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At least 127 records · Page 7

Electrochemical formation of bis(fluorosulfonyl)imide-derived solid-electrolyte interphase at Li-metal potential

Lithium bis(fluorosulfonyl)imide-based liquid electrolytes are promising for realizing high Coulombic efficiency and long cycle life for next-generation Li-metal batteries. However, the role of anions in the formation of solid-electrolyte interphase remains unclear. Herein, we combine electrochemical analyses and X-ray photoelectron spectroscopy measurements both with and without sample washing, together with computational simulations, to propose the reaction pathways of electrolyte decomposition and correlate the interphase component solubility with the efficacy of passivation. Additionally, we discovered that not all the products derived from interphase-forming reactions were incorporated into the resulting passivation layer, with a notable portion present in the liquid electrolyte. Further, we found that the high-performance electrolytes can afford a sufficiently passivating interphase with minimized electrolyte decomposition, by incorporating more anion-decomposition products. Overall, this work presents a systematic approach of coupling electrochemical and surface analyses to paint a comprehensive picture of solid-electrolyte interphase formation, while identifying key attributes of high-performance electrolytes for guiding future designs.

Yu, Weilai [Stanford University, CA (United States↗

Early Failure of Lithium–Sulfur Batteries at Practical Conditions: Crosstalk between Sulfur Cathode and Lithium Anode

Lithium–sulfur (Li–S) batteries are one of the most promising next-generation energy storage technologies due to their high theoretical energy and low cost. However, Li–S cells with practically high energy still suffer from a very limited cycle life with reasons which remain unclear. Here, through cell study under practical conditions, it is proved that an internal short circuit (ISC) is a root cause of early cell failure and is ascribed to the crosstalk between the S cathode and Li anode. The cathode topography affects S reactions through influencing the local resistance and electrolyte distribution, particularly under lean electrolyte conditions. The inhomogeneous reactions of S cathodes are easily mirrored by the Li anodes, resulting in exaggerated localized Li plating/stripping, Li filament formation, and eventually cell ISC. Manipulating cathode topography is proven effective to extend the cell cycle life under practical conditions. The findings of this work shed new light on the electrode design for extending cycle life of high-energy Li–S cells, which are also applicable for other rechargeable Li or metal batteries.

25 ENERGY STORAGE↗

Dual Functional Ni3S2@Ni Core-Shell Nanoparticles Decorating Nanoporous Carbon as Cathode Scaffolds for Lithium-Sulfur Battery with Lean Electrolytes

Lithium-sulfur batteries are very promising for next-generation energy storage. However, most studies use flooded electrolytes to achieve a high specific capacity at the expense of lowering the specific energy. Understanding lithium-sulfur battery performance with lean electrolytes is highly desirable. Herein, a modified Pechini method is developed to synthesize a nanoporous carbon host decorated with Ni3S2@Ni particles. Such a cathode delivers enhanced specific capacities with extended cycling life in lean electrolytes, due to the dual functions of the Ni3S2 shell, which can both facilitate reaction kinetics and promote electrolyte wetting. This work highlights a strategy to rationally design cathodes for highenergy lithium-sulfur batteries.

Zhang, Yulun↗

Molecular Ionic Composites: A New Class of Polymer Electrolytes to Enable All-Solid-State and High-Voltage Lithium Batteries (Final Project Report for DOE EERE VTO grant EE0008860)

Based on a newly discovered class of solid PE materials, that is, molecular ionic composites (MICs), the major goal of this project is to develop solid-state lithium conductors targeted for use in transportation applications. MICs form a mechanically stiff, electrochemically stable, and thermally stable matrix. Specific objectives include the following: (1) development of robust MIC electrolyte thin films (~ 20 µm) to serve as simultaneous nonflammable separators and dendrite-blocking Li + conductors, (2) electrochemical quantification of key performance metrics including electrolyte stability, interfacial reactions, and suitability/compatibility with a range of electrode materials, and (3) comprehensive investigation of ion transport mechanisms and electrode-electrolyte interfacial reactivity under practical operating conditions using NMR and synchrotron X-ray analyses.

