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At least 19 records

Metal–Organic Framework-derived Atomic Metal Sites Promoting Sulfur Cathode for All-Solid-State Lithium–Sulfur Batteries

All-solid-state lithium–sulfur batteries (ASSLSBs) offer high energy density and intrinsic safety; however, they still face major challenges, including sluggish redox kinetics and poor sulfur utilization. Incorporating conductive materials into sulfur cathodes is an effective strategy to mitigate these limitations. Here, a highly conductive cobalt–nitrogen–doped carbon (Co–NC) derived from a metal–organic framework (MOF) is introduced to accelerate charge transfer and promote reversible sulfur conversion. Co−NC provides atomically dispersed Co–N sites and conductive carbon pathways that correlate with improved charge transfer, sulfur utilization, and rate capability. Co–NC@S cathode delivers 1499 mAh g–1 at C/20 with a high sulfur loading (5 mg cm–2) and retains 1292 mAh g–1 after five cycles (vs 443 mAh g–1 without Co–NC). Moreover, Co–NC derived ASSLSB achieves 903 mAh g–1 at 5C at 60 °C. This work provides a practical and effective approach to develop high energy, high-rate ASSLSBs.

25 ENERGY STORAGE↗

Improving Cell-Level Specific Energy for All-Solid-State Lithium Sulfur Batteries

All-solid-state lithium-sulfur (Li-S) batteries are considered as one of the top choices toward 500 Wh/kg of specific energy, a key metric for an energy storage system to enable large regional electric aircrafts. Many obstacles remain, such as S utilization in the cathode, cyclability regarding both cathode and anode as well as electrode-electrolyte interfaces, and effective means to increase the S content within the all-solid-state cell architecture. The latter is directly related to cell-level specific energy when considering the weights of all battery cell components. In this presentation, we discuss the efforts in both cathode optimization and cell-level improvement toward increasing the overall specific energy. Various strategies for improving S utilization and reducing the solid electrolyte layer thickness will be presented.

Solid state batteries↗

Electrolyte strategies for practically viable all-solid-state lithium-sulfur batteries

All-solid-state lithium-sulfur batteries are a promising platform due to their high gravimetric energy density and enhanced safety. However, they face numerous challenges that currently obstruct commercial adoption. The key to overcoming these challenges lies in the rational selection and targeted development of solid-state electrolytes, where different materials classes present distinct trade-offs between performance and practicality. We assert that sulfide electrolytes offer the best compatibility with the cathode and anode requirements for practical sulfur cells, with halides and borohydrides also showing potential for use in the cathode with further development. We provide cell-level target parameters to ensure that the field moves consistently towards commercial relevance. Looking forward, we call for the adoption of the chlorinated argyrodite with a composition range of Li 6-x PS 5-x Cl 1+x (x = 0 - 0.5) as a standardized solid-state electrolyte to enable rigorous benchmarking across the field and accelerate battery development.

25 ENERGY STORAGE↗

Bridging the gap between academic research and industrial development in advanced all-solid-state lithium–sulfur batteries

The energy storage and vehicle industries are heavily investing in advancing all-solid-state batteries to overcome critical limitations in existing liquid electrolyte-based lithium-ion batteries, specifically focusing on mitigating fire hazards and improving energy density. All-solid-state lithium–sulfur batteries (ASSLSBs), featuring earth-abundant sulfur cathodes, high-capacity metallic lithium anodes, and non-flammable solid electrolytes, hold significant promise. Despite these appealing advantages, persistent challenges like sluggish sulfur redox kinetics, lithium metal failure, solid electrolyte degradation, and manufacturing complexities hinder their practical use. Further, to facilitate the transition of these technologies to an industrial scale, bridging the gap between fundamental scientific research and applied R&D activities is crucial. Our review will address the inherent challenges in cell chemistries within ASSLSBs, explore advanced characterization techniques, and delve into innovative cell structure designs. Furthermore, we will provide an overview of the recent trends in R&D and investment activities from both academia and industry. Building on the fundamental understandings and significant progress that has been made thus far, our objective is to motivate the battery community to advance ASSLSBs in a practical direction and propel the industrialized process.

25 ENERGY STORAGE↗

Overcoming the conversion reaction limitation at three-phase interfaces using mixed conductors towards energy-dense solid-state Li–S batteries

Lithium–sulfur (Li–S) all-solid-state batteries (ASSBs) hold great promise for next-generation safe, durable and energy-dense battery technology. However, solid-state sulfur conversion reactions are kinetically sluggish and primarily constrained to the restricted three-phase boundary area of sulfur, carbon and solid electrolytes, making it challenging to achieve high sulfur utilization. Here, in this study, we develop and implement mixed ionic–electronic conductors (MIECs) in sulfur cathodes to replace conventional solid electrolytes and invoke conversion reactions at sulfur–MIEC interfaces in addition to traditional three-phase boundaries. Microscopic and tomographic analyses reveal the emergence of mixed-conducting domains embedded in sulfur at sulfur–MIEC boundaries, helping promote the thorough conversion of active sulfur into Li 2 S. Consequently, substantially improved active sulfur ratios (up to 87.3%) and conversion degrees (>94%) are achieved in Li–S ASSBs with high discharge capacity (>1,450 mAh g –1 ) and long cycle life (>1,000 cycles). The strategy is also applied to enhance the active material utilization of other conversion cathodes.

