Controllable phase transition of Al³⁺ induced manganese dioxide from β- to δ-type and their Al-doped δ-type manganese dioxide for high-performance asymmetric supercapacitors

Abstract

Al-doped manganese dioxide (MnO₂) was synthesized by simple hydrothermal method, and a controllable phase transition of the MnO₂ crystal phase from β to δ was achieved. The effects of Al doping concentration on the structure and electrochemical properties of electrode materials were studied in detail. The results show that the controlled synthesis requires a synergy between KMnO₄, MnCl₂ and AlCl₃, and that Al³⁺ plays an important role. Compared with the pure phase MnO₂, the crystallinity of Al-doped MnO₂ decreases and the specific surface area increases, which provides more active sites for the electrode material. When 3 mmol Al³⁺ is added, the prepared MnO₂-3 has the largest specific capacitance and the highest rate performance. The energy density of the asymmetric supercapacitor (ASC) with MnO₂-3 as the positive electrode and activated carbon (AC) as the negative electrode can reach 18.4 W·h/kg at the power density of 400 W/kg, and the capacity can maintain 90% of the initial value after 20000 cycles, indicating that Al-doped MnO₂ has certain practical application value. This study provides favorable guidance for MnO₂ as a high performance electrode material.

Keywords

Al doping / MnO₂ / phase transformation / energy storage / supercapacitor

References

[1] PanH-q, JiaoX, ZhangW-c, et al.. Supercapacitor with ultra-high power and energy density enabled by nitrogen/oxygen-doped interconnected hollow carbon nano-onions. Chemical Engineering Journal, 2024, 484149663[J]

[2] WangY-b, ChenN-j, ZhouB, et al.. NH₃-induced in situ etching strategy derived 3D-interconnected porous MXene/carbon dots films for high performance flexible supercapacitors. Nano-Micro Letters, 2023, 151231[J]

[3] JiaB-b, ZhangB-h, CaiZ, et al.. Construction of amorphous/crystalline heterointerfaces for enhanced electrochemical processes. eScience, 2023, 32100112[J]

[4] MaH-y, KongD-b, XuY, et al.. Disassembly-reassembly approach to RuO₂/graphene composites for ultrahigh volumetric capacitance supercapacitor. Small, 2017, 13301701026[J]

[5] RakhiR B, ChenW, ChaD, et al.. Substrate dependent self-organization of mesoporous cobalt oxide nanowires with remarkable pseudocapacitance. Nano Letters, 2012, 12(5): 2559-2567[J]

[6] CaoJ-y, LiX-h, WangY-m, et al.. Materials and fabrication of electrode scaffolds for deposition of MnO₂ and their true performance in supercapacitors. Journal of Power Sources, 2015, 293: 657-674[J]

[7] YueT, ShenB-x, GaoP. Carbon material/MnO₂ as conductive skeleton for supercapacitor electrode material: A review. Renewable and Sustainable Energy Reviews, 2022, 158112131[J]

[8] BhatT S, JadhavS A, BeknalkarS A, et al.. MnO₂ core-shell type materials for high-performance supercapacitors: A short review. Inorganic Chemistry Communications, 2022, 141109493[J]

[9] TanggarnjanavalukulC, PhattharasupakunN, KongpatpanichK, et al.. Charge storage performances and mechanisms of MnO₂ nanospheres, nanorods, nanotubes and nanosheets. Nanoscale, 2017, 9(36): 13630-13639[J]

[10] YangW-y, PengD-n, KimuraH, et al.. Honeycomb-like nitrogen-doped porous carbon decorated with Co₃O₄ nanoparticles for superior electrochemical performance pseudo-capacitive lithium storage and supercapacitors. Advanced Composites and Hybrid Materials, 2022, 5(4): 3146-3157[J]

[11] DuW, WangX-n, ZhanJ, et al.. Biological cell template synthesis of nitrogen-doped porous hollow carbon spheres/MnO₂ composites for high-performance asymmetric supercapacitors. Electrochimica Acta, 2019, 296: 907-915[J]

[12] HouC-x, YangW-y, KimuraH, et al.. Boosted lithium storage performance by local build-in electric field derived by oxygen vacancies in 3D holey N-doped carbon structure decorated with molybdenum dioxide. Journal of Materials Science & Technology, 2023, 142: 185-195[J]

[13] JiangH-y, MuQ, KimuraH, et al.. Advanced ferroferric oxide-based composites for lithium-ion battery: Recent developments and future perspectives. Progress in Natural Science: Materials International, 2023, 33(6): 743-753[J]

[14] QinY-q, LuG-p, YangF, et al.. Heteroatom-doped transition metal hydroxides in energy storage and conversion: A review. Materials Advances, 2023, 4(5): 1226-1248[J]

[15] WangJ-z, WangZ, LiuN, et al.. Al doped Ni-Co layered double hydroxides with surface-sulphuration for highly stable flexible supercapacitors. Journal of Colloid and Interface Science, 2022, 615: 173-183[J]

[16] ZhangK-k, WangH, DuX-b, et al.. Reaction mechanism and structural evolution of tunnel-structured KCu₇S₄ nanowires in Li⁺/Na⁺-ion batteries. Advanced Functional Materials, 2024, 34462407105[J]

