Asymmetric Electrolytes Design for Aqueous Multivalent Metal Ion Batteries

With the rapid development of portable electronics and electric road vehicles,high-energy-density batteries have been becoming front-burner issues.Traditionally,homogeneous electrolyte cannot simultaneously meet diametrically opposed demands of high-potential cathode and low-potential anode,which are essential for high-voltage batteries.Meanwhile,homogeneous electrolyte is difficult to achieve bi-or multi-functions to meet different requirements of electrodes.In comparison,the asymmetric electrolyte with bi-or multi-layer disparate components can satisfy distinct requirements by playing different roles of each electrolyte layer and meanwhile compensates weakness of individual electrolyte.Consequently,the asymmetric electrolyte can not only suppress by-product sedimentation and continuous electrolyte decomposition at the anode while preserving active substances at the cathode for high-voltage batteries with long cyclic lifespan.In this review,we comprehensively divide asymmetric electrolytes into three categories:decoupled liquid-state electrolytes,bi-phase solid/liquid electrolytes and decoupled asymmetric solid-state electrolytes.The design principles,reaction mechanism and mutual compatibility are also studied,respectively.Finally,we provide a comprehensive vision for the simplification of structure to reduce costs and increase device energy density,and the optimization of solvation structure at anolyte/catholyte interface to realize fast ion transport kinetics.

Flexible aqueous Ca-ion full battery with super-flat discharge voltage plateau

Recently,multivalent metal-ion batteries have attracted considerable interests on the merits of their natural abundance and multielectron redox property.However,the development of Ca-ion battery is still in their preliminary stage because of the lack of suitable electrode material.The Ca-storage performance of the existing materials is still unsatisfactory with low capacity,poor cyclic stability,as well as sloping discharge profiles,which cannot provide stable energy output.In this work,transition metal oxide Sn-doped In2O3(ITO)has been explored as the aqueous Ca-ion battery anode,which could deliver a high discharge capacity of 71.2 mAh·g^(-1) with an ultra-flat discharge voltage plateau.The Ca storage mechanism was revealed to be reversible conversion reaction based on ex-situ X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),and transmission electron microscopy(TEM)characterizations.A flexible aqueous Ca-ion battery was subsequently assembled with zinc hexacyanoferrate(ZnHCF)cathode and ITO anode sandwiched by hydrogel electrolyte,which could deliver a high specific capacity of 75.3 mAh·g^(-1) at 0.4 A·g^(-1) with a flat output voltage plateau at around 0.8 V.The bendable and flexible Ca-ion battery with decent voltage output will pave the way for the energy storage devices towards practical applications in flexible and wearable electronics.