphene as anode and activated polyaniline-derived carbon nanorods as cathode. Chem Eng J, 2019, 370: 1485-1492 CrossRef Google Scholar

[50] Liu C, Zhang C, Song H, et al. Mesocrystal MnO cubes as anode for Li-ion capacitors. Nano Energy, 2016, 22: 290-300 CrossRef Google Scholar

[51] Choi HS, Im JH, Kim TH, et al. Advanced energy storage device: A hybrid batcap system consisting of battery-supercapacitor hybrid electrodes based on Li4Ti5O12-activated-carbon hybrid nanotubes. J Mater Chem, 2012, 22: 16986 CrossRef Google Scholar

[52] Yi R, Chen S, Song J, et al. High-performance hybrid supercapacitor enabled by a high-rate Si-based anode. Adv Funct Mater, 2014, 24: 7433-7439 CrossRef Google Scholar

  • Figure 1

    Schematic illustration of the (a) formation process and (b) conversion mechanism from the ZnMn-MOF of the MnO/PC.

  • Figure 2

    (a) XRD patterns of the ZnMn-MOF and MnO/PC. FESEM images of the (b) ZnMn-MOF and (c) MnO/PC. (d–g) TEM images at different magnifications and (h) EDS mapping image of the MnO/PC.

  • Figure 3

    (a) TGA curve, (b) Raman spectrum, and (c) N2 adsorption/desorption isotherm and the corresponding pore size distribution curve of the MnO/PC. High-resolution (d) Mn 3s, (e) C 1s and (f) O 1s XPS spectra of the MnO/PC.

  • Figure 4

    (a) CV curves at different scan rates of the MnO/PC, and (b) relationship and linear fitting results of the cathodic and anodic peak currents and scan rate used to determine the b value. (c) Separation of the capacitive and diffusion-controlled contributions of MnO/PC at a scan rate of 0.5 mV s−1. (d) The percentage of capacitive and diffusion-controlled contributions at different scan rates.

  • Figure 5

    (a) Cycling performance at 0.1 A g−1 of MnO/PC and Mn/C, and the coulombic efficiency of MnO/PC. (b) GCD curves for the initial five cycles of the MnO/PC. (c) Rate performance at specific currents ranging from 0.1 to 0.7 A g−1 of MnO/PC and Mn/C. (d) Typical GCD curves at different specific currents of MnO/PC. (e) Long-term cycling performance at a high specific current of 0.3 A g−1 of MnO/PC and MnO/C.

  • Figure 6

    TEM images of the MnO/PC tested after being cycled at a specific current of 0.1 A g−1 for 50 cycles: (a) overall morphology, and enlarged images showing (a) erosion, (b) fracture and (c) pulverization of MnO particles.

  • Figure 7

    Schematic illustration of the mechanism for the porous structure of AC used to buffer the volume change of MnO during Li+ storage.

  • Figure 8

    (a) Schematic illustration of the structure, (b) CV curves at scan rates ranging from 0.5 to 10 mV s−1, (c) GCD curves at specific currents ranging from 0.1 to 30 A g−1, and (d) long-term cycling performance and the coulombic efficiency of the MnO/PC//AC LIC. (e) Photographs of an LIC cell used to drive 10 blue LEDs at different durations. (f) Ragone plots of the MnO/PC//AC LIC and previously reported LICs.

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