Thermodynamic Origin-Based In Situ Electrochemical Construction of Reversible p-n Heterojunctions for Optimal Stability in Potassium Ion Storage.

Heterojunctions in electrode materials offer diverse improvements during the cycling process of energy storage devices, such as volume change buffering, accelerated ion/electron transfer, and better electrode structure integrity, however, obtaining optimal heterostructures with nanoscale domains remains challenging within constrained materials. A novel in situ electrochemical method is introduced to develop a reversible CuSe/PSe p-n heterojunction (CPS-h) from Cu3PSe4 as starting material, targeting maximum stability in potassium ion storage. The CPS-h formation is thermodynamically favorable, characterized by its superior reversibility, minimized diffusion barriers, and enhanced conversion post K+ interaction. Within CPS-h, the synergy of the intrinsic electric field and P-Se bonds enhance electrode stability, effectively countering the Se shuttling phenomenon. The specific orientation between CuSe and PSe leads to a 35° lattice mismatch generates large space at the interface, promoting efficient K ion migration. The Mott-Schottky analysis validates the consistent reversibility of CPS-h, underlining its electrochemical reliability. Notably, CPS-h demonstrates a negligible 0.005% capacity reduction over 10,000 half-cell cycles and remains stable through 2,000 and 4,000 cycles in full cells and hybrid capacitors, respectively. This study emphasizes the pivotal role of electrochemical dynamics in formulating highly stable p-n heterojunctions, representing a significant advancement in potassium-ion battery (PIB) electrode engineering.

Oxygen Vacancy-Tailored Schottky Heterojunction Activates Interface Dipole Amplification and Carrier Inversion for High-Performance Potassium-Ion Batteries.

An oxygen vacancy-tailored Schottky heterostructure composed of polyvinylpyrrolidone-assisted Bi2 Sn2 O7 (PVPBSO) nanocrystals and moderate work function graphene (mWFG, WF = 4.36 eV) is designed, which in turn intensifies the built-in voltage and interface dipole across the space charge region (SCR), leading to the inversion of majority carriers for facilitating K+ transport/diffusion behaviors. Thorough band-alignment experiments and interface simulations reveal the dynamics between deficient BSO and mWFG, and how charge redistribution within the SCR leads to carrier inversion, demonstrating the impact of different defect engineering degrees on the amplification of Schottky junctions. The ordered transport of bipolar carriers can boost electrons and K ions easily passing through the inner and outer surfaces of the heterostructure. With high activity and low resistance in electrochemical reactions, the PVPBSO/mWFG exhibits an attractive capacity of 430 mA h g-1 and a rate capability exceeding 2000 mA g-1 , accompanied by minimal polarization and efficient utilization of conversion-alloying reactions. The substantial cell capacity and high-redox plateau of PVPBSO/mWFG//PB contribute to the practical feasibility of high-energy full batteries, offering long-cycle retention and high-voltage output. This study emphasizes the direct importance of interface and junction engineering in improving the efficiency of diverse electrochemical kinetic and diffusion processes for potassium-ion batteries.

3D space-confined Co0.85Se architecture with effective interfacial stress relaxation as anode material reveals robust and highly loading potassium-ion batteries.

Conversion-type transition metal chalcogenide anodes could bring relatively high specific capacity in potassium ion storage due to multiple electron transport reactions, but often accompanying huge volume changes and resulting in low cycle life and rapid capacity fading.While electrode materials are closely packed, the contact at the interface during potassiation/depotassiation is similar to point-to-point contact, generating strong stress to make self-aggregation occur. In this work, we constructed a 3D carbon framework to confine Co0.85Se nanocrystals in three-dimensional space, both fulfilling the requirements of the material's size in the nano-scale and providing the largest contact area for releasing stress. With this optimization, nitrogen-doped carbon confined Co0.85Se nanocrystals (Co0.85Se@NC) reach an ultra-stable cycle life over 4000 times with a specific capacity of 190.9 mA h g-1 at 500 mA g-1 and provide 155.6 mA h g-1 at 10 A g-1 in the rate capability test. It also renders the areal capacity up to 1.03 mA h cm-2 at 500 mA g-1 in the high-mass loading test. Furthermore, based on the finite element analysis, the 3D confinement strategy has the lowest interfacial stress, ensuring Co0.85Se nanocrystals with high structural integrity. This strategy can relieve the stress issue in the conversion-type anode and demonstrate superior electrochemical performance even at high-loading mass electrodes.

Crystal Facet and Architecture Engineering of Metal Oxide Nanonetwork Anodes for High-Performance Potassium Ion Batteries and Hybrid Capacitors.

Metal oxides are considered as prospective dual-functional anode candidates for potassium ion batteries (PIBs) and hybrid capacitors (PIHCs) because of their abundance and high theoretic gravimetric capacity; however, due to the inherent insulating property of wide band gaps and deficient ion-transport kinetics, metal oxide anodes exhibit poor K+ electrochemical performance. In this work, we report crystal facet and architecture engineering of metal oxides to achieve significantly enhanced K+ storage performance. A bismuth antimonate (BiSbO4) nanonetwork with an architecture of perpendicularly crossed single crystal nanorods of majorly exposed (001) planes are synthesized via CTAB-mediated growth. (001) is found to be the preferential surface diffusion path for superior adsorption and K+ transport, and in addition, the interconnected nanorods gives rise to a robust matrix to enhance electrical conductivity and ion transport, as well as buffering dramatic volume change during insertion/extraction of K+. Thanks to the synergistic effect of facet and structural engineering of BiSbO4 electrodes, a stable dual conversion-alloying mechanism based on reversible six-electron transfer per formula unit of ternary metal oxides is realized, proceeding by reversible coexistence of potassium peroxide conversion reactions (KO2↔K2O) and BixSby alloying reactions (BiSb ↔ KBiSb ↔ K3BiSb). As a result, BiSbO4 nanonetwork anodes show outstanding potassium ion storage in terms of capacity, cycling life, and rate capability. Finally, the implementation of a BiSbO4 nanonetwork anode in the state-of-the-art full cell configuration of both PIBs and PIHCs shows satisfactory performance in a Ragone plot that sheds light on their practical applications for a wide range of K+-based energy storage devices. We believe this study will propose a promising avenue to design advanced hierarchical nanostructures of ternary or binary conversion-type materials for PIBs, PIHCs, or even for extensive energy storage.