Synthesis and supercapacitive performance of molybdenum-doped manganese dioxide electrode materials

YANG Tianshuo; WANG Jianren; GAO Faming

doi:10.19799/j.cnki.2095-4239.2026.0131

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Synthesis and supercapacitive performance of molybdenum-doped manganese dioxide electrode materials

Special Issue of Key Materials and Devices of Supercapacitors | 更新时间：2026-07-01

- Synthesis and supercapacitive performance of molybdenum-doped manganese dioxide electrode materials
- Energy Storage Science and Technology Vol. 15, Issue 5, Pages: 1704-1715(2026)
- 作者机构：
  
  1.天津科技大学化工与材料学院，天津 300457
  2.燕山大学环境与化学工程学院，河北秦皇岛 066000
- 作者简介：
- 基金信息：
- DOI：10.19799/j.cnki.2095-4239.2026.0131
  CLC： TB 34;TM 53
- Received：03 February 2026，
  
  Revised：2026-03-09，
  
  Published：28 May 2026
- 稿件说明：
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杨添铄, 王建韧, 高发明. 钼掺杂二氧化锰电极材料的制备及其超电性能研究[J]. 储能科学与技术, 2026, 15(5): 1704-1715.

YANG Tianshuo, WANG Jianren, GAO Faming. Synthesis and supercapacitive performance of molybdenum-doped manganese dioxide electrode materials[J]. Energy Storage Science and Technology, 2026, 15(5): 1704-1715.
杨添铄, 王建韧, 高发明. 钼掺杂二氧化锰电极材料的制备及其超电性能研究[J]. 储能科学与技术, 2026, 15(5): 1704-1715. DOI： 10.19799/j.cnki.2095-4239.2026.0131.

YANG Tianshuo, WANG Jianren, GAO Faming. Synthesis and supercapacitive performance of molybdenum-doped manganese dioxide electrode materials[J]. Energy Storage Science and Technology, 2026, 15(5): 1704-1715. DOI： 10.19799/j.cnki.2095-4239.2026.0131.

摘要

本研究针对二氧化锰（MnO

）材料在超级电容器领域内难以发挥自身高能量密度与高功率密度的问题，提出了一种“自下而上”的策略以实现二者的良好平衡。本策略通过引入与[MnO

]

晶胞参数相似的[MoO

]

单元，在水热过程中扰动[MnO

]

的组装，实现MnO

结构的精确调整；通过调节[MoO

]

浓度可以精确控制所得MnO

的形貌、晶型和内部缺陷；通过SEM与TEM测试证实了[MoO

]

对MnO

形貌的改变。XPS与HRTEM结果表明[MoO

]

将引入更多氧空位与无序结构。电化学测试结果表明，适度[MoO

]

浓度材料（Mo

0.05

-MnO

）在5 mV/s的扫速下表现出158.9 F/g的比质量电容，而当扫速提升至200 mV/s时依旧能保持68%的容量。通过原位阻抗技术观测了[MoO

]

对MnO

储能过程的影响，并得到不同浓度[MoO

]

掺入MnO

电极的扩散系数。结合有限元分析，适度的[MoO

]

导致的富含缺陷但局部有序的结构平衡了活性位点数量与离子扩散平衡时间，实现功率密度与能量密度的协同增强。本研究不仅提供了一种储能表现优秀的MnO

电极材料制备方法，还揭示了MnO

电极内部的构效关系，为下一代赝电容材料的设计提供理论指导与新思路。

Abstract

The practical application of manganese dioxide (MnO

) in superc

apacitors is limited by the difficulty of concurrently achieving high energy and power density. This study addresses this limitation through a "bottom-up" structural tuning strategy in which [MoO

]

units

whose octahedral parameters closely match those of the host [MnO

]

are introduced into the MnO

lattice during hydrothermal synthesis to perturb [MnO

]

octahedral assembly and enable precise structural modification. The [MoO

]

concentration proved to be a critical parameter governing the resulting morphology

crystal phase

and defect density. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed pronounced morphological changes upon [MoO

]

incorporation

while X-ray photoelectron spectroscopy (XPS) and high-resolution TEM (HRTEM) revealed the formation of additional oxygen vacancies and a disordered local structure. Electrochemical measurements showed that the optimally doped sample (Mo

0.05

-MnO

) achieved a specific capacitance of 158.9 F/g at 5 mV/s and retained 68% of this value at 200 mV/s. The role of [MoO

]

in charge storage was further investigated by in situ electrochemical impedance spectroscopy

from which ion diffusion coefficients were determined for electrodes across a range of doping levels. Finite element analysis indicated that moderate [MoO

]

doping produces a defect-rich yet locally ordered structure that optimally balances active-site density and ion diffusion relaxation time

thereby enhancing both energy and power density simultaneously. These findings establish a viable route for synthesizing high-performance Mo-doped MnO

electrodes and clarify the underlying structure-performance relationship

offering design guidelines for advanced pseudocapacitive materials.

