Negatively Charged Holey Titania Nanosheets Added Electrolyte to Realize Dendrite-Free Lithium Metal Battery

Electrolyte modulation and electrode structure design are two common strategies to suppress dendrites growth on Li metal anode. In this work, a self-adaptive electrode construction method to suppress Li dendrites growth is reported, which merges the merits of electrolyte modulation and electrode structure design strategies. In detail, negatively charged titania nanosheets with densely packed nanopores on them are prepared. These holey nanosheets in the electrolyte move spontaneously onto the anode under electrical field, building a mesoporous structure on the electrode surface. The as-formed porous electrode has large surface area with good lithiophilicity, which can efficiently transfer lithium ion (Li⁺) inside the electrode, and induce the genuine lithium plating/stripping. Moreover, the negative charges and nanopores on the sheets can also regulate the lithium-ion flux to promote uniform deposition of Li metal. As a result, the symmetric and full cells using the holey titania nanosheets containing electrolyte, show much better performance than the ones using electrolyte without holey nanosheets inside. This work points out a new route for the practical applications of Li-metal batteries.     

Clay-Originated Two-Dimensional Holey Silica Separator for Dendrite-Free Lithium Metal Anode

Lithium metal anode is the ultimate choice to obtain next-generation high-energy-density lithium batteries, while the dendritic lithium growth owing to the unstable lithium anode/electrolyte interface largely limits its practical application. Separator is an important component in batteries and separator engineering is believed to be a tractable and effective way to address the above issue. Separators can play the role of ion redistributors to guide the transport of lithium ions and regulate the uniform electrodeposition of Li. The electrolyte wettability, thermal shrinkage resistance, and mechanical strength are of importance for separators. Here, clay-originated two-dimensional (2D) holey amorphous silica nanosheets (ASN) to develop a low-cost and eco-friendly inorganic separator is directly adopted. The ASN-based separator has higher porosity, better electrolyte wettability, much higher thermal resistance, larger lithium transference number, and ionic conductivity compared with commercial separator. The large amounts of holes and rich surface oxygen groups on the ASN guide the uniform distribution of lithium-ion flux. Consequently, the Li//Li cell with this separator shows stable lithium plating/stripping, and the corresponding Li//LiFePO₄, Li//LiCoO_2, and Li//NCM523 full cells also show high capacity, excellent rate performance, and outstanding cycling stability, which is much superior to that using the commercial separator.     

Generalized Synthesis of Metal Oxide Nanosheets and Their Application as Li‐Ion Battery Anodes

Metal oxide nanosheets have attracted great attention in various fields, such as energy storage, catalysis, and sensors. Current synthesis methods of metal oxide nanosheets are laborious and not scalable. Herein, a facile and scalable method for the synthesis of metal oxide nanosheets is presented, which requires neither hydro‐/solvothermal conditions nor postsynthesis template removal. The synthesis is versatile, as evidenced by the wide variety of metal oxide nanosheets derived. Nanosheet properties such as crystallinity, crystallite size, and carbon content can be controlled by tuning the synthesis conditions. The metal oxide nanosheets demonstrate promising performance as Li‐ion battery anodes.     

Stable Li Metal Anodes via Regulating Lithium Plating/Stripping in Vertically Aligned Microchannels

Li anodes have been rapidly developed in recent years owing to the rising demand for higher‐energy‐density batteries. However, the safety issues induced by dendrites hinder the practical applications of Li anodes. Here, Li metal anodes stabilized by regulating lithium plating/stripping in vertically aligned microchannels are reported. The current density distribution and morphology evolution of the Li deposits on porous Cu current collectors are systematically analyzed. Based on simulations in COMSOL Multiphysics, the tip effect leads to preferential deposition on the microchannel walls, thus taking full advantage of the lightening rod theory of classical electromagnetism for restraining growth of Li dendrites. The Li anode with a porous Cu current collector achieves an enhanced cycle stability and a higher average Coulombic efficiency of 98.5% within 200 cycles. In addition, the resultant LiFePO₄/Li full battery demonstrates excellent rate capability and stable cycling performance, thus demonstrating promise as a current collector for high‐energy‐density, safe rechargeable Li batteries.     

