Strategies for pH regulation in aqueous zinc ion batteries

Liu, Mingqiang; Wang, Peiqingfen; Zhang, Wei; He, Hongzhen; He, Guanjie; Xu, Shusheng; Yao, Lu; Miller, Thomas S.

doi:10.1016/j.ensm.2024.103248

Cited by 16 publications

(3 citation statements)

References 95 publications

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“…The development of advanced energy storage technologies, such as batteries and supercapacitors, can help balance supply and demand in the power system and improve the stability and reliability of the power system. − Zinc-ion batteries (ZIBs) based on the ion insertion/extraction reaction are considered to be typical replacements for post-lithium-ion batteries due to their superior theoretical energy density, environmental friendliness, and economic benefits. , Despite these advantages, due to the two-electron process of Zn 2+ insertion/extraction, the ion migration energy barrier is large, the electrochemical polarization is high, and the host microstructure and phase structure are easily destroyed, which inhibit the voltage magnification and cycling performance of ZIBs . This phenomenon is particularly common in aqueous zinc-ion batteries (AZIBs) with MnO 2 as the cathode material.…”

Section: Introductionmentioning

confidence: 99%

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Wan,

Liu,

Xia

et al. 2024

Inorg. Chem.

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Rechargeable Zn-MnO 2 batteries using mild water electrolytes have garnered significant interest owing to their impressive theoretical energy density and eco-friendly characteristics. However, MnO 2 suffers from huge structural changes during the cycles, resulting in very poor stability at high charge−discharge depths. Briefly, the above problems are caused by slow kinetic processes and the dissolution of Mn atoms in the cycles. In this paper, a 2D homojunction electrode material (δ/ε-MnO 2 ) based on δ-MnO 2 and ε-MnO 2 has been prepared by a two-step electrochemical deposition method. According to the DFT calculations, the charge transfer and bonding between interfaces result in the generation of electronic states near the Fermi surface, giving δ/ε-MnO 2 a more continuous distribution of electron states and better conductivity, which is conducive to the rapid insertion/extraction of Zn 2+ and H + . Moreover, the strongly coupled Mn− O−Mn interfacial bond can effectively impede dissolution of Mn atoms and thus maintain the structural integrity of δ/ε-MnO 2 during the cycles. Accordingly, the δ/ε-MnO 2 cathode exhibits high capacity (383 mAh g −1 at 0.1 A g −1 ), superior rate performance (150 mAh g −1 at 5 A g −1 ), and excellent cycling stability over 2000 cycles (91.3% at 3 A g −1 ). Profoundly, this unique homojunction provides a novel paradigm for reasonable selection of different components.

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Section: Introductionmentioning

confidence: 99%

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Wan,

Liu,

Xia

et al. 2024

Inorg. Chem.

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“…20,21 Moreover, The issues of zinc electrode corrosion, passivation, hydrogen evolution, and dendrite growth are all closely related to pH. 22 The lower the pH, the more intense the corrosion and hydrogen evolution reactions. Different pH levels, as well as pH fluctuations, affect the formation of passivation products.…”

Section: Introductionmentioning

confidence: 99%

“…The decoupled high-voltage aqueous battery separator cannot effectively block the shuttle of H + /OH – , leading to a decrease in the electrolyte mixing performance . Aqueous flow batteries, which typically use cation exchange membranes, can also have an unbalanced state of OH – ions. , Moreover, The issues of zinc electrode corrosion, passivation, hydrogen evolution, and dendrite growth are all closely related to pH . The lower the pH, the more intense the corrosion and hydrogen evolution reactions.…”

Section: Introductionmentioning

confidence: 99%

In Situ Visualization of Ion Transport Processes in Aqueous Batteries

Chen,

Li,

Lian

et al. 2024

ACS Appl. Mater. Interfaces

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Aqueous rechargeable batteries are regarded as one of the most reliable solutions for electrochemical energy storage, and ion (e.g., H + or OH − ) transport is essential for their electrochemical performance. However, modeling and numerical simulations often fall short of depicting the actual ion transport characteristics due to deviations in model assumptions from reality. Experimental methods, including laser interferometry, Raman, and nuclear magnetic resonance imaging, are limited by the complexity of the system and the restricted detection of ions, making it difficult to detect specific ions such as H + and OH − . Herein, in situ visualization of ion transport is achieved by innovatively introducing laser scanning confocal microscopy. Taking neutral Zn−air batteries as an example and using a pH-sensitive probe, real-time dynamic pH changes associated with ion transport processes are observed during battery operation. The results show that after immersion in the zinc sulfate electrolyte, the pH near the Zn electrode changes significantly and pulsation occurs, which demonstrates the intense self-corrosion hydrogen evolution reaction and the periodic change in the reaction intensity. In contrast, the change in the pH of the galvanized electrode plate is weak, proving its significant corrosion inhibition effect. For the air electrode, the heterogeneity of ion transport during the discharging and charging process is presented. With an increase of the current density, the ion transport characteristics gradually evolve from diffusion dominance to convection-diffusion codominance, revealing the importance of convection in the ion transport process inside batteries. This method opens up a new approach of studying ion transport inside batteries, guiding the design for performance enhancement.

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Zinc Chemistries of Hybrid Electrolytes in Zinc Metal Batteries: From Solvent Structure to Interfaces

Chen,

Wang,

Wang

et al. 2024

Advanced Materials

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Along with the booming research on zinc metal batteries (ZMBs) in recent years, operational issues originated from inferior interfacial reversibility have become inevitable. Presently, single‐component electrolytes represented by aqueous solution, “water‐in‐salt,” solid, eutectic, ionic liquids, hydrogel, or organic solvent system are hard to undertake independently the task of guiding the practical application of ZMBs due to their specific limitations. The hybrid electrolytes modulate microscopic interaction mode between Zn2+ and other ions/molecules, integrating vantage of respective electrolyte systems. They even demonstrate original Zn2+ mobility pattern or interfacial chemistries mechanism distinct from single‐component electrolytes, providing considerable opportunities for solving electromigration and interfacial problems in ZMBs. Therefore, it is urgent to comprehensively summarize the zinc chemistries principles, characteristics, and applications of various hybrid electrolytes employed in ZMBs. This review begins with elucidating the chemical bonding mode of Zn2+ and interfacial physicochemical theory, and then systematically elaborates the microscopic solvent structure, Zn2+ migration forms, physicochemical properties, and the zinc chemistries mechanisms at the anode/cathode interfaces in each type of hybrid electrolytes. Among of which, the scotoma and amelioration strategies for the current hybrid electrolytes are actively exposited, expecting to provide referenceable insights for further progress of future high‐quality ZMBs.

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Strategies for pH regulation in aqueous zinc ion batteries

Cited by 16 publications

References 95 publications

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

In Situ Visualization of Ion Transport Processes in Aqueous Batteries

Zinc Chemistries of Hybrid Electrolytes in Zinc Metal Batteries: From Solvent Structure to Interfaces

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Strategies for pH regulation in aqueous zinc ion batteries

Cited by 16 publications

References 95 publications

Phase-Modified Strongly Coupled δ/ε-MnO2 Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Phase-Modified Strongly Coupled δ/ε-MnO2 Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

In Situ Visualization of Ion Transport Processes in Aqueous Batteries

Zinc Chemistries of Hybrid Electrolytes in Zinc Metal Batteries: From Solvent Structure to Interfaces

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Product

Resources

About

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

Phase-Modified Strongly Coupled δ/ε-MnO₂ Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries