Reviving Multivalent-Metal Anodes in Simple Salt Electrolytes via Component Modifier Design.

Using combinatory electrolyte blends represents an imperative avenue to achieve good magnesium (Mg)-metal anode compatibility and commercial feasibility in fields of promising rechargeable Mg batteries. However, fundamental challenges of how to manipulate component modifier reactivity on molecule level still remain to be solved. Here, molecular structure design concepts towards seeking bromophenyl complex-based component modifiers has been proposed according to implications of electron-donating and/or electron-withdrawing substituents on Br-C bond dissociation reactivity. Exceptional Mg electro-plating/stripping properties (a stable cycle life of 250 days in Mg//Cu asymmetric cells) have been firstly achieved in a simple salt electrolyte with 1-(3-bromophenyl)-N,N-dimethylmethanamine (BPDMA) as optimal component modifier. Comprehensive analyses disclose the unique electrochemically-active Br-containing ion-pairs formation, such as [(Mg2+)2(TFSI-)Br-]2+ and [(Mg2+)2(TFSI-)(Br-)(G2)2]2+, which results in the much thinner Br- containing and organic-inorganic mixed interphases on Mg-metal anodes. Furthermore, conventional MgSO4-based electrolytes and even calcium (Ca)-ion electrolytes can also be revived by similar strategy, demonstrating its generality and superiority.

Lithium Hydride in the Solid Electrolyte Interphase of Lithium-Ion Batteries as a Pulverization Accelerator of Silicon.

As a highly promising next-generation high-specific capacity anode, the industrial-scale utilization of micron silicon has been hindered by the issue of pulverization during cycling. Although numerous studies have demonstrated the effectiveness of regulating the inorganic components of the solid electrolyte interphase (SEI) in improving pulverization, the evolution of most key inorganic components in the SEI and their correlation with silicon failure mechanisms remain ambiguous. This study provides a clear and direct correlation between the lithium hydride (LiH) in the SEI and the degree of micron silicon pulverization in the battery system. The reverse lithiation behavior of LiH on micron silicon during de-lithiation exacerbates the localized stress in silicon particles and contributes to particle pulverization. This work successfully proposes a novel approach to decouple the SEI from electrochemical performance, which can be significant to decipher the evolution of critical SEI components at varied battery anode interfaces and analyze their corresponding failure mechanisms.

Deciphering the Lithium-Ion Conduction Mechanism of LiH in Solid-Electrolyte Interphase.

Lithium hydride (LiH) has been widely recognized as the critical component of the solid-electrolyte interphase (SEI) in Li batteries. Although the formation mechanism and structural model of LiH in SEI have been extensively reported, the role in electro-performance of LiH in SEI is still ambiguous and has proven challenging to explored due to the complicated structure SEI and the lack of advanced in situ experimental technology. In this study, the isotopic exchange experiments combined with isotopic tracer experiments is applied to solidly illustrate the superior conductivity and Li+ conduction behavior of the LiH in natural SEI. Importantly, in situ transmission electron microscopy analysis is utilized to visualize the self-electrochemical decomposition of LiH, which is significantly distinctive from LiF and Li2O. The critical experimental evidence discovered by the work demonstrates ion transport behaviors of key components in the SEI, which is imperative for designing novel SEI and augurs a new area in optimizing the performance of lithium batteries.

Fusion Bonding Technique for Solvent-Free Fabrication of All-Solid-State Battery with Ultrathin Sulfide Electrolyte.