Temperature-Dependent Chemical and Physical Microstructure of Li Metal Anodes Revealed through Synchrotron-Based Imaging Techniques

The Li metal anode has been long sought-after for application in Li metal batteries due to its high specific capacity (3860 mAh g⁻¹) and low electrochemical potential (−3.04 V vs the standard hydrogen electrode). Nevertheless, the behavior of Li metal in different environments has been scarcely reported. Herein, the temperature-dependent behavior of Li metal anodes in carbonate electrolyte from the micro- to macroscales are explored with advanced synchrotron-based characterization techniques such as X-ray computed tomography and energy-dependent X-ray fluorescence mapping. The importance of testing methodology is exemplified, and the electrochemical behavior and failure modes of Li anodes cycled at different temperatures are discussed. Moreover, the origin of cycling performance at different temperatures is identified through analysis of Coulombic efficiencies, surface morphology, and the chemical composition of the solid electrolyte interphase in quasi-3D space with energy-dependent X-ray fluorescence mappings coupled with micro-X-ray absorption near edge structure. This work provides new characterization methods for Li metal anodes and serves as an important basis toward the understanding of their electrochemical behavior in carbonate electrolytes at different temperatures.     

Ultrathin Lithiophilic 3D Arrayed Skeleton Enabling Spatial-Selection Deposition for Dendrite-Free Lithium Anodes

Lithium metal batteries are promising to become a new generation of energy storage batteries. However, the growth of Li dendrites and the volume expansion of the anode are serious constraints to their commercial implementation. Herein, a controllable strategy is proposed to construct an ultrathin 3D hierarchical host of honeycomb copper micromesh loaded with lithiophilic copper oxide nanowires (CMMC). The uniquely designed 3D hierarchical arrayed skeletons demonstrate a surface-preferred and spatial-selective effect to homogenize local current density and relieve the volume expansion, effectively suppressing the dendrite growth. Employing the constructed CMMC current collector in a half-cell, >400 cycles with 99% coulombic efficiency at 0.5 mA cm⁻² is performed. The symmetric battery cycles stably for >2000 h, and the full battery delivers a capacity of 166.6 mAh g⁻¹. This facile and controllable approach provides an effective strategy for constructing high-performance lithium metal batteries.     

Coordination Polymer to Atomically Thin,Holey, Metal‐Oxide Nanosheets for Tuning Band Alignment

Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal‐based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two‐unit cells. The process involves rapid exfoliation of bulk‐layered, MCPs (Ce‐, Ti‐, Zr‐based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high‐yield, room‐temperature, and template‐free approach to synthesize ultrathin holey nanosheets with high‐level functionalities.     

Bulk Nanostructured Materials Design for Fracture‐Resistant Lithium Metal Anodes

Li metal is an ideal anode for next‐generation batteries because of its high theoretical capacity and low potential. However, the unevenly distributed stress in Li metal anodes (LMAs) induced by volume fluctuation may cause the electrode to fracture easily, especially during high‐rate plating/stripping processes. Here fracture‐resistant LMAs using the concept of bulk nanostructured materials are designed via a metallurgical process. In bulk nanostructured Li (BNL), ionic conducting phases exist at grain boundaries, which promote Li⁺ transport. The refined Li grain size and precipitation hardening in BNL enhances the mechanical strength and fatigue endurance, alleviating the unevenly distributed stress and preventing electrode pulverization. Density functional theory is used to investigate the binding energy between Li and various kinds of oxides and SiO₂ is found to be optimal additive among screened oxides. BNL has 91% of the theoretical capacity of Li metal. In full cells with BNL anode, LiFePO₄ could deliver capacity of 90 mAh g^?1 at 10C, an order of magnitude higher than that in full cells with Li foil anode. This strategy is expected to pave the way for fracture‐resistant LMAs in high‐rate cycling with maximum capacity.     

Functional Separator Enabled by Covalent Organic Frameworks for High-Performance Li Metal Batteries

Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO₃H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800 h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g⁻¹ even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.     

In Situ Solid Electrolyte Interphase from Spray Quenching on Molten Li: A New Way to Construct High‐Performance Lithium‐Metal Anodes

Uncontrollable growth of Li dendrites and low utilization of active Li severely hinder its practical application. Construction of an artificial solid electrolyte interphase (SEI) on Li is demonstrated as one of the most effective ways to circumvent the above problems. Herein, a novel spray quenching method is developed in situ to fabricate an organic–inorganic composite SEI on Li metal. By spray quenching molten Li in a modified ether‐based solution, a homogeneous and dense SEI consisting of organic matrix embedded with inorganic LiF and Li₃N nanocrystallines (denoted as OIFN) is constructed on Li metal. Arising from high ionic conductivity and strong mechanical stability, the OIFN can not only effectively minimize the corrosion reaction of Li, but also greatly suppresses the dendrite growth. Accordingly, the OIFN‐Li anode presents prominent electrochemical performance with an enhanced Coulombic efficiency of 98.15% for 200 cycles and a small hysteresis of <450 mV even at ultrahigh current density up to 10 mA cm^?2. More importantly, during the full cell test with limited Li source, a high utilization of Li up to 40.5% is achieved for the OIFN‐Li anode. The work provides a brand‐new route to fabricate advanced SEI on alkali metal for high‐performance alkali‐metal batteries.     

