Deciphering Electrolyte Dominated Na+ Storage Mechanisms in Hard Carbon Anodes for Sodium-Ion Batteries.

Although hard carbon (HC) demonstrates superior initial Coulombic efficiency, cycling durability, and rate capability in ether-based electrolytes compared to ester-based electrolytes for sodium-ion batteries (SIBs), the underlying mechanisms responsible for these disparities remain largely unexplored. Herein, ex situ electron paramagnetic resonance (EPR) spectra and in situ Raman spectroscopy are combined to investigate the Na storage mechanism of HC under different electrolytes. Through deconvolving the EPR signals of Na in HC, quasi-metallic-Na is successfully differentiated from adsorbed-Na. By monitoring the evolution of different Na species during the charging/discharging process, it is found that the initial adsorbed-Na in HC with ether-based electrolytes can be effectively transformed into intercalated-Na in the plateau region. However, this transformation is obstructed in ester-based electrolytes, leading to the predominant storage of Na in HC as adsorbed-Na and pore-filled-Na. Furthermore, the intercalated-Na in HC within the ether-based electrolytes contributes to the formation of a uniform, dense, and stable solid-electrolyte interphase (SEI) film and eventually enhances the electrochemical performance of HC. This work successfully deciphers the electrolyte-dominated Na+ storage mechanisms in HC and provides fundamental insights into the industrialization of HC in SIBs.

Polyvinylpyrrolidone-Induced Uniform Surface-Conductive Polymer Coating Endows Ni-Rich LiNi0.8Co0.1Mn0.1O2 with Enhanced Cyclability for Lithium-Ion Batteries.

The Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode has attracted great interest owing to its low cost, high capacity, and energy density. Nevertheless, rapid capacity fading is a critical problem because of direct contact of NCM811 with electrolytes and hence restrains its wide applications. To prevent the direct contact, the surface inert layer coating becomes a feasible strategy to tackle this problem. However, to achieve a homogeneous surface coating is very challenging. Considering the bonding effect between NCM811, polyvinylpyrrolidone (PVP), and polyaniline (PANI), in this work, we use PVP as an inductive agent to controllably coat a uniform conductive PANI layer on NCM811 (NCM811@PANI-PVP). The coated PANI layer not only serves as a rapid channel for electron conduction, but also prohibits direct contact of the electrode with the electrolyte to effectively hinder side reaction. NCM811@PANI-PVP thus exhibits excellent cyclability (88.7% after 100 cycles at 200 mA g-1) and great rate performance (152 mA h g-1 at 1000 mA g-1). In situ X-ray diffraction and in situ Raman are performed to investigate the charge-discharge mechanism and the cyclability of NCM811@PANI-PVP upon electrochemical reaction. This surfactant-modulated surface uniform coating strategy offers a new modification approach to stabilize Ni-rich cathode materials for lithium-ion batteries.

Sub-20 nm Carbon Nanoparticles with Expanded Interlayer Spacing for High-Performance Potassium Storage.

Carbon materials are most promising candidates for potassium-ion battery (PIB) anodes because of their high electrical conductivities, rational potassium storage capabilities, and low costs. However, the large volume change during the K-ion insertion/extraction and the sluggish kinetics of K-ion diffusion inhibit the development of carbon-based materials for PIBs. Here, under the guidance of density functional theory, N/P-codoped ultrafine (≤20 nm) carbon nanoparticles (NP-CNPs) with an expanded interlayer distance, improved electrical conductivity, shortened diffusion distance of K ions, and promoted adsorption capability toward K ions are synthesized through a facile solvent-free method as a high-performance anode material for PIBs. The NP-CNPs show a high capacity of 270 mA h g-1 at 0.2 A g-1, a remarkable rate capability of 157 mA h g-1 at an extremely high rate of 5.0 A g-1, and an ultralong cycle life with a high capacity of 190 mA h g-1 and a retention of 86.4% at 1.0 A g-1 after 4000 cycles. The potassium storage mechanism and low volume expansion for NP-CNPs are revealed through cyclic voltammetry, in situ Raman, and ex situ XRD. This work paves a new way to design and fabricate carbon-based nanostructures with high reversible capacity, great rate capability, and stable long-term performance.