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High-voltage water-scarce hydrogel electrolytes enable mechanically safe stretchable Li-ion batteries

Soft Li-ion batteries, based on conventional organic electrolytes, face performance degradation challenges due to moisture penetration and safety concerns due to possible leakage of toxic fluorine compounds and flammable solvents under mechanical damage. We design a water-scarce hydrogel electrolyte with fluorine-free lithium salt to achieve wide electrochemical stability window (up to 3.11 volts) in ambient air without hermetic packaging while balancing high stretchability (1348%), ion conductivity (41 millisiemens per centimeter), and self-healing capabilities for mechanically and chemically safe stretchable Li-ion batteries. Molecular synergy between hydrophilicity and lithiophilicity of zwitterionic polymer backbone is revealed by molecular dynamics simulations. The battery exhibits capacity retention under harsh mechanical stresses—enduring stretching, twisting, folding, and multiple through-punctures by a needle—while self-healing from repeated through cuts by a razor blade. Stable ambient operation for 1 month over 500 charge-discharge cycles (average coulomb efficiency, 95%) is achieved. A prototype self-healing electronic system with embedded soft batteries demonstrates practical application as a durable embodied energy source.

Science & Technology - Other Topics

Sodium-Ion Battery Cathode with Dominating Copper and Oxygen Redox Chemistry

Sodium-ion batteries offer low-cost energy storage solutions for the grid and electric vehicles, leveraging the established "rocking-chair" Li-ion design and the natural abundance of sodium. However, SIBs face challenges such as relatively lower voltage and capacity than lithium-ion batteries, as well as dependence on nickel resources. Here, in this work, a new nickel-free cathode material, Na 0.75 Li 0.08 Cu 0.25 Mn 0.66 O 2 , was designed and synthesized. This material has a capacity of ~125 mAh/g and an average discharge voltage of 3.5 V. Notably, more than one-third of the capacity arises from lithium substitution of Cu (~8 mol.%) and high voltage activation to 4.6 V. Multimodal synchrotron x-ray characterization combining spectroscopy, microscopy, and scattering reveal the capacity is primarily from the redox of copper and oxygen, with a minor contribution from the manganese redox. Lithium substitution alters the phase transition mechanism from a two-phase transition in P3-Na 2/3 Cu 1/3 Mn 2/3 O 2 to a solid-solution in Na 0.75 Li 0.08 Cu 0.25 Mn 0.66 O 2 , enhancing the reversibility of this material.

25 ENERGY STORAGE

Observation of N-rich solid-electrolyte interphase by ToF-SIMS.

Formation of a stable solid electrolyte interphase (SEI) between lithium electrodes and electrolyte upon multiple charge/discharge cycles is crucial to a long-term lithium-ion battery performance. Addition of LiNO3 to lithium bis (fluorosulfonyl) imide/poly(ethylene oxide) (LiFSI/PEO) electrolyte leads to a durable SEI that is electrically insulating yet highly conductive to Li ions, chemically and electrochemically stable, physically uniform, and mechanically robust. ToF-SIMS was used here in combination with sputtering by a gaseous cluster ion beam (GCIB) to examine how the addition of a small proportion of LiNO3 to the LiFSI/PEO electrolyte affects the SEI composition. Negative ion ToF-SIMS spectra of the cycled samples display an intense m/z 26 peak associated with the SEI. Exact mass assignments and isotopic ratios indicate that this peak should be assigned as (CN-)-C-12, with little to no negative secondary ion signal arising from (LiF-)-Li-7. This CN- signal appears to arise from an N-rich portion of the SEI adjacent to the Li electrode that is depleted in LiF relative to the bulk electrolyte. The dearth of LiF- (and LiF+ from the positive ion spectra) is unexpected because LiF has been identified in the SEI in similar samples. Finally, GCIB sputtering indicates that the SEI adheres more strongly to the Li electrode than to the LiFSI/PEO electrolyte.