36 MATERIALS SCIENCE↗

Impact of electric vehicle battery recycling on reducing raw material demand and battery life-cycle carbon emissions in China

The rapid growth of electric vehicles (EVs) in China challenges raw material demand. This study evaluates the impact of recycling and reusing EV batteries on reducing material demand and carbon emissions. Integrating a national-level vehicle stock turnover model with life-cycle carbon emission assessment, we found that replacing nickel-cobalt-manganese batteries with lithium iron phosphate batteries with battery recycling can reduce lithium, cobalt, and nickel demand between 2021 and 2060 by up to 7.8 million tons (Mt) (67%), 12.4 Mt (96%), and 37.2 Mt (93%), respectively, significantly decreasing reliance on import. Moreover, battery recycling coupled with reuse can reduce carbon emissions by up to 6,532-6,864 Mt (36.0-37.9%), depending on four recycling methods employed. However, this reuse strategy delays battery recycling and risks lithium supply shortage, necessitating trade-offs between carbon reduction and material supply. Future technologies, such as lithium-sulfur and all-solid-state batteries, despite their energy efficiency, might exacerbate lithium shortage, underscoring the crucial need for increased lithium supply.

25 ENERGY STORAGE↗

Predictive Engineering of Interfaces and Cathodes for High-Performance All Solid-State Lithium-Sulfur Batteries

The primary goal of this project is to leverage data-driven methods and machine learning strategies to develop accurate multi-physics models for all-solid-state Li-S battery (ASLSB) materials that can capture electrochemical and transport phenomena over atomic to mesoscopic length/timescales. These models will be rigorously validated by synthesis and advanced characterization experiments. The team will leverage the predictive power of these models, alongside synthesis/characterization experiments and battery fabrication to address longstanding issues at the electrode/electrolyte interfaces in ASLSBs. The project’s proposed technology involves the following: (1) halide-doped solid sulfide electrolytes that can concurrently provide high Li + ion conductivity and suppress dendrite growth; (2) novel mesoporous cathode composed of super-P and carbon nanotubes co-infiltrated with sulfur and sulfide electrolyte, which hold potential to allow high sulfur loading and optimal ion/electron pathways; and (3) functionalization of sulfide electrolyte with ionic liquids to improve physical contact and minimize impedance at the cathode/electrolyte interface. Successful development of proposed predictive models (at multiple scales) will bridge this knowledge gap and will advance fundamental understanding of reaction chemistry, kinetics, charge transfer, and dendrite growth at electrified SSIs. This will enable predictive design of effective strategies to mitigate interfacial problems in ASSLSBs, including poor interfacial contact, interfacial impedance to Li + ion transport, and poor electron/ion conduction within cathodes. Ultimately, the fundamental knowledge gained will lead to development of high-performance ASSLSBs.

25 ENERGY STORAGE↗

Deciphering volume changes in Li-S solid-state battery components during cycling: Implication for advanced battery design

Here, in this work, we developed custom fixtures to investigate the mechanical and electrochemical behavior of all-solid-state lithium batteries during cycling under constant pressure and constant volume conditions. We successfully monitored vertical displacements during constant pressure cycling and pressure variations during constant volume cycling, allowing us decouple volume changes in the sulfur, Li 2 S cathodes, LixIn anode, and solid-state electrolyte. Scanning electron microscopy and electrochemical impedance spectroscopy confirmed that two structural changes occur during ASSLB cycling: (1) irreversible fractures in the active material particles, and (2) void formation within the electrode matrix. While the fractures in primary particles are permanent, void formation can be mitigated through stack pressure, which promotes particle rearrangement in the electrode matrix. Our findings emphasize the importance of stack pressure in maintaining the microscale integrity of all-solid-state lithium batteries, preventing void formation and enhance battery performance and durability.

Cell Design↗

Regenerative Solid Interfaces Enhance High-Performance All- Solid-State Lithium Batteries

All-solid-state Lithium batteries (ASSLBs) have gained widespread attention in recent years. However, their performance is still largely limited by the poor transport properties and stability of the solid-solid interfaces (SSIs). In this study, we report a new strategy for creating a reversible interface with good conductivity and self-adaptive mechanical properties for high-performance all-solid-state lithium batteries (ASSLBs). The interface is formed in situ from nanosized lithium iodide (LiI), a component of the solid-state electrolyte (SSE), which flows plastically along the SSE interfaces under high pressure due to its high ductility. Moreover, LiI segregates and enriches along the Li/SSE interfaces, reversibly enhancing Li plating/stripping due to its lithophilicity and high ionic conductivity. This dynamic LiI interface enables stable operation of metallic Li anode (>1000 h) at high current densities and elevated temperatures, and long-term cycling of all-solid-state Li-sulfur batteries (>250 cycles) with high sulfur utilization rate (>1400 mAh g-1) and areal capacity (>2 mAh cm-2). This study reveals a unique role of LiI in building robust SSIs and provides new insights into the design of novel SSEs and interfaces for high-performance ASSLBs.

