The Role of Al3+‐Based Aqueous Electrolytes in the Charge Storage Mechanism of MnOx Cathodes

Balland, Véronique; Mateos, Mickaël; Singh, Arvinder; Harris, Kenneth D. M.; Laberty‐Robert, Christel; Limoges, Benoı̂t

doi:10.1002/smll.202101515

Cited by 26 publications

(32 citation statements)

References 34 publications

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“…Aquo Al 3+ is a Brønsted weak acid, which can act as the proton-donor reservoir to sustain the acidic environment at the metal oxide/electrolyte interface during discharging. 40,41 We monitored the pH evolution during charging/discharging in these batteries via in situ pH measurements. As shown in Figure 4b, the pH value of the electrolyte in the Zn−(Al)Mn battery is stable during discharging.…”

Section: Resultsmentioning

confidence: 99%

Enabling Reversible MnO₂/Mn²⁺ Transformation by Al³⁺ Addition for Aqueous Zn–MnO₂ Hybrid Batteries

Qin

Song

Yang

et al. 2022

ACS Appl. Mater. Interfaces

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Aqueous rechargeable Zn−manganese dioxide (Zn−MnO 2 ) hybrid batteries based on dissolution−deposition mechanisms exhibit ultrahigh capacities and energy densities due to the two-electron transformation between MnO 2 /Mn 2+ . However, the reported Zn−MnO 2 hybrid batteries usually use strongly acidic and/or alkaline electrolytes, which may lead to environmental hazards and corrosion issues of the Zn anodes. Herein, we propose a new Zn−MnO 2 hybrid battery by adding Al 3+ into the sulfate-based electrolyte. The hybrid battery undergoes reversible MnO 2 /Mn 2+ transformation and exhibits good electrochemical performances, such as a high discharge capacity of 564.7 mAh g −1 with a discharge plateau of 1.65 V, an energy density of 520.8 Wh kg −1 , and good cycle life without capacity decay upon 2000 cycles. Experimental results and theoretical calculation suggest that the aquo Al 3+ with Brønsted weak acid nature can act as the proton-donor reservoir to maintain the electrolyte acidity near the electrode surface and prevent the formation of Zn 4 (OH) 6 (SO 4 )•0.5H 2 O during discharging. In addition, Al 3+ doping during charging introduces oxygen vacancies in the oxide structure and weakens the Mn− O bond, which facilitates the dissolution reaction during discharge. The mechanistic investigation discloses the important role of Al 3+ in the electrolyte, providing a new fundamental understanding of the promising aqueous Zn−MnO 2 batteries. KEYWORDS: Zn−MnO 2 hybrid batteries, MnO 2 /Mn 2+ transformation, Al 3+ addition, electrolyte engineering, high energy density

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Section: Resultsmentioning

confidence: 99%

Enabling Reversible MnO₂/Mn²⁺ Transformation by Al³⁺ Addition for Aqueous Zn–MnO₂ Hybrid Batteries

Qin

Song

Yang

et al. 2022

ACS Appl. Mater. Interfaces

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“…Moreover, the AAIB system is affected by water molecules; thus, the formation of a crystalline water framework on the cathode layer (complexity) during the (de)intercalation process was investigated using various instrumental techniques [54] . Previous studies on MnO 2 cathodes have proposed a mechanism based on reversible H + ‐coupled MnO 2 to Mn 2+ conversion, where hydrated Al 3+ acts as a proton donor [55] . This implies that it is also possible to react water molecules (H + ) with hydrated Al 3+ during intercalation into V 6 O 13 .…”

Section: Resultsmentioning

confidence: 99%

“…[54] Previous studies on MnO 2 cathodes have proposed a mecha-nism based on reversible H + -coupled MnO 2 to Mn 2 + conversion, where hydrated Al 3 + acts as a proton donor. [55] This implies that it is also possible to react water molecules (H + ) with hydrated Al 3 + during intercalation into V 6 O 13 . Consequently, the dissolution of metal ions (Al and Zn) and proton ions (H + ) occurs during the (de)intercalation process.…”

Section: Electrochemical Study Of Zn-al/3 M Al(otf) 3 /V 6 O 13 Aaibsmentioning

confidence: 99%

Multi‐Ionic Capacity of Zn‐Al/V₆O₁₃ Systems Enable Fast‐Charging and Ultra‐Stable Aqueous Aluminium‐Ion Batteries

