Guest Ion-Dependent Reaction Mechanisms of New Pseudocapacitive Mg₃ V₄ (PO₄ )₆ /Carbon Composite as Negative Electrode for Monovalent-Ion Batteries.

ABSTRACT: Polyanion-type phosphate materials, such as M₃ V₂ (PO₄ )₃ (M = Li/Na/K), are promising as insertion-type negative electrodes for monovalent-ion batteries including Li/Na/K-ion batteries (lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs)) with fast charging/discharging and distinct redox peaks. However, it remains a great challenge to understand the reaction mechanism of materials upon monovalent-ion insertion. Here, triclinic Mg₃ V₄ (PO₄ )₆ /carbon composite (MgVP/C) with high thermal stability is synthesized via ball-milling and carbon-thermal reduction method and applied as a pseudocapacitive negative electrode in LIBs, SIBs, and PIBs. In operando and ex situ studies demonstrate the guest ion-dependent reaction mechanisms of MgVP/C upon monovalent-ion storage due to different sizes. MgVP/C undergoes an indirect conversion reaction to form Mg⁰ , V⁰ , and Li₃ PO₄ in LIBs, while in SIBs/PIBs the material only experiences a solid solution with the reduction of V³⁺ to V²⁺ . Moreover, in LIBs, MgVP/C delivers initial lithiation/delithiation capacities of 961/607 mAh g^-1 (30/19 Li⁺ ions) for the first cycle, despite its low initial Coulombic efficiency, fast capacity decay for the first 200 cycles, and limited reversible insertion/deinsertion of 2 Na⁺ /K⁺ ions in SIBs/PIBs. This work reveals a new pseudocapacitive material and provides an advanced understanding of polyanion phosphate negative material for monovalent-ion batteries with guest ion-dependent energy storage mechanisms.

SUBMITTER: Fu Q 

PROVIDER: S-EPMC10104641 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature