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At least 109 records · Page 6

A comprehensive review on liquid electrolyte design for low-temperature lithium/sodium metal batteries

Lithium/sodium metal batteries (LMBs/SMBs) possess immense potential for various applications due to their high energy density. Nevertheless, LMBs/SMBs are highly susceptible to the detrimental effects of an unstable solid electrolyte interphase (SEI) and dendrites during practical applications, particularly pronounced in low-temperature environments. Furthermore, sluggish ion transportation further compromises the cycling stability of LMBs/SMBs at low temperatures. To achieve stable operation of LMBs/SMBs at low temperatures, researchers have made numerous efforts including electrolyte optimization aimed at creating stable SEIs and suppressing the metal dendrites under low temperature conditions. Despite the significant advancements made recently in the liquid electrolyte design, there remains considerable hurdle in electrolyte engineering for practical low-temperature, high energy density LMBs/SMBs, calling for a profound comprehension of the intricate interplay between the electrochemical reaction kinetics and electrolyte compositions. Here, this review provides a thorough overview of various strategies in optimizing liquid electrolytes covering weakly solvating electrolytes, concentration-designed electrolytes, and solvation structure-designed electrolytes, to address the challenges faced by LMBs/SMBs at low temperatures, including slow reaction kinetics and the difficulties in Li + /Na + solvation/desolvation. Furthermore, this review discusses future prospects for the advancement of this field, intending to provide valuable insights and support for subsequent research undertakings.

25 ENERGY STORAGE↗

Self-Healing Lithium Dendrites through Spontaneous Passivating Layer Formation for Stable Solid-State Lithium–Metal Batteries

All-solid-state lithium–metal batteries have attracted significant attention, owing to their high energy density and superior safety. However, lithium–metal penetration through the solid electrolyte, leading to short-circuiting, remains a critical failure mode that demands comprehensive mitigation strategies. Most existing strategies are effective only prior to the initiation of lithium-dendrite formation and fail once dendrites begin to propagate through the electrolyte. In this study, we propose a self-healing mechanism in which the penetrated lithium reacts with a self-healing agent to form a passivating layer along the particle boundaries. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated into a Li 6 PS 5 Cl solid electrolyte as the self-healing agent to suppress lithium-dendrite propagation even after dendrite formation initiated under high current densities. The self-healing induced by LiTFSI was verified through comprehensive experimental analyses and was further demonstrated in a full-cell configuration. Moreover, LiTFSI incorporation plays an important role in increasing the critical current density by reducing the overall electronic conductivity of the solid electrolyte and facilitating the formation of a robust LiF-containing solid-electrolyte interphase.

25 ENERGY STORAGE↗

Superionic conducting vacancy-rich β-Li 3 N electrolyte for stable cycling of all-solid-state lithium metal batteries

The advancement of all-solid-state lithium metal batteries requires breakthroughs in solid-state electrolytes (SSEs) for the suppression of lithium dendrite growth at high current densities and high capacities (>3 mAh cm -2 ) and innovation of SSEs in terms of crystal structure, ionic conductivity and rigidness. Here we report a superionic conducting, highly lithium-compatible and air-stable vacancy-rich β-Li 3 N SSE. This vacancy-rich β-Li 3 N SSE shows a high ionic conductivity of 2.14 × 10 -3 S cm -1 at 25 °C and surpasses almost all the reported nitride-based SSEs. A Li- and N-vacancy-mediated fast lithium-ion migration mechanism is unravelled regarding vacancy-triggered reduced activation energy and increased mobile lithium-ion population. All-solid-state lithium symmetric cells using vacancy-rich β-Li 3 N achieve breakthroughs in high critical current densities up to 45 mA cm -2 and high capacities up to 7.5 mAh cm -2 , and ultra-stable lithium stripping and plating processes over 2,000 cycles. The high lithium compatibility mechanism of vacancy-rich β-Li 3 N is unveiled as intrinsic stability to lithium metal. In addition, β-Li 3 N possesses excellent air stability through the formation of protection surfaces. All-solid-state lithium metal batteries using the vacancy-rich β-Li 3 N as SSE interlayers and lithium cobalt oxide (LCO) and Ni-rich LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) cathodes exhibit excellent battery performance. Extremely stable cycling performance is demonstrated with high capacity retentions of 82.05% with 95.2 mAh g -1 over 5,000 cycles at 1.0 C for LCO and 92.5% with 153.6 mAh g -1 over 3,500 cycles at 1.0 C for NCM83. Utilizing the vacancy-rich β-Li 3 N SSE and NCM83 cathodes, the all-solid-state lithium metal batteries successfully accomplished mild rapid charge and discharge rates up to 5.0 C, retaining 60.47% of the capacity. Notably, these batteries exhibited a high areal capacity, registering approximately 5.0 mAh cm -2 for the compact pellet-type cells and around 2.2 mAh cm -2 for the all-solid-state lithium metal pouch cells.

