Experimentally validated design principles of heteroatom-doped-graphene-supported calcium single-atom materials for non-dissociative chemisorption solid-state hydrogen storage.

Non-dissociative chemisorption solid-state storage of hydrogen molecules in host materials is promising to achieve both high hydrogen capacity and uptake rate, but there is the lack of non-dissociative hydrogen storage theories that can guide the rational design of the materials. Herein, we establish generalized design principle to design such materials via the first-principles calculations, theoretical analysis and focused experimental verifications of a series of heteroatom-doped-graphene-supported Ca single-atom carbon nanomaterials as efficient non-dissociative solid-state hydrogen storage materials. An intrinsic descriptor has been proposed to correlate the inherent properties of dopants with the hydrogen storage capability of the carbon-based host materials. The generalized design principle and the intrinsic descriptor have the predictive ability to screen out the best dual-doped-graphene-supported Ca single-atom hydrogen storage materials. The dual-doped materials have much higher hydrogen storage capability than the sole-doped ones, and exceed the current best carbon-based hydrogen storage materials.

New Insights into the Effects of Zr Substitution and Carbon Additive on Li3-xEr1-xZrxCl6 Halide Solid Electrolytes.

Halide solid electrolytes have been considered as the most promising candidates for practical high-voltage all-solid-state lithium-ion batteries (ASSLIBs) due to their moderate ionic conductivity and good interfacial compatibility with oxide cathode materials. Aliovalent ion doping is an effective strategy to increase the ionic conductivity of halide electrolytes. However, the effects of ion doping on the electrochemical stability window of halide electrolytes and carbon additive on electrochemical performance are still unclear by far. Herein, a series of Zr-doped Li3-xEr1-xZrxCl6 halide solid electrolytes (SEs) are synthesized through a mechanochemical method and the effects of Zr substitution on the ionic conductivity and electrochemical stability window are systematically investigated. Zr doping can increase the ionic conductivity, whereas it narrows the electrochemical stability window of the Li3ErCl6 electrolyte simultaneously. The optimized Li2.6Er0.6Zr0.4Cl6 electrolyte exhibits both a high ionic conductivity of 1.13 mS cm-1 and a high oxidation voltage of 4.21 V. Furthermore, carbon additives are demonstrated to be beneficial for achieving high discharge capacity and better cycling stability and rate performance for halide-based ASSLIBs, which are completely different from the case of sulfide electrolytes. ASSLIBs with uncoated LiCoO2 cathode and carbon additives exhibit a high discharge capacity of 147.5 mAh g-1 and superior cycling stability with a capacity retention of 77% after 500 cycles. This work provides an in-depth understanding of the influence of ion doping and carbon additives on halide solid electrolytes and feasible strategies to realize high-energy-density ASSLIBs.

A Redox Couple Strategy Enables Long-Cycling Li- and Mn-Rich Layered Oxide Cathodes by Suppressing Oxygen Release.

Li- and Mn-rich layered oxides (LMROs) are considered the most promising cathode candidates for next-generation high-energy lithium-ion batteries. The poor cycling stability and fast voltage fading resulting from oxygen release during charging, however, severely hinders their practical application. Herein, a strategy of introducing an additional redox couple is proposed to eliminate the persistent problem of oxygen release. As a proof of concept, the cycling stability of Li1.2 Ni0.13 Co0.13 Mn0.54 O2 , which is a typical LMRO cathode, is substantially enhanced with the help of the S2- /SO3 2- redox couple, and the capacity shows no decay with a retention of 100% after 700 cycles at 1C, far superior to the bare counterpart (61.7%). The surface peroxide ions (O2 2- ) are readily chemically reduced back to immobile O2- by S2- during charging, accompanied by the formation of SO3 2- , which plays a critical role in stabilizing the oxygen lattice and eventually inhibiting the release of oxygen. More importantly, the S2- ions are regenerated during the following discharging process and participate in the chemical redox reaction again. The findings shed light on a potential direction to tackle the poor cycling stability of high-energy anion-redox cathode materials for rechargeable metal-ion batteries.

A Novel Tin-Bonded Silicon Anode for Lithium-Ion Batteries.

Poor cyclic stability and low rate performance due to dramatic volume change and low intrinsic electronic conductivity are the two key issues needing to be urgently solved in silicon (Si)-based anodes for lithium-ion batteries. Herein, a novel tin (Sn)-bonded Si anode is proposed for the first time. Sn, which has a high electronic conductivity, is used to bond the Si-anode material and copper (Cu) current collector together using a hot-pressed method with a temperature slightly above the melting point of Sn. The cycling performance of the electrode is studied using a galvanostatic method. Nanoindentation and peeling tests are conducted to measure the mechanical strength of the electrodes. Direct current polarization and galvanostatic intermittent titration techniques are applied to assess the conductivity of the composites. Electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy are conducted to evaluate the effect of the coating layer on the cycling ability of the composites. The Sn-bonded Si anodes show superior cycling stability and high rate performance with an improved initial Coulombic efficiency. Analyses reveal that the low-melting-point Sn helps to markedly improve the electronic conductivity of the electrodes and serves as a metallic binder as well to enhance the adhesive strength of the electrode. It is hopeful that this novel Sn-bonded Si anode provides a new insight for the development of advanced Si-based anodes for LIBs.

In Situ Encapsulation of the Nanoscale Er2O3 Phase To Drastically Suppress Voltage Fading and Capacity Degradation of a Li- and Mn-Rich Layered Oxide Cathode for Lithium Ion Batteries.

A novel strategy of in situ precipitation and encapsulation of the Er2O3 phase on the Li(Li0.2Ni0.13Co0.13Mn0.54)O2 (LNCMO) cathode material for lithium ion batteries is proposed for the first time. The Er2O3 phase is precipitated from the bulk of the LNCMO material and encapsulated onto its entire surface during the calcining process. Electrochemicial performance is investigated by a galvanostatic charge and discharge test. The structure and morphology are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy. The results show that an about 10 nm Er2O3 layer is successfully encapsulated onto the entire surface of the LNCMO matrix material. This unique nanoscale Er2O3 encapsulation can significantly prevent the LNCMO cathode material from being corroded by electrolytes and stabilize the crystal structure of the LNCMO cathode during cycling. Therefore, the prepared Er2O3-coated LNCMO composite exhibits excellent cycling performace and a high initial Coulombic efficiency.