Yu, Zhaoxin↗

In operando neutron imaging characterizations of all-solid-state batteries

The surge in electric vehicle demand has propagated the extensive application of lithium-ion batteries (LIBs) in recent years. Gaining significant traction due to their promising high-energy density and elevated safety over traditional LIBs, all-solid-state Li batteries (ASLBs) have nonetheless been faced with hurdles relating to battery performance. These include concerns with interfacial compatibility, structural stability, Li dendrite inhibition, and large-scale manufacturing. To tackle these issues, it is necessary to employ advanced characterization methods to comprehend the intrinsic mechanisms within ASLBs. In this article, we advocate for the use of neutron imaging as a nondestructive approach for the operando visualization of ASLBs. We draw comparisons with other operando visualization strategies, underline the benefits of neutron imaging, and discuss its potential applicability in the scrutiny of all-solid-state Li metal batteries and all-solid-state Li-sulfur batteries. Neutron imaging provides valuable insights into the dynamics of Li concentration, reaction mechanisms, and transport constraints in ASLBs. These insights are pivotal in contributing to the evolution of high-performance all-solid-state batteries.

25 ENERGY STORAGE↗

Li 2 GeS 3 : Lithium Ionic Conductor with an Unprecedented Structural Type

Lithium-ion batteries (LIBs) are widely used in electric vehicles, mobile electronic devices, and large-scale stationary energy storage systems. However, their liquid electrolytes present significant safety concerns due to their inherent flammability. To address this, the focus has shifted toward all-solid-state batteries (ASSBs) utilizing inorganic solid electrolytes that promise enhanced safety. In this work, we report the discovery of a new crystal structural type of Li-ion conductor, Li 2 GeS 3 , with a unique structure, synthesized by a solid-state reaction from Li 2 S and GeS 2 . It was first reported in 2000 with an orthorhombic unit cell, but its detailed crystal structure remains veiled. Here, we have unveiled its structure for the first time, employing an ab initio structure determination technique from powder X-ray and time-of-flight neutron diffraction data. The compound has an unprecedented crystal structural type with a hexagonal $P6_1$ symmetry and a unit cell of α = 6.79364(4) Å and c = 17.90724(14) Å. Its structure is comprised of a distorted hexagonal close-packed arrangement of sulfur anions with three asymmetric metal atoms: Li1, Li2, and Ge are in tetrahedral cavities surrounded by sulfur atoms. The ionic conductivity of Li 2 GeS 3 was measured to be 1.63 × 10 –8 S cm –1 at 303 K and 2.45 × 10 –7 S cm –1 at 383 K. Bond valence energy landscape calculations revealed three-dimensional lithium diffusion pathways within the structure. This novel crystal structure in Li 2 GeS 3 holds the potential for developing high-performance ionic conductors through suitable chemical substitution and offers valuable insights into designing new ionic conductors for ASSBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Operando Neutron Imaging of Lithium Flux and Gradient Cathode Design for Enhanced Kinetics in High‐Loading All‐Solid‐State Li─S Batteries

All-solid-state Li–sulfur batteries (ASSLSBs) are considered promising candidates for next-generation energy storage owing to their inherent safety, high energy density, and abundant sulfur resources. However, slow redox kinetics greatly limit sulfur utilization during solid-solid sulfur reactions, leading to significant challenges to achieve efficient performance in high-mass-loading ASSLSBs. Here, operando neutron image is employed to directly visualize, for the first time, that sluggish Li + transport kinetics and the uneven distribution of Li + during cathodic reactions are critical factors limiting sulfur conversion. To address this issue, gradient cathode architectures comprising three and five layers are designed, in which catholyte concentrations are strategically varied to optimize Li-ion flux and enhance ionic conductivity of the whole composite cathode electrode. Operando neutron imaging distinctly visualizes and confirms that three-layer gradient approach significantly enhances Li-ion mobility, resulting in more uniform redox reactions and greatly improved sulfur utilization compared to traditional non-gradient structures. Consequently, the three-layer gradient cathode achieves superior rate performance and reduced electrode polarization at high sulfur mass loadings of 4.5 and 6.0 mg cm −2 . Furthermore, the applicability and scalability of this design are demonstrated in a five-layer gradient cathode architecture, achieving an impressive discharge specific capacity increase from 656 mAh g −1 (three-layer gradient) to 1232 mAh g −1 at 1/20 C for ultra-high sulfur loading of 7.5 mg cm −2 . In conclusion, this innovative gradient cathode design offers substantial advancements in understanding and overcoming Li-ion transport limitations, paving the way toward practical, high-energy-density ASSLSBs.

25 ENERGY STORAGE↗