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.

Multilevel carbon architecture of subnanoscopic silicon for fast‐charging high‐energy‐density lithium‐ion batteries

Silicon(Si)is widely used as a lithium‐ion‐battery anode owing to its high capacity and abundant crustal reserves.However,large volume change upon cycling and poor conductivity of Si cause rapid capacity decay and poor fast‐charging capability limiting its commercial applications.Here,we propose a multilevel carbon architecture with vertical graphene sheets(VGSs)grown on surfaces of subnanoscopically and homogeneously dispersed Si–C composite nanospheres,which are subsequently embedded into a carbon matrix(C/VGSs@Si–C).Subnanoscopic C in the Si–C nanospheres,VGSs,and carbon matrix form a three‐dimensional conductive and robust network,which significantly improves the conductivity and suppresses the volume expansion of Si,thereby boosting charge transport and improving electrode stability.The VGSs with vast exposed edges considerably increase the contact area with the carbon matrix and supply directional transport channels through the entire material,which boosts charge transport.The carbon matrix encapsulates VGSs@Si–C to decrease the specific surface area and increase tap density,thus yielding high first Coulombic efficiency and electrode compaction density.Consequently,C/VGSs@Si–C delivers excellent Li‐ion storage performances under industrial electrode conditions.In particular,the full cells show high energy densities of 603.5 Wh kg^(−1)and 1685.5 Wh L^(−1)at 0.1 C and maintain 80.7%of the energy density at 3 C.

Macroporous Directed and Interconnected Carbon Architectures Endow Amorphous Silicon Nanodots as Low‑Strain and Fast‑Charging Anode for Lithium‑Ion Batteries

Fabricating low-strain and fast-charging silicon-carbon composite anodes is highly desired but remains a huge challenge for lithium-ion batteries.Herein,we report a unique silicon-carbon composite fabricated by uniformly dis-persing amorphous Si nanodots(SiNDs)in carbon nanospheres(SiNDs/C)that are welded on the wall of the macroporous carbon framework(MPCF)by vertical graphene(VG),labeled as MPCF@VG@SiNDs/C.The high dispersity and amor-phous features of ultrasmall SiNDs(~0.7 nm),the flexible and directed electron/Li+transport channels of VG,and the MPCF impart the MPCF@VG@SiNDs/C more lithium storage sites,rapid Li+transport path,and unique low-strain property during Li+storage.Consequently,the MPCF@VG@SiNDs/C exhibits high cycle stability(1301.4 mAh g^(-1) at 1 A g^(-1) after 1000 cycles without apparent decay)and high rate capacity(910.3 mAh g^(-1),20 A g^(-1))in half cells based on industrial electrode standards.The assembled pouch full cell delivers a high energy density(1694.0 Wh L^(-1);602.8 Wh kg^(-1))and an excellent fast-charging capability(498.5 Wh kg^(-1),charging for 16.8 min at 3 C).This study opens new possibilities for preparing advanced silicon-carbon com-posite anodes for practical applications.

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.

Monolayer MoS_(2)Fabricated by In Situ Construction of Interlayer Electrostatic Repulsion Enables Ultrafast Ion Transport in Lithium-Ion Batteries

High theoretical capacity and unique layered structures make MoS_(2)a promising lithium-ion battery anode material.However,the anisotropic ion transport in layered structures and the poor intrinsic conductivity of MoS_(2)lead to unacceptable ion transport capability.Here,we propose in-situ construction of interlayer electrostatic repulsion caused by Co^(2+)substituting Mo^(4+)between MoS_(2)layers,which can break the limitation of interlayer van der Waals forces to fabricate monolayer MoS_(2),thus establishing isotropic ion transport paths.Simultaneously,the doped Co atoms change the electronic structure of monolayer MoS_(2),thus improving its intrinsic conductivity.Importantly,the doped Co atoms can be converted into Co nanoparticles to create a space charge region to accelerate ion transport.Hence,the Co-doped monolayer MoS_(2)shows ultrafast lithium ion transport capability in half/full cells.This work presents a novel route for the preparation of monolayer MoS_(2)and demonstrates its potential for application in fast-charging lithium-ion batteries.