25 ENERGY STORAGE↗

Single-Ion Conducting Polymer Electrolytes for Solid-State Lithium–Metal Batteries: Design, Performance, and Challenges

Realizing solid-state lithium batteries with higher energy density and enhanced safety compared to the conventional liquid lithium-ion batteries is one of the primary research and development goals set for next-generation batteries in this decade. In this regard, polymer electrolytes have been widely researched as solid electrolytes due to their excellent processability, flexibility, and low weight. With high cationic transference numbers (t Li + close to 1), single-ion conducting polymer electrolytes (SICPEs) have tremendous advantages compared to polymer electrolyte systems (t Li + < 0.4) because of their potential to reduce the buildup of ion concentration gradients and suppress growth of lithium dendrites. The current review covers the fundamentals of SICPEs, including anionic unit synthesis, polymer structure design, and film fabrication, along with simulation and experimental results in solid-state lithium–metal battery applications. Overall, a perspective on current challenges, possible solutions, and potential research directions of SICPEs is also discussed to provide the research community with the critical technical aspects that may advance SICPEs as solid electrolytes in next-generation energy storage systems.

25 ENERGY STORAGE↗

Uniform lithiophilic layers in 3D current collectors enable ultrastable solid electrolyte interphase for high-performance lithium metal batteries

Uniform lithium plating/stripping during charging/discharging in 3D lithiophilic current collectors (3DLCC) is essential to suppress growth of lithium dendrites and to mitigate infinite volume variations of lithium metal for long-lived lithium metal batteries. Additionally, this study reveals the decisive role played by uniformity of the lithiophilic layer of the 3DLCC in achieving uniform lithium plating/stripping. Herein, a series of metal oxide-based 3DLCCs are successfully fabricated with a simple and an ultrafast solution combustion method, from which formation of a uniform and stable lithium dendrite-free solid electrolyte interphase via a uniform lithiophilic layer is demonstrated. Taking Co 3 O 4 as the lithiophilic material deposited on a nickel foam as the 3DLCC (Co@NF) for a proof of concept, the loading amount of Co 3 O 4 , closely correlated with the uniformity of the Co 3 O 4 layer, is modulated to optimize its lithium ion hosting performances. With a uniform Co 3 O 4 layer grown in the 3DLCC, an ultralow nucleation overpotential of 33.4 mV is achieved in half-cell tests at 1 mA cm -2 and 1 mAh cm -2 , and a high Coulombic efficiency of 97.1% is maintained after 210 cycles under a severe cycling condition of 2 mA cm -2 and 1 mAh cm -2 . A small polarization voltage of 13 mV together with an ultralong cycle life of 2400 h at 0.5 mA cm -2 and 1 mAh cm -2 in symmetric Li cells is achieved. Moreover, the composite Li anode delivers sensational rate capability and cyclability in full-cells. This work not only provides new and valuable insights into the interphasial chemistry of solid electrolyte interphase layers, but also sheds light on the development of ultrastable lithium metal batteries.

25 ENERGY STORAGE↗

Three-dimensional Zn-based alloys for dendrite-free aqueous Zn battery in dual-cation electrolytes

Aqueous zinc-ion batteries, in terms of integration with high safety, environmental benignity, and low cost, have attracted much attention for powering electronic devices and storage systems. However, the interface instability issues at the Zn anode caused by detrimental side reactions such as dendrite growth, hydrogen evolution, and metal corrosion at the solid (anode)/liquid (electrolyte) interface impede their practical applications in the fields requiring long-term performance persistence. Despite the rapid progress in suppressing the side reactions at the materials interface, the mechanism of ion storage and dendrite formation in practical aqueous zinc-ion batteries with dual-cation aqueous electrolytes is still unclear. Herein, we design an interface material consisting of forest-like three-dimensional zinc-copper alloy with engineered surfaces to explore the Zn plating/stripping mode in dual-cation electrolytes. The three-dimensional nanostructured surface of zinc-copper alloy is demonstrated to be in favor of effectively regulating the reaction kinetics of Zn plating/stripping processes. The developed interface materials suppress the dendrite growth on the anode surface towards high-performance persistent aqueous zinc-ion batteries in the aqueous electrolytes containing single and dual cations. This work remarkably enhances the fundamental understanding of dual-cation intercalation chemistry in aqueous electrochemical systems and provides a guide for exploring high-performance aqueous zinc-ion batteries and beyond.