[17] GodaE S, Ur RehmanA, PanditB, et al.. Al-doped Co₉S₈ encapsulated by nitrogen-doped graphene for solid-state asymmetric supercapacitors. Chemical Engineering Journal, 2022, 428132470[J]

[18] ChenX, LongC-l, LinC-p, et al.. Al and Co co-doped α-Ni(OH)₂/graphene hybrid materials with high electrochemical performances for supercapacitors. Electrochimica Acta, 2014, 137: 352-358[J]

[19] ZengY-h, CongY, JiangT-t, et al.. Sea urchin-like Al-doped MnO₂ nanowires with excellent cycling stability for supercapacitor. International Journal of Electrochemical Science, 2019, 14(5): 4350-4360[J]

[20] HuZ-m, XiaoX, ChenC, et al.. Al-doped α-MnO₂ for high mass-loading pseudocapacitor with excellent cycling stability. Nano Energy, 2015, 11: 226-234[J]

[21] GuoY, LiL, SongL, et al.. Co²⁺ induced phase transformation from δ- to α-MnO₂ and their hierarchical α-MnO₂@δ-MnO₂ nanostructures for efficient asymmetric supercapacitors. Journal of Materials Chemistry A, 2019, 7(20): 12661-12668[J]

[22] LiuS-b, HuangH, YangC-g, et al.. Electrochemical activation enabling structure reconstruction of Fe-doped MnO₂ for enhancing pseudocapacitive storage. Chemical Engineering Journal, 2022, 441135967[J]

[23] DevarajS, MunichandraiahN. Effect of crystallographic structure of MnO₂ on its electrochemical capacitance properties. The Journal of Physical Chemistry C, 2008, 112(11): 4406-4417[J]

[24] ZhangX-h, LiuX-y, LiB-x, et al.. Rapid microwave synthesis of δ-MnO₂ microspheres and their electrochemical property. Journal of Materials Science: Materials in Electronics, 2013, 24(7): 2189-2196[J]

[25] XieM, LinM-x, FengC, et al.. Coupling Zn²⁺ doping and rich oxygen vacancies in MnO₂ nanowire toward advanced aqueous zinc-ion batteries. Journal of Colloid and Interface Science, 2023, 645: 400-409[J]

[26] WangJ-y, ZhouJ-t, van ZalingeH, et al.. Hollow SiC@MnO₂ nanospheres with tunable core size and shell thickness for excellent electromagnetic wave absorption. Chemical Engineering Journal, 2023, 471144769[J]

[27] HeS-m, MoZ-l, ShuaiC, et al.. Pre-intercalation δ-MnO₂ zinc-ion hybrid supercapacitor with high energy storage and ultra-long cycle life. Applied Surface Science, 2022, 577151904[J]

[28] ZhangS, YangF, CaoX-h, et al.. Enhanced uranium separation by charge enabling γ-MnO₂ with oxygen vacancies. Journal of Hazardous Materials, 2023, 459132112[J]

[29] LiX-m, QuJ-q, XuJ-m, et al.. K-preintercalated MnO₂ nanosheets as cathode for high-performance Zn-ion batteries. Journal of Electroanalytical Chemistry, 2021, 895115529[J]

[30] YangP, ZhengD-y, ZhuP-h, et al.. Biocarbon with large specific surface area and tunable pore structure from binary molten salt templating for supercapacitor applications. Chemical Engineering Journal, 2023, 472144785[J]

[31] BaoY-h, XuH, ZhuY-q, et al.. Pore regulation and surface modification collaboratively enhance biomass porous carbon anchoring azure A for stable supercapacitor electrode. Industrial Crops and Products, 2024, 210118176[J]

[32] SelloniA. Anatase shows its reactive side. Nature Materials, 2008, 7(8): 613-615[J]

[33] RongS-p, ZhangP-y, LiuF, et al.. Engineering crystal facet of α-MnO₂ nanowire for highly efficient catalytic oxidation of carcinogenic airborne formaldehyde. ACS Catalysis, 2018, 8(4): 3435-3446[J]

[34] van SantenR A. Complementary structure sensitive and insensitive catalytic relationships. Accounts of Chemical Research, 2009, 42(1): 57-66[J]

[35] VittadiniA, SelloniA, RotzingerF P, et al.. Structure and energetics of water adsorbed at TiO₂ anatase (101) and (001) surfaces. Physical Review Letters, 1998, 81(14): 2954-2957[J]

[36] SamuelE, JoshiB, KimY I, et al.. ZnO/MnO_a nanoflowers for high-performance supercapacitor electrodes. ACS Sustainable Chemistry & Engineering, 2020, 8(9): 3697-3708[J]

[37] PatilS S, PatilP S. 3D Bode analysis of nickel pyrophosphate electrode: A key to understanding the charge storage dynamics. Electrochimica Acta, 2023, 451142278[J]

[38] ChenW, YanL-c, SongZ-h, et al.. NiMn₂O₄/CoS nanostructure electrode material for flexible asymmetric supercapacitors. Electrochimica Acta, 2024, 491144329[J]

[39] GuoW, YuC, LiS-f, et al.. Strategies and insights towards the intrinsic capacitive properties of MnO₂ for supercapacitors: Challenges and perspectives. Nano Energy, 2019, 57: 459-472[J]

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