Accessing the 2 V VV/VIV redox process of vanadyl phosphate cathode for aqueous batteries

Shi, Hua‐Yu; Wu, Wanlong; Yang, Xianpeng; Jia, Zhongqiu; Lin, Zhitao; Qin, Zengming; Song, Yu; Guo, Di; Sun, Xiaoqi

doi:10.1016/j.jpowsour.2021.230270

Cited by 6 publications

(2 citation statements)

References 59 publications

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“…[13,14] However, the reactivity of VOPO 4 is usually limited by the partial reduction of V 5+ during the synthesis process, reducing the amount of inserted Na + upon the first discharge and thus leading to an inferior actual capacity. [15,16] To address this issue, Cao's group directly synthesized a layered NaVOPO 4 cathode material by chemically pre-intercalating Na ions in VOPO 4 , delivering a promising discharge capacity of 144 mAh g −1 at 0.05 C. [17] Yu's team expanded the interlayer spacing of VOPO 4 nanosheets (from 0.74 to 1.06 nm) to ameliorate the sodium-ion diffusion via controlled organic molecules intercalation, achieving an improved reversible capacity of 155 mAh g −1 at 0.1 C. [18] Manthiram and co-workers effectively enhanced the electrical conductivity of VOPO 4 by incorporating reduced graphene oxide, and fascinating rate performance of 72 mAh g −1 at 0.5 C was demonstrated. [19] Despite encouraging progresses have been made, the above-mentioned studies mainly focused on the structure modification and component design of VOPO 4 .…”

Section: Introductionmentioning

confidence: 99%

Unveiling the Anionic Redox Chemistry in Phosphate Cathodes for Sodium‐Ion Batteries

Jian

Shen

Zhao

et al. 2023

Adv Funct Materials

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Anionic redox chemistry has aroused increasing attention in sodium‐ion batteries (SIBs) by virtue of the appealing additional capacity. However, up to now, anionic redox reaction has not been reported in the mainstream phosphate cathodes for SIBs. Herein, the ultrathin VOPO4 nanosheets are fabricated as promising cathodes for SIBs, where the oxygen redox reaction is first activated accompanied by reversible ClO4− (from the electrolyte) insertion/extraction. As a result, the VOPO4 cathode harvests a record‐high capacity (168 mAh g−1 at 0.1 C) among its counterparts ever reported. Moreover, the ClO4− insertion efficiently expands the interlayer spacing of VOPO4 and accelerates the ion diffusion, enabling an unprecedentedly high rate performance (69 mAh g−1 at 30 C). Via systematic ex situ characterizations and theoretical computations, the anionic redox chemistry and charge storage mechanism upon cycling are thoroughly elucidated. This study opens up a new avenue toward high‐energy phosphate cathodes for SIBs by triggering anionic redox reactions.

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Section: Introductionmentioning

confidence: 99%

Unveiling the Anionic Redox Chemistry in Phosphate Cathodes for Sodium‐Ion Batteries

Jian

Shen

Zhao

et al. 2023

Adv Funct Materials

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“…However, there are few reports on the electrochemical intercalation of different cations in aqueous electrolytes. Literature data mainly report the electrochemical intercalation of zinc [3,12,[21][22][23][24] and aluminium ions [7,11] in aqueous electrolytes. The electrochemical measurements use a composite electrode comprising active mass particles, conductive additives, and a polymeric binder.…”

Section: Introductionmentioning

confidence: 99%

The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte

et al. 2022

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Layered VOPO4·2H2O is synthesized by the sonochemical method. An X-ray powder diffraction is used to examine the crystal structure, while scanning electron microscopy is used to reveal the morphology of the powder. The crystal structure refinement is performed in the P4/nmmZ space group. The electrochemical intercalation of several cations (Na+, Mg2+, Ca2+, and Al3+) in saturated nitrate aqueous solutions is investigated. The most notable reversible activity is found for the cycling in aluminium nitrate aqueous solution in the voltage range from −0.1 to 0.8 V vs. SCE. During the preparation of the electrode, it is observed that the structure is prone to changes that have not been recorded in the literature so far. Namely, the use of conventional binder PVDF in NMP solution deteriorates the structure and lowers the powder’s crystallinity, while the use of Nafion solution causes the rearrangement of the atoms in a new crystal form that can be described in the monoclinic P21/c space group. Consequently, these structural changes affect electrochemical performances. The observed differences in electrochemical performances are a result of structural rearrangements.

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Quantifying and Suppressing Proton Intercalation to Enable High‐Voltage Zn‐Ion Batteries

Wang

Blanc

et al. 2021

Advanced Energy Materials

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Rechargeable Zn‐ion batteries (ZIBs) are widely regarded as promising candidates for large‐scale energy storage applications. Like most multivalent battery systems (based on Zn, Mg, Ca, etc.), further progress in ZIB development relies on the discovery and design of novel cathode hosts capable of reversible Zn2+ (de)intercalation. Herein, this work employs VPO4F as a ZIB cathode and explores ensuing intercalation mechanisms along with interfacial dynamics during cycling to quantify the water dynamics in concentrated electrolytes and/or hybrid aqueous‐non aqueous (HANEs) electrolyte(s). Like most oxide‐based cathode materials, proton (H+) intercalation dominates electrochemical activity during discharge of ZnxHyVPO4F in aqueous media due to the hydroxylated nature of the interface. Such H+ electrochemistry diminishes low‐rate and/or long‐term electrochemical performance of ZIBs which inhibits implementation for practical applications. Thus, quantification of the water dynamics in various electrolytes is demonstrated for the first time. Detailed investigations of water mobility in various concentrated electrolytes and HANEs systems enable the design of an electrolyte that enhances aqueous anodic stability and suppresses water/proton activity during discharge. Tuning Zn2+/H+ intercalation kinetics simultaneously allows for a high voltage (1.9 V) and long‐lasting aqueous zinc‐ion battery: Zn|Zn(OTf)2·nH2O‐PC|ZnxHyVPO4F.

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Accessing the 2 V VV/VIV redox process of vanadyl phosphate cathode for aqueous batteries

Cited by 6 publications

References 59 publications

Unveiling the Anionic Redox Chemistry in Phosphate Cathodes for Sodium‐Ion Batteries

Unveiling the Anionic Redox Chemistry in Phosphate Cathodes for Sodium‐Ion Batteries

The Influence of a Binder in a Composite Electrode: The Case Study of Vanadyl Phosphate in Aqueous Electrolyte

Quantifying and Suppressing Proton Intercalation to Enable High‐Voltage Zn‐Ion Batteries

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