25 ENERGY STORAGE↗

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High‐Energy Li‐S Batteries

Abstract Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium–sulfur (Li‐S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li‐S pouch cells. Herein, we demonstrate that a rational combination of selenium doping, core–shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm −2 ) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm −2 ) with a low electrolyte/sulfur ratio (10 μL mg −1 ). This research further demonstrates a durable Li‐Se/S pouch cell with high specific capacity, validating the potential practical applications.

Zhao, Chen↗

Beyond the Polysulfide Shuttle and Lithium Dendrite Formation: Addressing the Sluggish Sulfur Redox Kinetics for Practical High-Energy Li-S Batteries

Electrolyte modulation simultaneously suppresses polysulfide the shuttle effect and lithium dendrite formation of lithium-sulfur (Li-S) batteries. However, the sluggish S redox kinetics, especially under high S loading and lean electrolyte operation, has been ignored, which dramatically limits the cycle life and energy density of practical Li-S pouch cells. In this work, we demonstrate that a rational combination of selenium doping, core-shell hollow host structure, and fluorinated ether electrolytes enables ultrastable Li stripping/plating and essentially no polysulfide shuttle as well as fast redox kinetics. Thus, high areal capacity (>4 mAh cm -2 ) with excellent cycle stability and Coulombic efficiency were both demonstrated in Li metal anode and thick S cathode (4.5 mg cm -2 ) with a low electrolyte/sulfur ratio (10 mu L mg(-1)). Overall, this research further demonstrates a durable Li-Se/S pouch cell with high specific capacity, validating the potential practical applications.

25 ENERGY STORAGE↗

Molecular Engineering Enabled Stable Deep Eutectic Amide-Based Electrolyte for High-Temperature Lithium–Metal Batteries

The development of advanced lithium-metal batteries (LMBs), such as high-temperature LMBs and high-energy-density LMBs, has critical requirements for electrolytes. However, conventional electrolytes suffer from thermal instability and insufficient electrolyte/Li interfacial compatibility, severely limiting their utilization in high-temperature LMBs. Herein, we design a high-temperature N-methylacetamide (NMAc)-based deep eutectic electrolyte (DEE) by molecular engineering on a solvation structure via a sacrificial additive of vinyl ethylene carbonate (VEC). Specifically, VEC interacts with the Li prior to NMAc, facilitating the formation of a solid electrolyte interphase to inhibit the reaction between Li and NMAc. The stable VEC-DEE effectively suppresses the growth of lithium dendrites and ensures the battery a cycling stability of 550 cycles at 80 °C. Additionally, we also demonstrate the application of VEC-DEE in high-energy-density LMBs with a high mass loading of 2.5 mAh/cm 2 . In conclusion, this research opens a new avenue for the rational design of advanced high-temperature electrolytes.

25 ENERGY STORAGE↗

Preliminary investigation of a sealed, remotely activated silver-zinc battery

Methods necessary to provide a remotely activated, silver zinc battery capable of an extended activated stand while in a sealed condition were investigated. These requirements were to be accomplished in a battery package demonstrating an energy density of at least 35 watt hours per pound. Several methods of gas suppression were considered in view of the primary nature of this unit and utilized the electroplated dendritic zinc electrode. Amalgamation of the electrode provided the greatest suppression of gas at the zinc electrode. The approach to extending the activated stand capability of the remotely activated battery was through evaluation of three basic methods of remote, multi-cell activation; 1) the electrolyte manifold, 2) the gas manifold and 3) the individual cell. All three methods of activation can be incorporated into units which will meet the minimum energy density requirement.