25 ENERGY STORAGE↗

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗

Direct deposit of catalyst on the membrane of direct feed fuel cells

An improved direct liquid-feed fuel cell having a solid membrane electrolyte for electrochemical reactions of an organic fuel. Catalyst utilization and catalyst/membrane interface improvements are disclosed. Specifically, the catalyst layer is applied directly onto the membrane electrolyte.

Chun, William↗

In Situ Construction of Uniform and Robust Cathode–Electrolyte Interphase for Li-Rich Layered Oxides

The high-energy-density Li-rich layered oxides (LLOs) as promising cathodes for Li-ion batteries suffer from the dissolution of transition metals (especially manganese) and severe side reactions in conventional electrolytes, which greatly deteriorate their electrochemical performance. Herein, an in situ “anchoring + pouring” synergistic cathode-electrolyte interphase (CEI) construction is realized by using 1,3,6-hexanetricarbonitrile (HTCN) and tris(trimethylsilyl) phosphate (TMSP) electrolyte additives to alleviate the challenges of an LLO (Li 1.13 Mn 0.517 Ni 0.256 Co 0.097 O 2 ). HTCN with three nitrile groups can tightly anchor transition metals by coordinative interaction to form the CEI framework, and TMSP will electrochemically decompose to reshape the CEI layer. The uniform and robust in situ constructed CEI layer can suppress the transition metal dissolution, shield the cathode against diverse side reactions, and significantly improve the overall electrochemical performance of the cathode with a discharge voltage decay of only 0.5 mV/cycle -1 . Further investigations based on a series of experimental techniques and theoretical calculations have revealed the composition of in situ constructed CEI layers and their distribution, including the enhanced HTCN anchoring effect after lattice densification of LLOs. Finally, this study provides insights into the in situ CEI construction for enhancing the performance of high-energy and high-voltage cathode materials through effective, convenient and economical electrolyte approaches.

25 ENERGY STORAGE↗

Development of Next Generation Hierarchical Hybrid Cu-Si anode Batteries via Direct-Ink Writing Application: End of (6th) Month Report - November 2025

Sustainable renewable energy continues to be in dire need to effectively combat global warming. Emerging technology for electric vehicles/ devices remains in high demand that is not only lower in cost, more efficient, but safer in comparison to commercial materials on the market. Although first-generation lithium-ion batteries have exhibited extensive commercial application, conventional graphite no longer meets this increasing demand as an efficient anode material. Due to the fact that graphite has a subpar theoretical specific capacity (372 mAh g -1 ), thus significant limitations in rate capability (for potential faster charging at higher C-rates currently commercially available.). Alternatively, silicon has gained significant attention as a superior candidate to potentially surpass graphite. Due to silicon’s exceedingly high theoretical capacity (4,200 mAh g -1 ) in comparison to standard graphite, its abundance thus in turn it’s low-cost, in addition to exhibiting a significantly low working potential (< 0.4 V vs Li/Li + ). However, one of the main (and most detrimental) challenges is silicon’s tendency to expand in volume (> 300%) upon discharge as it begins the lithiation process. As a direct result, it causes not only for the particles to both crack and pulverize under mechanical stress as the volume continues to expand and contract during cycling. Upon assembling the cell, it needs to undergo ‘charging’ for initially discharging/ ‘activating’ the cell, otherwise commonly known as the ‘formation’ step. As a result a solid electrolyte interface (SEI) layer begins to form at the anode surface because some of the electrolyte begins to react during the formation process. However, this (SEI) layer is deemed as a ‘protective’ interlayer because in theory it prevents further reaction as the cell continues to cycle. However, due to the volume change it causes significant degradation at the interface. As cracking starts to occur at the anode surface, it results in a ‘new’ altered surface with each cycle that causes further reaction with the electrolyte as a byproduct quickly consuming active Li/ and more electrolyte. Thus, fracturing this ‘protective layer,’ causing significantly higher impedance as a result, and in turn a decline in capacity due to active Li-loss. In addition to the active material exfoliating off from the current collector, further contributing to the steady decline in capacity and overall performance. Current state of the art Si-anode batteries on the market range between a maximum content of 5-10 Si wt%. It has been previously reported Tesla has utilized SiO x -C anodes containing 5 wt% Si within their ‘Model 3/ Model X’ electric vehicles. However, more recent ‘Model 3’ vehicles have started to incorporate 10 Si wt%, in which they were able to increase their energy density upwards by approximately 30%. Recent effort has been focused on continuing to increase the wt% of Si being utilized, eventually to 100 wt% of Si, to maximize the energy density even further.

