Highly Efficient Aligned Ion‑Conducting Network and Interface Chemistries for Depolarized All‑Solid‑State Lithium Metal Batteries

Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.

3D printing critical materials for rechargeable batteries: from materials, design and optimization strategies to applications

Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nanoscale to macroscale.This technique offers excellent manufacturing flexibility,geometric designability,cost-effectiveness,and eco-friendliness.Recent studies have focused on the utilization of 3D-printed critical materials for EESDs,which have demonstrated remarkable electrochemical performances,including high energy densities and rate capabilities,attributed to improved ion/electron transport abilities and fast kinetics.However,there is a lack of comprehensive reviews summarizing and discussing the recent advancements in the structural design and application of 3D-printed critical materials for EESDs,particularly rechargeable batteries.In this review,we primarily concentrate on the current progress in 3D printing(3DP)critical materials for emerging batteries.We commence by outlining the key characteristics of major 3DP methods employed for fabricating EESDs,encompassing design principles,materials selection,and optimization strategies.Subsequently,we summarize the recent advancements in 3D-printed critical materials(anode,cathode,electrolyte,separator,and current collector)for secondary batteries,including conventional Li-ion(LIBs),Na-ion(SIBs),K-ion(KIBs)batteries,as well as Li/Na/K/Zn metal batteries,Zn-air batteries,and Ni–Fe batteries.Within these sections,we discuss the 3DP precursor,design principles of 3D structures,and working mechanisms of the electrodes.Finally,we address the major challenges and potential applications in the development of 3D-printed critical materials for rechargeable batteries.

Realizing Highly Reversible Zinc Anode via Controlled-current Pre-deposition

Aqueous zinc ion batteries have been considered as the prominent candidate in the next-generation batteries for its low cost,safety and high theoretical capacity.Nonetheless,formation of zinc dendrites and side reactions at the electrode/electrolyte interface during the zinc plating/stripping process affect the cycling reversibility of the zinc anode.Regulation of the zinc plating/stripping process and realizing a highly reversible zinc anode is a great challenge.Herein,we applied a simple and effective approach of controlled-current zinc pre-deposition at copper mesh.At the current density of 40 mA cm^(-2),where the electron/ion transfers are both continuous and balanced,the Zn@CM-40 electrode with the(002)crystal plane orientation and the compactly aligned platelet morphology was successfully obtained.Compared with the zinc foil,the Zn@CM-40 exhibits greatly enhanced reversibility in the repeated plating/stripping(850 h at 1 mA cm^(-2))for the symmetric battery test.A series of characterization techniques including electrochemical analyses,XRD,SEM and optical microscopy observation,were used to demonstrate the correlation between the structure of pre-deposited zinc layer and the cycling stability.The COSMOL Multiphysics modeling demonstrates a more uniform electric field distribution in the Zn@CM than the zinc foil due to the aligned platelet morphology.Furthermore,the significant improvement is also achieved in a Zn||MnO_(2)full battery with a high capacity-retention(87%vs 47.8%).This study demonstrates that controlled-current electrodeposition represents an important strategy to regulate the crystal plane orientation and the morphology of the pre-deposited zinc layer,hence leading to the highly reversible and dendrite-free zinc anode for high-performance zinc ion batteries.

Realizing high-voltage aqueous zinc-ion batteries with expanded electrolyte electrochemical stability window

Aqueous zinc-ion batteries(AZIBs) have aroused significant research interest around the world in the past decade. The use of low-cost aqueous electrolytes and a metallic Zn anode with a suitable redox potential and high energy density make AZIBs a potential alternative to commercial Li-ion batteries in the development of next-generation batteries. However, owing to the narrow electrochemical stability window(ESW) of aqueous electrolytes, the choice of cathode materials is limited, because of which AZIBs exhibit a relatively low operating voltage and energy density. Hence, expanding the ESW of aqueous electrolytes is important for the development of practical AZIBs. This paper systematically reviews the electrolyte engineering strategies being explored to broaden the ESW of AZIBs. An in-depth analysis of high-voltage AZIBs is also presented. We suggest that the realization of high-voltage AZIBs depends on the synergistic development of suitable electrolytes and cathode materials. In addition, the cost associated with their fabrication as well as the use of standardized electrochemical tests should be considered during the design of high-voltage AZIBs.

Achieving better aqueous rechargeable zinc ion batteries with heterostructure electrodes

Aqueous rechargeable zinc ion batteries(ARZIBs)have received unprecedented attention owing to the low cost and high-safety merits.However,their further development and application are hindered by the issues of electrodes such as cathode dissolution,zinc anode dendrite,passivation,as well as sluggish reaction kinetics.Designing heterostructure electrodes is a powerful method to improve the electrochemical performance of electrodes by grafting the advantages of functional materials onto the active materials.In this review,various modified heterostructure electrodes with optimized electrochemical performance and wider applications are introduced.Moreover,the synergistic effect between active materials and functional materials are also in-depth analyzed.The specific modification methods are divided into interphase modification(electrode-electrolyte interphase and electrode-current collector interphase)and structure optimization.Finally,the conclusion and future perspective on the optimization mechanism of functional materials,and the cost issue of practical heterostructure electrodes in ARZIBs are also proposed.It is expected that this review can promote the further development of ARZIBs towards practical utility.

Illumining phase transformation dynamics of vanadium oxide cathode by multimodal techniques under operando conditions

Subtle structural changes during electrochemical processes often relate to the degradation of electrode materials.Characterizing the minute-variations in complementary aspects such as crystal structure,chemical bonds,and electron/ion conductivity will give an in-depth understanding on the reaction mechanism of electrode materials,as well as revealing pathways for optimization.Here,vanadium pentoxide (V2O5),a typical cathode material suffering from severe capacity decay during cycling,is characterized by in-situ X-ray diffraction (XRD) and in-situ Raman spectroscopy combined with electrochemical tests.The phase transitions of V2O5 within the 0-1 LiN ratio are characterized in detail.The V--O and V-V distances became more extended and shrank compared to the original ones after charge/discharge process,respectively.Combined with electrochemical tests,these variations are vital to the crystal structure cracking,which is linked with capacity fading.This work demonstrates that chemical bond changes between the transition metal and oxygen upon cycling serve as the origin of the capacity fading.