A Gradient Doping Strategy toward Superior Electrochemical Performance for Li-Rich Mn-Based Cathode Materials.

Lithium-rich layered oxides (LLOs) are concerned as promising cathode materials for next-generation lithium-ion batteries due to their high reversible capacities (larger than 250 mA h g-1 ). However, LLOs suffer from critical drawbacks, such as irreversible oxygen release, structural degradation, and poor reaction kinetics, which hinder their commercialization. Herein, the local electronic structure is tuned to improve the capacity energy density retention and rate performance of LLOs via gradient Ta5+ doping. As a result, the capacity retention elevates from 73% to above 93%, and the energy density rises from 65% to above 87% for LLO with modification at 1 C after 200 cycles. Besides, the discharge capacity for the Ta5+ doped LLO at 5 C is 155 mA h g-1 , while it is only 122 mA h g-1 for bare LLO. Theoretical calculations reveal that Ta5+ doping can effectively increase oxygen vacancy formation energy, thus guaranteeing the structure stability during the electrochemical process, and the density of states results indicate that the electronic conductivity of the LLOs can be boosted significantly at the same time. This strategy of gradient doping provides a new avenue to improve the electrochemical performance of the LLOs by modulating the local structure at the surface.

In Situ Growth of CoP Nanosheet Arrays on Carbon Cloth as Binder-Free Electrode for High-Performance Flexible Lithium-Ion Batteries.

Cobalt phosphide (CoP) is considered as one of the most promising candidates for anode in lithium-ion batteries (LIBs) owing to its low-cost, abundant availability, and high theoretical capacity. However, problems of low conductivity, heavy aggregation, and volume change of CoP, hinder its practical applicability. In this study, a binder-free electrode is successfully prepared by growing CoP nanosheets arrays directly on a carbon cloth (CC) via a facile one-step electrodeposition followed by an in situ phosphorization strategy. The CoP@CC anode exhibits good interfacial bonding between the CoP and CC, which can improve the conductivity of the integrated electrode. More importantly, the 3D network structure composed of CoP nanosheets and CC provides sufficient space to alleviate the volume expansion of CoP and shorten the electron/ion transport paths. Moreover, the support of CC effectively prevents the agglomeration of CoP. Based on these advantages, when CoP@CC is paired with the NCM523 cathode, the full cell delivers a high discharge capacity 919.6 mAh g-1 (2.1 mAh cm-2 ) after 200 cycles at 0.5 A g-1 . The feasibility and safety of producing pouch cells are also explored, which show good flexibility and safety despite rigorous strikes (mechanical damage and severe deformations), implying a great potential for practical applications.

ZnO quantum dot-modified rGO with enhanced electrochemical performance for lithium-sulfur batteries.

Lithium-sulfur batteries are considered the most promising next-generation energy storage devices. However, problems like sluggish reaction kinetics and severe shuttle effect need to be solved before the commercialization of Li-S batteries. Here, we successfully prepared ZnO quantum dot-modified reduced graphene oxide (rGO@ZnO QDs), and first introduced it into Li-S cathodes (rGO@ZnO QDs/S). Due to its merits of a catalysis effect and enhancing the reaction kinetics, low surface impedance, and efficient adsorption of polysulfide, rGO@ZnO QDs/S presented excellent rate capacity with clear discharge plateaus even at a high rate of 4C, and superb cycle performance. An initial discharge capacity of 998.8 mA h g-1 was delivered, of which 73.3% was retained after 400 cycles at a high rate of 1C. This work provides a new concept to introduce quantum dots into lithium-sulfur cathodes to realize better electrochemical performance.

Hierarchical zinc oxide/reduced graphene oxide composite: Preparation route, mechanism study and lithium ion storage.

A novel and simple approach to preparing hierarchical zinc oxide/reduced graphene oxide (ZnO/RGO@RGO) composite is demonstrated using few-layered graphene oxide (GO) and metal zinc as starting materials following combined processes, including in-situ metal zinc reduction and catalyzed GO deoxygenation. Metal zinc can directly reduce GO sheets in aqueous GO suspension at room temperature to obtain a porous composite precursor (ZnO/RGO) with ZnO nanoparticles anchored on the RGO sheets. Then another RGO protecting layer is directly coated on the ZnO/RGO precursor to obtain the hierarchical ZnO/RGO@RGO composite. In this step, the exposed ZnO nanoparticles on the surface of ZnO/RGO play the role of catalyst to accelerate the deoxygenation of GO from the extra added GO aqueous suspension under mild hydrothermal condition. The reaction mechanism of metal zinc with GO aqueous suspension has been explored and the catalyst role of ZnO has been verified in this work. The prepared ZnO/RGO@RGO composite exhibited both stable cycling performance and good rate capability as anode for lithium-ion batteries. The method to prepare ZnO/RGO composite is economic and eco-friendly, and the ZnO catalyzing GO reduction opens a new approach to prepare graphene derivates.

Carbon Wrapped Ni3S2 Nanocrystals Anchored on Graphene Sheets as Anode Materials for Lithium-Ion Battery and the Study on Their Capacity Evolution.

Ni3S2 nanocrystals wrapped by thin carbon layer and anchored on the sheets of reduced graphene oxide (Ni3S2@C/RGO) have been synthesized by a spray-coagulation assisted hydrothermal method and combined with a calcination process. Cellulose, dissolved in Thiourea/NaOH aqueous solution is chosen as carbon sources and mixed with graphene oxide via a spray-coagulation method using graphene suspension as coagulation bath. The resulted cellulose/graphene suspension is utilized as solvent for dissolving of Ni(NO3)2 and then used as raw materials for hydrothermal preparation of the Ni3S2@C/RGO composites. The structure of the composites has been investigated and their electrochemical properties are evaluated as anode material for lithium-ion batteries. The Ni3S2@C/RGO sample exhibits increasing reversible capacities upon cycles and shows a superior rate performance as well. Such kinds of promising performance have been ascribed to the wrapping effect of carbon layer which confines the dislocation of the polycrystals formed upon cycles and the enhanced conductivity as the integration of RGO conductive substrate. Discharge capacities up to 850 and 630 mAh·g-1 at current densities of 200 and 5000 mA·g-1, respectively, are obtained. The evolution of electrochemical performance of the composites with structure variation of the encapsulated Ni3S2 nanocrystals has been revealed by ex-situ TEM and XRD measurements.