RESUMO
Silicon (Si)-based anodes are currently considered a feasible solution to improve the energy density of lithium-ion batteries owing to their sufficient specific capacity and natural abundance. However, Si-based anodes exhibit low electric conductivities and large volume changes during cycling, which could easily trigger continuous breakdown/reparation of the as-formed solid-electrolyte-interphase (SEI) layer, seriously hampering their practical application in current battery technology. To control the chemoelectrochemical instability of the conventional SEI layer, we herein propose the introduction of elemental sulfur into nonaqueous electrolytes, aiming to build a sulfur-mediated gradient interphase (SMGI) layer on Si-based anodes. The SMGI layer is generated through the domino reactions (i.e., electrochemical cascade reactions) involving the electrochemical reductions of elemental sulfur followed by nucleophilic substitutions of fluoroethylene carbonate, which endows the corresponding SEI layer with strong elasticity and chemomechanical stability and enables rapid transportation of Li+ ions. Consequently, the prototype Si||LiNi0.8Co0.1Mn0.1O2 cells attain a high-energy density of 622.2 W h kg-1 and a capacity retention of 88.8% after 100 cycles. Unlike previous attempts based on sophisticated chemical modifications of electrolyte components, this study opens a new avenue in interphase design for long-lived and high-energy rechargeable batteries.
RESUMO
The particle morphology of LiNiO2 (LNO), the final product of Co-free high-Ni layered oxide cathode materials, must be engineered to prevent the degradation of electrochemical performance caused by the H2-H3 phase transition. Introducing a small amount of dopant oxides (Nb2O5 as an example) during the electrolysis synthesis of the Ni(OH)2 precursor facilitates the engineering of the primary particles of LNO, which is quick, simple, and inexpensive. In addition to the low concentration of Nb that entered the lattice structure, a combination of advanced characterizations indicates that the obtained LNO cathode material contains a high concentration of Nb in the primary particle boundaries in the form of lithium niobium oxide. This electrolysis method facilitated LNO (EMF-LNO) engineering successfully, reducing primary particle size and increasing particle packing density. Therefore, the EMF-LNO cathode material with engineered morphology exhibited increased mechanical strength and electrical contact, blocked electrolyte penetration during cycling, and reduced the H2-H3 phase transition effects.
RESUMO
Cobalt-free LiNiO2 cathode materials offer a higher energy density at a lower cost than high Co-containing cathode materials. However, Ni(OH)2 precursors for LiNiO2 cathodes are traditionally prepared by the coprecipitation method, which is expensive, complex, and time-consuming. Herein, we report a fast, facile, and inexpensive electrolysis process to prepare a Ni(OH)2 precursor, which was mixed with LiOH/LiNO3 salts to obtain a LiNiO2 cathode material. A combination of advanced characterization techniques revealed that the LiNiO2 cathode material prepared in this way exhibited an excellent layered structure with negligible Li/Ni site mixing and surface structural distortion. Electrochemical cycling of the LiNiO2 cathode material showed an initial discharge capacity of 235.2 mA h/g and a capacity retention of 80.2% after 100 cycles (at 1 C) between 2.75 and 4.3 V. The degradation of the cycling performance of the LiNiO2 cathode material was mainly attributed to the formation of a surface solid-electrolyte interface and a â¼5 nm rock salt-like structure, while the bulk structure of the cathode after cycling was generally stable.