Wheat, C. G.↗

Effect of diffusion constant on the morphology of dendrite growth in lithium metal batteries

Lithium dendrites can lead to a short circuit and battery failure, and developing strategies for their suppression is of considerable importance. In this work, we study the growth of dendrites in a simple model system where the solvent is a continuum and the lithium ions are hard spheres that can deposit by sticking to existing spheres or the electrode surface. Using stochastic dynamics simulations, we investigate the effect of applied voltage and diffusion constant on the growth of dendrites. We find that the diffusion constant is the most significant factor, and the inhomogeneity of the electric field does not play a significant role. Additionally, the growth is most pronounced when the applied voltage and diffusion constant are both low. We observe a structural change from broccoli to cauliflower shape as the diffusion constant is increased. The simulations suggest that a control of electrolyte parameters that impact lithium diffusion might be an attractive route to controlling dendrite growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface film effects on drop tube undercooling studies

The effects of various gaseous atmospheric constituents on drop-tube solidified samples of elemental metals were examined from a microstructural standpoint. All specimens were prepared from the purest available elements, so effects of impurities should not account for the observed effects. The drop-tube gas has a definite effect on the sample microstructure. Most dramatically, the sample cooling rate is effected. Some samples receive sufficient cooling to solidify in free fall while others do not, splating at the end of the drop tube in the sample catcher. Gases are selectively absorbed into the sample. Upon solidification gas can become less soluble and as a result forms voids within the sample. The general oxidation/reduction characteristics of the gas also affect sample microstructures. In general, under the more favorable experimental conditions including reducing atmospheric conditions and superheatings, examination of sample microstructures indicates that nucleation has been suppressed. This is indicated by underlying uniform dendrite spacings throughout the sample and with a single dendrite orientation through most of the sample. The samples were annealed yielding a few large grains and single or bi-crystal samples were commonly formed. This was especially true of samples that were inadvertently greatly superheated. This is in contrast with results from a previous study in which surface oxides were stable and contained numerous sites of nucleation. The number of nucleation events depends upon the surface state of the specimen as determined by the atmosphere and is consistent with theoretical expectations based upon the thermodynamic stability of surface oxide films. Oxide-free specimens are characterized by shiny surfaces, with no observable features under the scanning electron microscope at 5000X.

Ethridge, E. C.↗

Developing a model for the impact of non-conformal lithium contact on electro-chemo-mechanics and dendrite growth

Lithium dendrite growth hinders the use of lithium metal anodes in commercial batteries. We present a 3D model to study the mechanical and electrochemical mechanisms that drive microscale plating. With this model, we investigate electrochemical response across a lithium protrusion characteristic of rough anode surfaces, representing the separator as a porous polymer in non-conformal contact with a lithium anode. The impact of pressure on separator morphology and electrochemical response is of particular interest, as external pressure can improve cell performance. We explore the relationships between plating propensity, stack pressure, and material properties. External pressure suppresses lithium plating due to interfacial stress and separator pore closure, leading to inhomogeneous plating rates. For moderate pressures, dendrite growth is completely suppressed, as plating will occur in the electrolyte-filled gaps between anode and separator. In fast-charging conditions and systems with low electrolyte diffusivities, the benefits of pressure are overridden by ion transport limitations.

25 ENERGY STORAGE↗

Formation of Stable Interphase of Polymer-in-Salt Electrolyte in All-Solid-State Lithium Batteries

The integration of solid-polymer electrolytes into all-solid-state lithium batteries is highly desirable to overcome the limitations of current battery configurations that have a low energy density and severe safety concerns. Polyacrylonitrile is an appealing matrix for solid-polymer electrolytes; however, the practical utilization of such polymer electrolytes in all-solid-state cells is impeded by inferior ionic conductivity and instability against a lithium-metal anode. In this work, we show that a polymer-in-salt electrolyte based on polyacrylonitrile with a lithium salt as the major component exhibits a wide electrochemically stable window, a high ionic conductivity, and an increased lithium-ion transference number. The growth of dendrites from the lithium-metal anode was suppressed effectively by the polymer-in-salt electrolyte to increase the safety features of the batteries. In addition, we found that a stable interphase was formed between the lithium-metal anode and the polymer-in-salt electrolyte to restrain the uncontrolled parasitic reactions, and we demonstrated an all-solid-state battery configuration with a LiFePO 4 cathode and the polymer-in-salt electrolyte, which exhibited a superior cycling stability and rate capability.

Gao, Hongcai↗