For preparing next-generation sulfide all-solid-state batteries (ASSBs), the solvent-free manufacturing process has huge potential for the advantages of economic, thick electrode, and avoidance of organic solvents. However, the dominating solvent-free process is based on the fibrillation of polytetrafluoroethylene, suffering from poor mechanical property and electrochemical instability. Herein, a continuously solvent-free paradigm of fusion bonding technique is developed. A percolation network of thermoplastic polyamide (TPA) binder with low viscosity in viscous state is constructed with Li6PS5Cl (LPSC) by thermocompression (≤5 MPa), facilitating the formation of ultrathin LPSC film (≤25 µm). This composite sulfide film (CSF) exhibits excellent mechanical properties, ionic conductivity (2.1 mS cm-1), and unique stress-dissipation to promote interface stabilization. Thick LiNi0.83Co0.11Mn0.06O2 cathode can be prepared by this solvent-free method and tightly adhered to CSF by interfacial fusion of TPA for integrated battery. This integrated ASSB shows high-energy-density feasibility (>2.5 mAh cm-2 after 1400 cycles of 9200 h and run for more than 10 000 h), and energy density of 390 Wh kg-1 and 1020 Wh L-1. More specially, high-voltage bipolar cell (≥8.5 V) and bulk-type pouch cell (326 Wh kg-1) are facilely assembled with good cycling performance. This work inspires commercialization of ASSBs by a solvent-free method and provides beneficial guiding for stable batteries.

Understanding the Cathode-Electrolyte Interfacial Chemistry in Rechargeable Magnesium Batteries.

Rechargeable magnesium batteries (RMBs) have garnered significant attention due to their potential to provide high energy density, utilize earth-abundant raw materials, and employ metal anode safely. Currently, the lack of applicable cathode materials has become one of the bottleneck issues for fully exploiting the technological advantages of RMBs. Recent studies on Mg cathodes reveal divergent storage performance depending on the electrolyte formulation, posing interfacial issues as a previously overlooked challenge. This minireview begins with an introduction of representative cathode-electrolyte interfacial phenomena in RMBs, elaborating on the unique solvation behavior of Mg2+, which lays the foundation for interfacial chemistries. It is followed by presenting recently developed strategies targeting the promotion of Mg2+ desolvation in the electrolyte and alternative cointercalation approaches to circumvent the desolvation step. In addition, efforts to enhance the cathode-electrolyte compatibility via electrolyte development and interfacial engineering are highlighted. Based on the abovementioned discussions, this minireview finally puts forward perspectives and challenges on the establishment of a stable interface and fast interfacial chemistry for RMBs.

Interphase Regulation by Multifunctional Additive Empowering High Energy Lithium-Ion Batteries with Enhanced Cycle Life and Thermal Safety.

High energy density lithium-ion batteries (LIBs) adopting high-nickel layered oxide cathodes and silicon-based composite anodes always suffer from unsatisfied cycle life and poor safety performance, especially at elevated temperatures. Electrode /electrolyte interphase regulation by functional additives is one of the most economic and efficacious strategies to overcome this shortcoming. Herein, cyano-groups (-CN) are introduced into lithium fluorinated phosphate to synthesize a novel multifunctional additive of lithium tetrafluoro (1,2-dihydroxyethane-1,1,2,2-tetracarbonitrile) phosphate (LiTFTCP), which endows high nickel LiNi0.8 Co0.1 Mn0.1 O2 /SiOx -graphite composite full cell with an ultrahigh cycle life and superior safety characteristics, by adding only 0.5 wt % LiTFTCP into a LiPF6 -carbonate baseline electrolyte. It is revealed that LiTFTCP additive effectively suppresses the HF generation and facilitates the formation of a robust and heat-resistant cyano-enriched CEI layer as well as a stable LiF-enriched SEI layer. The favorable SEI/CEI layers greatly lessen the electrode degradation, electrolyte consumption, thermal-induced gassing and total heat-releasing. This work illuminates the importance of additive molecular engineering and interphase regulation in simultaneously promoting the cycling and thermal safety of LIBs with high-nickel NCMxyz cathode and silicon-based composite anode.

A Perspective on Uniform Plating Behavior of Mg Metal Anode: Diffusion Limited Theory versus Nucleation Theory.