Shavandi, Seyedeh Reyhaneh

Li 21 Ge 8 P 3 S 34 : New Lithium Superionic Conductor with Unprecedented Structural Type

Abstract Lithium superionic conductors are pivotal for enabling all‐solid‐state batteries, which aim to replace liquid electrolytes and enhance safety. Herein, we report the discovery of an unprecedented lithium superionic conductor, Li 21 Ge 8 P 3 S 34 , featuring a novel structural type and a new composition in the Li–Ge–P–S system. This material exhibits high lithium ionic conductivity of approximately 1.0 mS cm −1 at 303 K with a low activation energy of 0.20(1) eV. It's unique crystal structure was elucidated using three‐dimensional electron diffraction (3D ED) and further refined through combined powder X‐ray and neutron diffraction analyses. The structure consists of alternating two‐dimensional slabs: one of corner‐sharing GeS 4 tetrahedra and the other of isolated PS 4 tetrahedra, enabling efficient lithium‐ion transport through a tetrahedrally interconnected network of 1D, 2D, and 3D diffusion pathways. This distinctive structural motif provides a novel design strategy for next‐generation solid electrolytes, broadening the structural landscape of lithium superionic conductors. With further advancements in compositional tuning and interfacial engineering, Li 21 Ge 8 P 3 S 34 could contribute to the development of high‐performance all‐solid‐state batteries.

Chemistry

Research and Development on Advanced Electrochemical Energy Storage Devices Enabling a Spectrum of Electrified Vehicles

The USABC Advanced Battery development plan had the following three focus areas: 1. Existing technology validation, implementation, and cost reduction 2. Identification of the next viable technology with emphasis on the potential to meet USABC cost and energy density goals. 3. Support high-risk, high-reward battery technology R&D The primary aim of this project was focused on the barriers that most impede wider public adoption of electrification in vehicles-cost, energy density, low-temp performance, calendar life, and improvements in abuse tolerance. The specific objectives are as follows: Cost Reduction: drive to significantly reduce battery cost to be in-line with the $\$$100/kWh or less (by the end of calendar year 2020) DOE cost goals. Additionally, goals of $\$$75/KWh were set for 2023 aligned with fast charge and some offset of energy density. Energy Density Increase: focus on improving the cell-level specific energy and energy densities to >350 watt hours per kilogram (Wh/kg) and >750Wh/L. Low Temperature Performance Increase: strive toward developments that improve the discharge power and eliminate or dramatically reduce the life limiting lithium plating associated with regenerative braking at low temperatures, during the program. Calendar Life Increase: drive to achieve a 15-year calendar life. Abuse Tolerance Improvement: strive to develop improvements in Li-ion abuse tolerance and/or development of electrochemical energy storage technologies with inherently better response to abuse circumstances. Emerging Areas: initiate new programs that address emerging technologies that arise during the contract period.

25 ENERGY STORAGE

Interface-induced fast Li+ transport in mixed ionic–electronic conductors

Interfacial instability between lithium metal and solid-state electrolytes limits the performance of all-solid-state lithium metal batteries (ASSLBs), leading to parasitic reactions, non-uniform Li+ flux, and dendrite growth. Here, we develop a composite interlayer composed of the anti-perovskite Li2OHCl0.75Br0.25 (AP) and carbon nanotubes (CNTs) to enhance both interfacial stability and ionic transport. The AP–CNT interlayer exhibits enhanced Li+ conductivity arising from interfacial electron transfer from AP to CNTs, which generates a built-in electric field that facilitates Li+ migration. Lithium symmetric cells incorporating this interlayer achieve a high critical current density of 2.4 mA cm−2 at 55 °C. This design integrates chemical robustness with coupled ion–electron transport, offering a generalizable strategy for safe, dendrite-free, and high-performance ASSLBs.