Kim

Selvamani

et al. 2022

ChemElectroChem

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Rechargeable, cost‐efficient aqueous aluminium‐ion batteries (AAIBs) possess abundant trivalent charge carriers with high volumetric energy densities. However, the rapid and irreversible formation of Al2O3 passivation films on aluminium‐ion (AI) anodes while using aqueous electrolytes limits their development. Herein, Zn metal was used as the anode, and Al3+ was locally deposited on the Zn anode during charging. V6O13 with a mixed vanadium state of V4+/V5+ was chosen as the cathode because of its efficient ion diffusion (solid state) and high electron conductivity. The Zn−Al/3 M Al(OTF)3/V6O13 cell exhibited high current density and excellent long‐term cycling stability, demonstrating a very high specific capacity of ∼100 mAh g−1 at a current density of 3 A g−1 and Coulombic efficiency of ∼100 % with reversible stability over 1400 cycles. Furthermore, the V6O13 cathode exhibited a multi‐ionic capacity of Zn2+‐ and H+‐ions during the Al deposition/dissolution reaction in AAIBs, demonstrating high safety and stability for fast charging.

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“…During the charge and discharge process, instead of Al 3 + intercalation and extraction, the aluminium hexaaquo complex [Al(H 2 O) 6 ] 3 + serves as the proton source and acts as H + charge carriers to realize reversible proton insertion/ extraction. [25] The second proposed mechanism can be described by the following reaction:…”

Section: Al Metal Anode Reaction Mechanismmentioning

confidence: 99%

Anode Materials for Rechargeable Aqueous Al‐Ion Batteries: Progress and Prospects

2022

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Rechargeable aqueous Al‐ion batteries (AIBs) have attracted more attention as potential energy storage systems due to their low cost, high safety, and environmental friendliness. As a crucial role in AIBs, efforts have been devoted to exploring suitable anode material over the past decade. Herein, the latest advances in using Al3+ intercalation and Al deposition anode materials are critically discussed, including current challenges, reaction mechanisms, and achievable electrochemical properties. This review aims to provide a summary of the strategies proposed to date to overcome the anode issues restricting the present rechargeable aqueous AIBs. Emphasis is placed on alleviating the passivation and corrosion problems of metallic Al anode for realizing rechargeable aqueous AIBs with high energy density. Finally, some suggestions are put forward for the guidance of future research directions on the optimization of anode materials in the expectation of promoting further development of rechargeable aqueous AIBs.

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The Role of Al³⁺‐Based Aqueous Electrolytes in the Charge Storage Mechanism of MnO_x Cathodes

Cited by 26 publications

References 34 publications

Enabling Reversible MnO₂/Mn²⁺ Transformation by Al³⁺ Addition for Aqueous Zn–MnO₂ Hybrid Batteries

Enabling Reversible MnO₂/Mn²⁺ Transformation by Al³⁺ Addition for Aqueous Zn–MnO₂ Hybrid Batteries

Multi‐Ionic Capacity of Zn‐Al/V₆O₁₃ Systems Enable Fast‐Charging and Ultra‐Stable Aqueous Aluminium‐Ion Batteries

Anode Materials for Rechargeable Aqueous Al‐Ion Batteries: Progress and Prospects

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The Role of Al3+‐Based Aqueous Electrolytes in the Charge Storage Mechanism of MnOx Cathodes

Cited by 26 publications

References 34 publications

Enabling Reversible MnO2/Mn2+ Transformation by Al3+ Addition for Aqueous Zn–MnO2 Hybrid Batteries

Enabling Reversible MnO2/Mn2+ Transformation by Al3+ Addition for Aqueous Zn–MnO2 Hybrid Batteries

Multi‐Ionic Capacity of Zn‐Al/V6O13 Systems Enable Fast‐Charging and Ultra‐Stable Aqueous Aluminium‐Ion Batteries

Anode Materials for Rechargeable Aqueous Al‐Ion Batteries: Progress and Prospects

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The Role of Al³⁺‐Based Aqueous Electrolytes in the Charge Storage Mechanism of MnO_x Cathodes

Enabling Reversible MnO₂/Mn²⁺ Transformation by Al³⁺ Addition for Aqueous Zn–MnO₂ Hybrid Batteries

Enabling Reversible MnO₂/Mn²⁺ Transformation by Al³⁺ Addition for Aqueous Zn–MnO₂ Hybrid Batteries

Multi‐Ionic Capacity of Zn‐Al/V₆O₁₃ Systems Enable Fast‐Charging and Ultra‐Stable Aqueous Aluminium‐Ion Batteries