Utilizing metal anode is the most attractive way to meet the urgent demand for rechargeable batteries with high energy density. Unfortunately, the formation of dendrites, which is caused by uneven plating behavior, always threaten the safety of the batteries. To explore the origin of different plating behavior and predict the plating morphology of anode under a variety of operating conditions, multifarious models have been developed. However, abuse of models has led to conflictive views. In this perspective, to clarify the controversial reports on magnesium (Mg) metal plating behavior, the previously proposed models are elaborated that govern the plating process. Through linking various models and clarifying their boundary conditions, a scheme is drawn to illustrate the strategy for achieving the most dense and uniform plating morphology, which also explains the seemingly contradictory of diffusion limited theory and nucleation theory on uniform plating. This perspective will undoubtedly enhance the understanding on the metal anode plating process and provide meaningful guidance for the development of metal anode batteries.

Self-Standing Single-Ion Borate Salt-Based Polymer Electrolyte for Lithium Metal Batteries.

Polymer electrolytes (PEs) with excellent flexibility and superior compatibility toward lithium (Li) metal anodes have been deemed as one of the most promising alternatives to liquid electrolytes. However, conventional lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based dual-ion PEs suffer from a low Li ion transference number and notorious Li dendrite growth. Here, a single-ion conducting polyborate salt without any fluorinated groups, polymeric lithium dihydroxyterephthalic acid borate (PLDPB), is presented for addressing the issues of Li metal batteries. Owing to a nearly immovable bulky anion and the presence of a rigid benzene structure, the PLDPB@poly(ethylene oxide) (PEO) PE exhibits an ultrahigh Li ion transference number (0.94) and excellent mechanical strength, which could significantly restrict the growth of Li dendrites. Postmortem analysis reveals that a fluorine-free solid electrolyte interphase (SEI) enriched with B-O and benzene-containing species is formed on the surface of the Li metal anode, thereby facilitating elimination of excessive parasitic reactions and simultaneously suppressing the formation of Li dendrites. Consequently, the LiFePO4/Li cells with PLDPB@PEO PEs show an improved long-term cycling performance and high capacity retention (90.0%) and Coulombic efficiency (99.9%) after 500 cycles. This work may inspire new ideas to boost the development of single-ion conducting salts for dendrite-free Li metal batteries.

Transforming a Primary Li-SOCl2 Battery into a High-Power Rechargeable System via Molecular Catalysis.

Li-SOCl2 batteries possess ultrahigh energy densities and superior safety features at a wide range of operating temperatures. However, the Li-SOCl2 battery system suffers from poor reversibility due to the sluggish kinetics of SOCl2 reduction during discharging and the oxidation of the insulating discharge products during charging. To achieve a high-power rechargeable Li-SOCl2 battery, herein we introduce the molecular catalyst I2 into the electrolyte to tailor the charging and discharging reaction pathways. The as-assembled rechargeable cell exhibits superior power density, sustaining an ultrahigh current density of 100 mA cm-2 during discharging and delivering a reversible capacity of 1 mAh cm-2 for 200 cycles at a current density of 2 mA cm-2 and 6 mAh cm-2 for 50 cycles at a current density of 5 mA cm-2. Our results reveal the molecular catalyst-mediated reaction mechanisms that fundamentally alter the rate-determining steps of discharging and charging in Li-SOCl2 batteries and highlight the viability of transforming a primary high-energy battery into a high-power rechargeable system, which has great potential to meet the ever-increasing demand of energy-storage systems.

Interelectrode Talk in Solid-State Lithium-Metal Batteries.