关键词

Keywords

references

HU Y T, WU Y, WANG J. Manganese-oxide-based electrode materials for energy storage applications: How close are we to the theoretical capacitance?[J]. Advanced Materials, 2018, 30(47): 1802569. DOI:10.1002/adma.201802569.

XIANG W C, LIU S Z, TRESS W. Interfaces and interfacial layers in inorganic perovskite solar cells[J]. Angewandte Chemie International Edition, 2021, 60(51): 26440-26453. DOI:10.1002/anie.202108800.

LI Q, WANG Z L, LI G R, et al. Design and synthesis of MnO 2 /Mn/MnO 2 sandwich-structured nanotube arrays with high supercapacitive performance for electrochemical energy storage[J ] . Nano Letters, 2012, 12(7): 3803-3807.

ZHANG Y X, CUI X S, FU J C, et al. Commercial-level mass-loading MnO 2 with ion diffusion channels for high-performance aqueous energy storage devices[J ] . Journal of Materials Chemistry A, 2021, 9(33): 17945-17954. DOI:10.1039/d1ta04850c.

LIU J Y, BAO J L, ZHANG X, et al. MnO 2 -based materials for supercapacit or electrodes: Challenges, strategies and prospects[J ] . RSC Advances, 2022, 12(55): 35556-35578.

SINGU B S, YOON K R. Porous manganese oxide nanospheres for pseudocapacitor applications[J]. Journal of Alloys and Compounds, 2017, 695: 771-778. DOI:10.1016/j.jallcom.2016. 08.239.

COSTENTIN C, PORTER T R, SAVÉANT J M. How do pseudocapacitors store energy? theoretical analysis and experimental illustration[J]. ACS Applied Materials & Interfaces, 2017, 9(10): 8649-8658.

BALL P. Cleaning the seas with blue diesel[J]. Nature Materials, 2021, 20(12): 1588. DOI:10.1038/s41563-021-01164-3.

WANG J J, WANG J G, QIN X P, et al. Superfine MnO 2 nanowires with rich defects toward boosted zinc ion storage performance[J ] . ACS Applied Materials & Interfaces, 2020, 12(31): 34949-34958. DOI:10.1021/acsami.0c08812.

MENG J X, XU L S, MA Q X, et al. Modulating crystal and interfacial properties by W-gradient doping for highly stable and long life Li-rich layered cathodes[J]. Advanced Functional Materials, 2022, 32(19): 2113013. DOI:10.1002/adfm.202113013.

YAO S Y, WANG S Y, LIU R C, et al. Delocalizing the d-electrons spin states of Mn site in MnO 2 for anion-intercalation energy storage[J ] . Nano Energy, 2022, 99: 107391. DOI:10.1016/j.nanoen.2022.107391.

HUANG S G, SUN J, YAN J, et al. Enhanced high-temperature cyclic stability of Al-doped manganese dioxide and morphology evolution study through in situ NMR under high magnetic field[J ] . ACS Applied Materials & Interfaces, 2018, 10(11): 9398-9406.

ZHANG N, JI Y R, WANG J C, et al. Understanding of the charge storage mechanism of MnO 2 -based aqueous zinc-ion batteries: Reaction processes and regulation strategies[J ] . Journal of Energy Chemistry, 2023, 82: 423-463. DOI:10.1016/j.jechem. 2023.03.052.

CHEN Y, LIN C, CHEN X, et al. Modulating the structure of interlayer/layer matrix on δ-MnO 2 via cerium doping‐engineering toward high-performance aqueous zinc ion batteries[J ] . Advanced Energy Materials, 2024, 14(35): 2304303.

CHRISTIANSEN A F, FJELLVÅG H, KJEKSHUS A, et al. Synthesis and characterization of molybdenum(VI) oxide sulfates and crystal structures of two polymorphs of MoO 2 (SO 4 )[J ] . Journal of the Chemical Society, Dalton Transactions, 2001(6): 806-815.

WU Z K, PEACOCK C L, LANSON B, et al. Transformation of co-containing birnessite to todorokite: Effect of Co on the transformation and implications for Co mobility[J]. Geochimica et Cosmochimica Acta, 2019, 246: 21-40. DOI:10.1016/j.gca.2018. 11.001.

LI K, CHEN C, ZHANG H B, et al. Effects of phase structure of MnO 2 and morphology of δ-MnO 2 on toluene catalytic oxidation[J ] . Applied Surface Science, 2019, 496: 143662. DOI:10.1016/j.apsusc.2019.143662.

GAO F Y, TANG X L, YI H H, et al. In-situ DRIFTS for the mechanistic studies of NO oxidation over α- MnO 2 , β-MnO 2 and γ-MnO 2 catalysts[J ] . Chemical Engineering Journal, 2017, 322: 525-537. DOI:10.1016/j.cej.2017.04.006.

CHU K, LIU Y P, LI Y B, et al. Multi-functional Mo-doping in MnO 2 nanoflowers toward efficient and robust electrocatalytic nitrogen fixation[J ] . Applied Catalysis B: Environmental, 2020, 264: 118525. DOI:10.1016/j.apcatb.2019.118525.

ZHOU J, QIN L F, XIAO W, et al. Oriented growth of layered-MnO 2 nanosheets over α-MnO 2 nanotubes for enhanced room-temperature HCHO oxidation[J ] . Applied Catalysis B: Environmental, 2017, 207: 233-243. DOI:10.1016/j.apcatb.2017. 01.083.

UEMATSU T, MIYAMOTO Y, OGASAWARA Y, et al. Molybdenum-doped α-MnO 2 as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation[J ] . Catalysis Science & Technology, 2016, 6(1): 222-233.

ZHANG N Q, LI L C , GUO Y Z, et al. A MnO 2 -based catalyst with H 2 O resistance for NH 3 -SCR: Study of catalytic activity and reactants-H 2 O competitive adsorption[J ] . Applied Catalysis B: Environmental, 2020, 270: 118860. DOI:10.1016/j.apcatb.2020. 118860.

ZHAO Y X, CHANG C, TENG F, et al. Defect-engineered ultrathin δ -MnO 2 nanosheet arrays as bifunctional electrodes for efficient overall water splitting[J ] . Advanced Energy Materials, 2017, 7(18): 1700005. DOI:10.1002/aenm.201700005.

HE F Y, FENG W J, CHEN X R, et al. Flower-like polymorphic MnO x constructed by in situ L-T transition with superior performance in the catalytic ozonation of dimethyl sulfide under humid conditions[J ] . ACS ES & T Engineering, 2024, 4(12): 3010-3020.

BOYD S, GANESHAN K, TSAI W Y, et al. Effects of interlayer confinement and hydration on capacitive charge storage in birnessite[J]. Nature Materials, 2021, 20(12): 1689-1694. DOI:10.1038/s41563-021-01066-4.

BROUSSE T, BÉLANGER D, LONG J W. To be or not to be pseudocapacitive?[J]. Journal of the Electrochemical Society, 2015, 162(5): A5185-A5189. DOI:10.1149/2.0201505jes.

YANG W H, SU Z A, XU Z H, et al. Comparative study of α-, β-, γ- and δ-MnO 2 on toluene oxidation: Oxygen vacancies and reaction intermediates[J ] . Applie d Catalysis B: Environmental, 2020, 260: 118150. DOI:10.1016/j.apcatb.2019.118150.

XIA A, YU W R, YI J, et al. Synthesis of porous δ-MnO 2 nanosheets and their supercapacitor performance[J ] . Journal of Electroanalytical Chemistry, 2019, 839: 25-31. DOI:10.1016/j.jelechem.2019.02.059.

ALI G A M, YUSOFF M M, SHAABAN E R, et al. High performance MnO 2 nanoflower supercapacitor electrode by electrochemical recycling of spent batteries[J ] . Ceramics International, 2017, 43(11): 8440-8448. DOI:10.1016/j.ceramint. 2017.03.195.

CAO J Y, WANG Y M, ZHOU Y, et al. High voltage asymmetric supercapacitor based on MnO 2 and graphene electrodes[J ] . Journal of Electroanalytical Chemistry, 2013, 689: 201-206. DOI:10.1016/j.jelechem.2012.10.024.

HATZELL K B, FAN L, BEIDAGHI M, et al. Composite manganese oxide percolating networks as a suspension electrode for an asymmetric flow capacitor[J]. ACS Applied Materials & Interfaces, 2014, 6(11): 8886-8893.

SARAVANAKUMAR B, PURUSHOTHAMAN K K, MURALIDHARAN G. MnO 2 grafted V 2 O 5 nanostructures: Formation mechanism, morphology and supercapacitive features[J ] . CrystEngComm, 2014, 16(46): 10711-10720.

WU Z S, REN W C, WANG D W, et al. High-energy MnO 2 nanowire/graphene and graphene asymmetric electrochemical capacitors[J ] . ACS Nano, 2010, 4(10): 5835-5842.

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