He, Chenche

Interface Design for High‐Performance All‐Solid‐State Lithium Batteries

All‐solid‐state batteries suffer from high interface resistance and lithium dendrite growth leading to low Li plating/stripping Coulombic efficiency (CE) of <90% and low critical current density at high capacity. Here, in this work, both challenges are simultaneously addressed and the Li plating/stripping CE is significantly increased to 99.6% at 0.2 mA cm −2 /0.2 mAh cm −2 , and critical current density (CCD) of > 3.0 mA cm −2 /3.0 mAh cm −2 by inserting a mixed ionic‐electronic conductive (MIEC) and lithiophobic LiF‐C‐Li 3 N‐Bi nanocomposite interlayer between Li 6 PS 5 Cl electrolyte and Li anode. The highly lithiophobic LiF‐C‐Li 3 N‐Bi interlayer with high ionic conductivity (10 −5 S cm −1 ) and low electronic conductivity (3.4×10 −7 S cm −1 ) enables Li to plate on the current collector (CC) surface rather than on Li 6 PS 5 Cl surface avoiding Li 6 PS 5 Cl electrolyte reduction. During initial Li plating on CC, Li penetrates into porous LiF‐C‐Li 3 N‐Bi interlayer and lithiates Bi nanoparticles into Li 3 Bi. The lithiophilic Li 3 Bi and Li 3 N nanoparticles in LiF‐C‐Li 3 N‐Li 3 Bi sub‐interlayer will move to CC along with plated Li, forming LiF‐C/Li 3 N‐Li 3 Bi lithiophobic/lithiophilic sublayer during the following Li stripping. This interlayer enables Co 0.1 Fe 0.9 S 2 /Li 6 PS 5 Cl/Li cell with an areal capacity of 1.4 mAh cm −2 to achieve a cycle life of >850 cycles at 150 mA g −1 . The lithiophobic/lithiophilic interlayer enables solid‐state metal batteries to simultaneously achieve high energy and long cycle life.

25 ENERGY STORAGE

High‐Performance Rechargeable Lithium‐Chlorine Batteries with ALD Conformal Starburst Porous Graphene Positive Electrodes

Abstract Rechargeable alkali metal‐chlorine batteries are emerging as a promising high‐energy‐density solution. However, they confront significant challenges, including the primary issue stemming from the weak binding affinity of cathode materials for Cl 2 , which leads to a sluggish and inadequate supply of Cl 2 during the redox reactions, resulting in a shortened cycle life and low Coulombic efficiency (CE), particularly when operating at ultrahigh specific capacity outputs. Herein, an Al 2 O 3 ‐skinned heterostructured starburst porous graphene with conformal metasurfaces (Al 2 O 3 @rGO) is reported, crafted from a hierarchical porous starburst graphene arranged in a unique layered structure by the PTFE microemulsion skin effect, leveraging subsequent fluidized bed atomic layer deposition (FBALD) of Al 2 O 3 groups. Al 2 O 3 @rGO features superhydrophilicity, effective adsorption, fast kinetics from stable dynamic respiratory interface, high electrical and thermal conductivity anisotropy, intelligent thermal management and safe operation over a wide temperature range. Consequently, the Li‐Cl 2 @Al 2 O 3 @rGO battery achieves an ultrahigh discharge specific capacity of 5000 mAh g −1 at ≈100% CE, and even delivers stable cycling over 200 cycles with 2000 mAh g −1 at an average CE of 99.8% under low temperature environment of ‐40 °C. The scalable heterostructure approach offers a sustainable perspective of the development of functionalized metamaterials and metasurfaces for next‐generation safe and energy‐dense batteries and broader applications.

Chemistry

Rinse-Free, Sodium-Efficient Synthesis of O3-Type Layered Oxide Materials Enabled by Acetate Precursors