Solid-state lithium-metal batteries have been identified as a strategic research direction for the electric vehicle industry because of their promising high energy density and potential characteristic safety. However, the intrinsic mechanical properties of solid materials cause inevitable electro-chemo-mechanical failure of electrodes and electrolytes during charging and discharging; these failure mechanisms include lithium penetration and formation of cracks and voids, which pose a serious challenge for the long cycle life of solid-state lithium-metal batteries. Here, a short overview of the recent advances with a view to understand this challenge is provided. Furthermore, new insights into the cross-talk behavior between the cathode and lithium-metal anode are provided based on the non-uniform Li+ flux inducing interactional electro-chemo-mechanical failure. Furthermore, guidelines for designing stable solid-state lithium-metal batteries and research directions to figure out the interelectrode-talk-related electro-chemo-mechanical failure mechanism are presented, which can be significant for accelerating the development of solid-state lithium batteries.

A Spidroin-Inspired Hierarchical-Structure Binder Achieves Highly Integrated Silicon-Based Electrodes.

As a promising component for next-generation high-energy lithium-ion batteries, silicon-based electrodes have attracted increasing attention by virtue of their ultrahigh theoretical specific capacities. Nevertheless, fast capacity fading posed by tremendous silicon-based electrode volume changes during cycling remains a huge challenge before large-scale applications. In this work, an aqueous-oil binary solution based blend (AOB) binder characterized by a spidroin-like hierarchical structure for tolerating the huge volume changes of silicon-based electrodes is developed. In the AOB binder, the polymer, containing hydrophobic tetrazole groups, denoted as PPB, and the water-soluble amorphous poly(acrylic acid), mimick the ß-sheet and α-helix structure of spidroin, respectively. Benefitting from such biomimetic design, the AOB binder enables both high tensile strength and elasticity, and strong electrode adhesion, therefore apparently stabilizing the silicon-based electrode structure and rendering prolonged electrode cycle life. Such a strategy endows 3.3 Ah soft package cells assembled with Si/C composite anode and NCM811 cathode with a discharge specific capacity of 2.92 Ah after 700 cycles. This work marks a milestone in developing state-of-the-art silicon-based electrodes toward high-energy-density lithium-battery applications.

Revealing Capacity Degradation of Ge Anodes in Lithium-Ion Batteries Triggered by Interfacial LiH.

The Germanium (Ge), as a fast-charging and high specific capacity (1568 mAh g-1 ) alloy anode, is greatly hampered in practical application by poor cyclability. To date, the understanding of cycling performance degradation remains elusive. This study illustrates that, contrary to conventional beliefs, most of the Ge material in failed anodes still retains good integrity and does not undergo severe pulverization. It is revealed that capacity degradation is clearly correlated to the interfacial evolution of lithium hydride (LiH). Tetralithium germanium hydride (Li4 Ge2 H), as a new species derived from LiH, is identified as the culprit of Ge anode degradation, which is the dominant crystalized component in an ever-growing and ever-insulating interphase. The significantly increased thickness of the solid electrolyte interface (SEI) is accompanied by the accumulation of insulating Li4 Ge2 H upon cycling, which severely retards the charge transport process and ultimately triggers the anode failure. We believe that the comprehensive understanding of the failure mechanism presented in this study is of great significance to promoting the design and development of alloy anode for the next generation of lithium-ion batteries.

A Novel Potassium Salt Regulated Solvation Chemistry Enabling Excellent Li-Anode Protection in Carbonate Electrolytes.

In lithium-metal batteries (LMBs), the compatibility of Li anode and conventional lithium hexafluorophosphate-(LiPF6 ) carbonate electrolyte is poor owing to the severe parasitic reactions. Herein, to resolve this issue, a delicately designed additive of potassium perfluoropinacolatoborate (KFPB) is unprecedentedly synthesized. On the one hand, KFPB additive can regulate the solvation structure of the carbonate electrolyte, promoting the formation of Li+ FPB- and K+ PF6 - ion pairs with lower lowest unoccupied molecular orbital (LUMO) energy levels. On the other hand, FPB- anion possesses strong adsorption ability on Li anode. Thus, anions can preferentially adsorb and decompose on the Li-anode surface to form a conductive and robust solid-electrolyte interphase (SEI) layer. Only with a trace amount of KFPB additive (0.03 m) in the carbonate electrolyte, Li dendrites' growth can be totally suppressed, and Li||Cu and Li||Li half cells exhibit excellent Li-plating/stripping stability upon cycling. Encouragingly, KFPB-assisted carbonate electrolyte enables high areal capacity LiCoO2 ||Li, LiNi0.8 Co0.1 Mn0.1 O2 (NCM811)||Li, and LiNi0.8 Co0.05 Al0.15 O2 (NCA)||Li LMBs with superior cycling stability, showing its excellent universality. This work reveals the importance of designing novel additives to regulate the solvation structure of carbonate electrolytes in improving its interface compatibility with the Li anode.