Bending‐Tolerant Anodes for Lithium‐Metal Batteries

Bendable energy‐storage systems with high energy density are demanded for conformal electronics. Lithium‐metal batteries including lithium–sulfur and lithium–oxygen cells have much higher theoretical energy density than lithium‐ion batteries. Reckoned as the ideal anode, however, Li has many challenges when directly used, especially its tendency to form dendrite. Under bending conditions, the Li‐dendrite growth can be further aggravated due to bending‐induced local plastic deformation and Li‐filaments pulverization. Here, the Li‐metal anodes are made bending tolerant by integrating Li into bendable scaffolds such as reduced graphene oxide (r‐GO) films. In the composites, the bending stress is largely dissipated by the scaffolds. The scaffolds have increased available surface for homogeneous Li plating and minimize volume fluctuation of Li electrodes during cycling. Significantly improved cycling performance under bending conditions is achieved. With the bending‐tolerant r‐GO/Li‐metal anode, bendable lithium–sulfur and lithium–oxygen batteries with long cycling stability are realized. A bendable integrated solar cell–battery system charged by light with stable output and a series connected bendable battery pack with higher voltage is also demonstrated. It is anticipated that this bending‐tolerant anode can be combined with further electrolytes and cathodes to develop new bendable energy systems.     

Lithiophilic 3D Nanoporous Nitrogen‐Doped Graphene for Dendrite‐Free and Ultrahigh‐Rate Lithium‐Metal Anodes

The key bottlenecks hindering the practical implementations of lithium‐metal anodes in high‐energy‐density rechargeable batteries are the uncontrolled dendrite growth and infinite volume changes during charging and discharging, which lead to short lifespan and catastrophic safety hazards. In principle, these problems can be mitigated or even solved by loading lithium into a high‐surface‐area, conductive, and lithiophilic porous scaffold. However, a suitable material that can synchronously host a large loading amount of lithium and endure a large current density has not been achieved. Here, a lithiophilic 3D nanoporous nitrogen‐doped graphene as the sought‐after scaffold material for lithium anodes is reported. The high surface area, large porosity, and high conductivity of the nanoporous graphene concede not only dendrite‐free stripping/plating but also abundant open space accommodating volume fluctuations of lithium. This ingenious scaffold endows the lithium composite anode with a long‐term cycling stability and ultrahigh rate capability, significantly improving the charge storage performance of high‐energy‐density rechargeable lithium batteries.     

Hierarchically Nanoporous 3D Assembly Composed of Functionalized Onion‐Like Graphitic Carbon Nanospheres for Anode‐Minimized Li Metal Batteries

Despite the recent attention for Li metal anode (LMA) with high theoretical specific capacity of ≈ 3860 mA h g^?1, it suffers from not enough practical energy densities and safety concerns originating from the excessive metal load, which is essential to compensate for the loss of Li sources resulting from their poor coulombic efficiencies (CEs). Therefore, the development of high‐performance LMA is needed to realize anode‐minimized Li metal batteries (LMBs). In this study, high‐performance LMAs are produced by introducing a hierarchically nanoporous assembly (HNA) composed of functionalized onion‐like graphitic carbon building blocks, several nanometers in diameter, as a catalytic scaffold for Li‐metal storage. The HNA‐based electrodes lead to a high Li ion concentration in the nanoporous structure, showing a high CE of ≈ 99.1%, high rate capability of 12 mA cm^?2, and a stable cycling behavior of more than 750 cycles. In addition, anode‐minimized LMBs are achieved using a HNA that has limited Li content ( ≈ 0.13 mg cm^?2), corresponding to 6.5% of the cathode material (commercial NCM622 ( ≈ 2 mg cm^?2)). The LMBs demonstrate a feasible electrochemical performance with high energy and power densities of ≈ 510 Wh kg_electrode^?1 and ≈ 2760 W kg_electrode^?1, respectively, for more than 100 cycles.