Sodium-ion batteries (SIBs) are a sustainable alternative to lithium-ion systems for global electrification, with O3-type layered oxide cathodes offering high specific capacity and feasibility of scalable synthesis. Industrial co-precipitation synthesis of these cathodes typically uses transition metal sulfates, requiring extensive water rinsing to remove Na 2 SO 4 impurities, a process that consumes significant water and risks residual inactive phases if incomplete. Here, this work introduces a rinse-free, resource-efficient approach using metal acetate precursors. Residual sodium acetate in non-rinsed precursors decomposes during sintering to generate Na 2 CO 3 in situ, partially substituting an external sodium resource (e.g., NaOH and Na 2 CO 3 ) and reducing its consumption by ∼18–20%. Phase-pure O3-Na 1.0 Ni 1/3 Fe 1/3 Mn 1/3 O 2 (NFM111) cathodes synthesized via this method exhibit microstructure and electrochemical performance comparable to rinsed sulfate-derived counterparts, with initial capacities of 141 mAh g −1 at C/20 (7.5 mA g −1 ). By eliminating rinsing and minimizing sodium reagent use, this acetate-based route enhances sustainability and scalability of layered oxide production for SIBs.

acetate vs. sulfate

Strategic Melamine Coating on Lithium Metal for Li 3 N-Rich Solid Electrolyte Interphase and Improved Battery Cycling Stability

The practical applications of lithium (Li) metal batteries (LMBs) are limited by challenges such as dendrite formation and unstable solid electrolyte interphase (SEI), especially at higher C-rates. Here, this study introduces melamine-coated Li metal anodes (LMAs), forming a Li 3 N-rich SEI layer that improves ionic conductivity and mechanical stability. The optimized melamine-coated LMA demonstrated uniform coverage resulting in denser Li deposition, nearly doubled cycle life (~148 cycles at 0.5 C, 1C = 4.1 mA cm -2 ), compared to Bare-Li. These findings emphasize that coating materials-induced beneficial SEI components could lead to improvement of LMB performance.

Batteries

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.

Yap, Kyra M. K. [University of California, Berkele

Improving Ionic Conformality Across Polymer Electrolyte|Electrode Interfaces

Maintaining uniform ionic transport at electrode|electrolyte interfaces, i.e., ionic conformality, remains challenging in polymer electrolyte (PE)-based solid-state batteries. Morphological conformality does not necessarily imply ionic conformality. In PEs, which typically consist of a mechanically supporting component and distinct ionically conductive components, the rearrangement or depletion of mobile ion-conductive domains at interfaces can disrupt ionic transport pathways. Such localized ionic depletion contributes to interfacial instability and capacity degradation in high-voltage lithium-metal batteries. Herein, an electrolyte design approach aimed at minimizing interfacial heterogeneities is demonstrated through compositional adjustments, characterized by spatially resolved structural and chemical X-ray techniques and NMR diffusometry to elucidate ion transport dynamics. This approach improves ionic conformality at electrode interfaces, enhancing cycling stability in Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) coin and pouch cells cycled at high voltages. These results contribute to understanding interfacial behaviors in multiphase PEs and inform strategies for improving stability across solid-state battery interfaces.

36 MATERIALS SCIENCE

A quantitative imaging framework for lithium morphology: Linking deposition uniformity to cycle stability in lithium metal batteries

Characterizing the morphology of lithium (Li) is crucial for developing long-lasting lithium metal batteries. It is well established that more uniform Li deposition correlates with better cell performance. Li morphology is often characterized through qualitative analysis of scanning electron microscopy (SEM) images; however, there are no widely accepted metrics to quantitatively describe deposition uniformity. Here, we propose a framework to quantify uniformity through SEM image analysis via the index of dispersion (ID) metric, which is defined and presented in the context of Li metal batteries. We also explore experimental impacts of sampling protocols onIDmeasurements. Our results demonstrate that theIDmetric is highly sensitive to variations in deposition uniformity, including the coexistence and uniformity of multiple morphologies, uniformity within a single morphology, and particle size distribution uniformity. Furthermore, it is demonstrated that uniformity, as measured by theID, can be related to the average potential of Li||Li symmetric cells over cycling. Higher capacity cycling leads to more pronounced changes in bothIDand average cell potential. Local minima/maxima are found consistently in bothIDand average cell potential immediately before cells short-circuit, which we suggest may indicate a collapse of the microstructure prior to failure. We put forward this framework as a more robust approach to quantify Li deposition uniformity, advancing the development of Li metal batteries that are safer and longer lasting.

