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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2023 · IF 9.9

Quinone-amine polymer nanospheres with enhanced redox activity for aqueous proton storage

Jun Yang,Panrun Shao,Xinran Zhao,Yunhong Liao,Chao Yan

One of the biggest obstacles to the development of aqueous proton batteries (APBs), despite numerous optimization techniques, is the preparation and use of high-performance electrode materials. In this work, to improve the high solubility, limited capacity and poor cycle life of small organic molecules in APBs, homogeneous dispersed quinone-amine polymer nanospheres (PQANS) (average diameter: 220 nm) were synthesized by a polymerization reaction based on 3,3′-diaminobenzidine (DAB) and benzoquinone (BQ), making them suitable for proton storage in aqueous systems. As an anode for APBs, the obtained PQANS exhibits an improved reversible capacity of 126.2 mAh/g at 1 A/g after 300 cycles. The durable stable measurement of PQANS at 10 A/g was also conducted with a specific capacity of 66.8 mAh/g after 12,000 cycles. A series of in situ or ex situ measurements were used to establish the superior H + storage mechanism of PQANS. A novel reaction mechanism of redox enhancement was revealed due to the existence of more carbonyl groups after the first cycle. Theoretical calculations were conducted to help illustrate the principle of binding protons with functional groups in PQANS. Finally, a PQANS anode-based aqueous proton full battery was constructed to demonstrate its potential application, which exhibits a specific capacity of 50.6 mAh/g at 1 A/g (600 cycles). This work provides a reference for preparing high-performance polymer-based electrode materials in aqueous batteries.

研究领域: 材料科学 · 电化学 · 储能技术
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ACS Nano · 2024 · IF 15.8

Enhancing Zn2+/H+ Joint Charge Storage in MnO2: Concurrently Tailoring Mn’s Local Electron Density and O’s p-Band Center

Haijian Huang,Hao Feng,Ziyu He,Yanan Huang,Jiawei Xu,Chengzhi Hu,Zhangxian Chen,Zeheng Yang,Weixin Zhang

Enhancing proton storage in the zinc-ion battery cathode material of MnO2 holds promise in promoting its electrochemical performance by mitigating the intense Coulombic interaction between divalent zinc ions and the host structure. However, challenges persist in addressing the structural instability caused by Jahn–Teller effects and accurately modulating H+ intercalation in MnO2. Herein, the doping of high-electronegativity Sb with fully occupied d-orbital in MnO2 is reported. The Sb doping strategy engenders the formation of Mn–O–Sb path in the structure with a strong dipole polarization field, which facilitates the delocalization of eg orbital electron in Mn and thus mitigates the Jahn–Teller effects. Simultaneously, adjusting the level of Sb doping in MnO2 leads to modulation of the p-band center of O, optimizing its interaction with hydrogen and thereby enhancing proton storage. Consequently, MnO2 doped with 6% Sb exhibits commendable performance in both rate capability and cycling endurance, delivering 113 mAh g–1 at 2 A g–1 after 2000 cycles. This investigation underscores the crucial role of electronic structural engineering in elevating the electrochemical performance of cathode materials for zinc-ion batteries.

CAS / MDL: 6923-52-0
研究领域: 材料科学 · 电化学
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ELECTROCHIMICA ACTA · 2025 · IF 5.6

Stable Proton Storage in α-MoO3 via a Bifunctional Molecular Crowding Electrolyte

Xiang Cai,Shijun Tang,Zi-min An,Qiyao Shao,Kuixuan Zhang,Huan Liu

Layered molybdenum trioxide (α-MoO 3 ) storing protons exhibits a high theoretical capacity and extraordinary rate capability and can be used as a reliable anode material for aqueous proton batteries. But a severe dissolution issue during operation always results in rapid failure in battery performance. Herein, a bifunctional molecular crowding electrolyte was engineered to address this issue. The high-concentration inert polymer, polyethylene glycol 400, reduces the free water activity of the electrolyte and the low-concentration solute, trifluoromethanesulfonic acid, forms a proton-rich electrolyte environment under such a water-poor condition thanks to its intrinsic superacidity, both of which favour the reverse shift of the dissolution equilibrium, and with the latter enabling the electrolyte with high ion conductivity as well. Thus, the α-MoO 3 electrode in the above electrolyte shows a longer lifespan without sacrificing its rate capability. The analysis on charge storage mechanisms by X-ray powder diffraction technique demonstrates that α-MoO 3 undergoes bare proton-involved multistep two-phase and solid-solution reactions, where only the two-phase reaction between hydrogen molybdenum bronze II and III phases and the solid-solution reactions of themselves are reversible.

研究领域: 材料化学 · 电化学 · 能源存储 · 无机化学 · 固体化学 · 电池技术 · 功能材料
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Small · 2023 ·Vol. 20 ·期 2 ·2305386 · IF 13.3

Vanadium Hexacyanoferrate Prussian Blue Analogs for Aqueous Proton Storage: Excellent Electrochemical Properties and Mechanism Insights

Jun Yang,Wenxiu Hou,Lingqian Ye,Guoyu Hou,Chao Yan,Yu Zhang

The significant attraction toward aqueous proton batteries (APBs) is attributable to their expedited kinetics, elevated safety profile, and economical feasibility. Nevertheless, their practical implement is significantly blocked by the unsatisfactory energy density due to the limited cathode materials. Herein, vanadium hexacyanoferrate Prussian blue analog (VOHCF) is introduced as a potentially favorable cathode material for APBs. The findings demonstrate that this VOHCF electrode exhibits a notable reversible capacity of 102.7 mAh g −1 and exceptional cycling stability, with 95.4% capacity retention over 10 000 cycles at 10 A g −1 . It is noteworthy that this is the detailed instance of VOHCF being proposed as a cathode for APBs. Combining the in situ characterization techniques and theoretical simulations, the origins of excellent proton storage performance are revealed as the multiple redox mechanisms with double active centers of ─C≡N group and V═O bond in VOHCF as well as the robust structure stability. A proton full cell with excellent performance is further achieved by coupling the VOHCF cathode and diquinoxalino[2,3-a:2′,3′-c] phenazine (HATN) anode, demonstrating the great potential of VOHCF in practical applications. This work could provide fundamental understanding to the development of feasible cathode materials for proton storage device.

研究领域: 材料科学 · 电化学 · 能源存储
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