Unveiling the dynamic Li+-solvent interaction evolution in lithium metal batteries.

The interfacial chemistry during plating/stripping between electrolytes with different concentrations and Li metal is firstly in situ visualized by in situ Fourier transform infrared spectroscopy (FTIR) and simulated by density functional theory (DFT) calculations. It is verified that different Li+-solvent interaction evolutions at interfaces during the Li+ stripping and plating processes result in different interfacial stability. This work uncovers the critical role of Li+-solvent interaction evolution for the stability of the interface between the solvent and Li metal anode.

Robust Transport: An Artificial Solid Electrolyte Interphase Design for Anode-Free Lithium-Metal Batteries.

One of the most challenging issues in the practical implementation of high-energy-density anode-free lithium-metal batteries (AFLMBs) is the sharp capacity attenuation caused by the mechanical degradation of the solid electrolyte interphase (SEI). However, developing an artificial SEI to address this issue remains a challenge due to the trade-off between ionic conductivity and mechanical robustness for general ionic conducting films. In this study, a tenacious composite artificial SEI with integrated heterostructure of lithium fluoride (LiF) and lithium phosphorus oxynitride (LiPON) is prepared using a co-sputtering approach to achieve both high ionic conductivity and fracture toughness. The embedded LiF domain has an extremely high Young's modulus and surface energy compared with those of bulk LiPON film, enabling a significant increase in fracture toughness by an order of magnitude. Most importantly, the interface between LiPON and LiF in the integrated structure generates additional fast Li+ -transport pathways, providing the artificial SEI with a conductivity higher than 10-6 S cm-1 . Consequently, the artificial SEI implementation significantly increases the cycling lifetime of the corresponding AFLMBs by >250%. This study highlights the importance of fracture toughness for the structural integrity of batteries and provides suggestions for designing viable SEI materials for high-performance AFLMBs.

Epitaxial Electrocrystallization of Magnesium via Synergy of Magnesiophilic Interface, Lattice Matching, and Electrostatic Confinement.

Rechargeable magnesium batteries are particularly advantageous for renewable energy storage systems. However, the inhomogeneous Mg electrodeposits greatly shorten their cycle life under practical conditions. Herein, the epitaxial electrocrystallization of Mg on a three-dimensional magnesiophilic host is implemented via the synergy of a magnesiophilic interface, lattice matching, and electrostatic confinement effects. The vertically aligned nickel hydroxide nanosheet arrays grown on carbon cloth (abbreviated as "Ni(OH)2@CC") have been delicately designed, which satisfy the essential prerequisite of a low lattice geometrical misfit with Mg (about 2.8%) to realize epitaxial electrocrystallization. Simultaneously, the ionic crystal nature of Ni(OH)2 displays a periodic and hillock-like electrostatic potential field over its exposed facets, which can precisely capture and confine the reduced Mg0 species onto the local electron-enriched sites at the atomic level. The Ni(OH)2@CC substrate undergoes sequential Mg-ion intercalation, underpotential deposition, and electrocrystallization processes, during which the uniform, lamellar Mg electrodeposits with a locked crystallographic orientation are formed. Under practical conditions (10 mA cm-2 and 10 mAh cm-2), the Ni(OH)2@CC substrate exhibits stable Mg stripping/plating cycle performances over 600 h, 2 orders of magnitude longer than those of the pristine copper foil and carbon cloth substrates.