Science & Technology - Other Topics

Three-chamber electrochemical reactor for selective lithium extraction from brine

Efficient lithium recovery from geothermal brines is crucial for the battery industry. Current electrochemical separation methods struggle with the simultaneous presence of Na + , K + , Mg 2+ , and Ca 2+ because these cations are similar to Li + , making it challenging to separate effectively. We address these challenges with a three-chamber reactor featuring a polymer porous solid electrolyte in the middle layer. This design improves the transference number of Li + (t Li+ ) by 2.1 times compared to the two-chamber reactor and also reduces the chlorine evolution reaction, a common side reaction in electrochemical lithium extraction, to only 6.4% in Faradaic Efficiency. Employing a lithium-ion conductive glass ceramic (LICGC) membrane, the reactor achieved high t Li+ of 97.5% in LiOH production from simulated brine, while the concentrations of Na + K + , Mg 2+ , and Ca 2+ are below the detection limit. Electrochemical experiments and surface analysis elucidated the cation transport mechanism, highlighting the impact of Na + on Li + migration at the LICGC interface.

Science & Technology - Other Topics

Asymmetric pathways for lithium extraction and recovery based on the two-phase equilibrium of layered oxides

Electrochemical intercalation offers a promising platform for Li + extraction. However, only limited types of electrode materials have been investigated. The challenge to broaden and tailor materials for electrochemical intercalation-based Li + extraction lies in the lack of understanding of material’s response upon co-intercalation of multiple ions, therefore, paired process design to enable reversible Li + extraction and recovery. Here, we showcase the design of asymmetric ion pathways for Li + extraction and recovery for host material with complex Li + and Na + interaction using layered cobalt oxide as a model material. The two-phase equilibrium of Na 0.48 CoO 2 and Li 0.94 CoO 2 governs Li + selectivity when a high depth of intercalation is achieved (low vacancy level). We show that the relative rate between ion exchange and intercalation is critical to determine the ion pathways. The relationship can be quantitatively compared using the average pseudo ion exchange rate (C pseudoIX ) and the intercalation rate (C inter ). The ion pathways at the three regimes with C pseudoIX > C inter , C pseudoIX ~ C inter , and C pseudoIX < C inter are constructed. By selecting the optimized ion pathway and particle size, we demonstrate 9.7×10 4 Li + selectivity with 99% purity Li + recovery from an initial 1:1000 Li: Na molar ratio solution using 115 mAh/g specific capacity.

electrochemistry

Interlayer Design for Halide Electrolytes in All‐Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state lithium‐metal batteries (ASSLMBs) are promising for transportation electrification due to their superior safety and high energy density. Lithium halide electrolytes provide excellent processing flexibility, high ionic conductivity, and anodic stability (>4.1 V), making them highly compatible with high‐voltage cathodes, surpassing sulfide electrolytes (<2.1 V). Nevertheless, halide electrolytes suffer from low cathodic stability and form an electronically conductive interphase with lithium, resulting in a critical current density (CCD) of nearly zero. Herein, Li 3 YbCl 6 electrolytes are synthesized that are kinetically stable with lithium by forming an electronic insulating solid electrolyte interphase. Guided by critical overpotential criteria, a PI 3 interlayer is designed that transforms into Li 6 PI 3 upon contact with lithium, substantially reducing the interfacial resistance of Li 3 YbCl 6 against lithium to 34 Ω and achieving a high critical overpotential of 114 mV. By substituting Yb with Lu, Li 3 LuCl 6 electrolytes with Li 6 PI 3 interlayers reach a CCD of 1.0 mA cm −2 at a capacity of 1.0 mAh cm −2 , comparable to sulfide electrolytes but with higher oxidation stability. Additionally, Li 6 PI 3 enables stable cycling of Li//Li cells with Li 3 LuCl 6 electrolytes at 0.5 mA cm −2 for 400 cycles and maintains 86.5% capacity in Li//LiCoO 2 cells after 220 cycles at 30 °C, paving the way for high‐performance ASSLMBs.

Chemistry