Uneven Stripping Behavior, an Unheeded Killer of Mg Anodes.

Uniform magnesium (Mg) plating/stripping under high areal capacity utilization is critical for the practical application of Mg-metal anodes in rechargeable Mg batteries. However, the failure of the Mg-metal anode when cycling under a practical areal capacity (>4 mA h cm-2 ), is of rising concern. The mechanism behind these failures remains controversial. In this work, it is illustrated that the initial plating Mg can be undoubtedly uniform in a wide range of current densities (≤5 mA cm-2 ) and under a practical areal capacity (6 mA h cm-2 ). However, an unusual self-accelerating pit growth is observed in the Mg stripping side under moderate current densities (0.1-1 mA cm-2 ), which severely deteriorates the anode integrity and subsequent Mg plating uniformity, causing failure of the Mg-metal anode or short circuit of the battery. The stripping morphology depends on the applied current density, as non-uniformity versus the current density displays a volcano plot during the stripping process. Through in situ spectroscopy, it is illustrated that this current-dependent behavior is determined by the evolution of chlorine-containing complex ions near the interface. This research reminds that the plating/stripping process of the Mg-metal anode must be considered comprehensively for practical Mg-metal batteries.

Charge-Compensation in a Displacement Mg2+ Storage Cathode through Polyselenide-Mediated Anion Redox.

Chalcogenides have been viewed as important conversion-type Mg2+ -storage cathodes to fulfill the high volumetric energy density promise of magnesium (Mg) batteries. However, the low initial Columbic efficiency and the rapid capacity degradation remain challenges for the chalcogenide cathodes, as the clear Mg2+ -storage mechanism has yet to be clarified. Herein, we illustrate that the charge storage mechanism of the Cu2-x Se cathode is a reversible displacement reaction along with a polyselenide (PSe) mediated solution process of anion-compensation. The unique anion redox improves charge storage, while the dissolution of PSe also leads to performance degradation. To address this issue, we introduce Mo6 S8 into the Cu2-x Se cathode to immobilize PSe, which significantly improves performance, especially the reversible capacity (from 140 mAh g-1 to 220 mAh g-1 ). This work provides inspiration for the modification of the Mg2+ -storage cathode, which is a milestone for high-performance Mg batteries.

Current Design Strategies for Rechargeable Magnesium-Based Batteries.

As a next-generation electrochemical energy storage technology, rechargeable magnesium (Mg)-based batteries have attracted wide attention because they possess a high volumetric energy density, low safety concern, and abundant sources in the earth's crust. While a few reviews have summarized and discussed the advances in both cathode and anode materials, a comprehensive and profound review focusing on the material design strategies that are both representative of and peculiar to the performance improvement of rechargeable Mg-based batteries is rare. In this mini-review, all nine of the material design strategies and approaches to improve Mg-ion storage properties of cathode materials have been comprehensively examined from both internal and external aspects. Material design concepts are especially highlighted, focusing on designing "soft" anion-based materials, intercalating solvated or complex ions, expanding the interlayer of layered cathode materials, doping heteroatoms into crystal lattice, size tailoring, designing metastable-phase materials, and developing organic materials. To achieve a better anode, strategies based on the artificial interlayer design, efficient electrolyte screening, and alternative anodes exploration are also accumulated and analyzed. The strategy advances toward Mg-S and Mg-Se batteries are summarized. The advantages and disadvantages of all-collected material design strategies and approaches are critically discussed from practical application perspectives. This mini-review is expected to provide a clear research clue on how to rationally improve the reliability and feasibility of rechargeable Mg-based batteries and give some insights for the future research of Mg-based batteries as well as other multivalent-ion battery chemistries.