36 MATERIALS SCIENCE↗

Structural and chemical evolutions of a magnesium vanadium oxide cathode under electrochemical cycling in magnesium batteries

The design of cathode materials that remain chemically and structurally stable during repetitive ion insertion and extraction poses a significant challenge in developing multivalent batteries. The cycling stability of traditional metal oxide-based cathode is challenged by sluggish diffusion of multivalent cations and parasitic reactivity at interfacial regimes, including the cathode electrolyte interphase layer (CEI). Understanding the reactions at the cathode-electrolyte interface, particularly those induced by non-stoichiometric surface layers, is a crucial design parameter for both cathode materials and electrolytes. Here, in this study, we employed multimodal analysis, including in situ and ex situ X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) to examine the surface reactions and subsequent structural and chemical evolutions of the CEI on high voltage magnesium vanadium oxide (MgV 2 O 4 ) spinel cathode during the Mg 2+ insertion/extraction processes. The results revealed that the presence of non-stoichiometric surface layers in the magnesium vanadium oxide cathode drive the decomposition of bis(trifluoromethanesulfonyl)imide (TFSI - ) anion, leading to the formation of the CEI layer. The CEI layer could inhibit the Mg 2+ ion transfer processes. Accompanying this reactivity-driven degradation, the magnesium vanadium oxide cathode undergoes pulverization, forming clusters of nanosized particles. This process likely improves cycling ability by creating new intercalation sites and shortening the diffusion pathway for the Mg 2+ cations. This study demonstrates that controlling surface stoichiometry and engineering morphological properties are critical design parameters for high performance cathodes for multivalent batteries.

25 ENERGY STORAGE↗

Protective anode coatings for high energy batteries

Materials for coating a metal anode in a high energy battery, anodes coated with the materials, and batteries incorporating the coated anodes are provided. Also provided are batteries that utilize the materials as electrolytes. The coatings, which are composed of binary, ternary, and higher order metal and/or metalloid oxides, nitrides, fluorides, chlorides, bromides, sulfides, and carbides limit the reactions between the electrolyte and the metal anode in a battery, thereby improving the performance of the battery, relative to a battery that employs a bare anode.

Hegde, Vinay Ishwar↗

Protective anode coatings for high energy batteries

Materials for coating a metal anode in a high energy battery, anodes coated with the materials, and batteries incorporating the coated anodes are provided. Also provided are batteries that utilize the materials as electrolytes. The coatings, which are composed of binary, ternary, and higher order metal and/or metalloid oxides, nitrides, fluorides, chlorides, bromides, sulfides, and carbides limit the reactions between the electrolyte and the metal anode in a battery, thereby improving the performance of the battery, relative to a battery that employs a bare anode.

Hegde, Vinay Ishwar↗

Increasing Ionic Conductivity of Poly(ethylene oxide) by Reaction with Metallic Li

Poly(ethylene oxide) (PEO) was the first lithium-ion conducting polymer developed 50 years ago and is still the most popular electrolyte matrix for solid-state lithium metal batteries. While many studies focus on increasing PEO ionic conductivity through doping with Li salts, little work has addressed using PEO and Li directly to generate Li + -conducting species in situ. Reaction between PEO and Li leads to ionic conductivity largely from Li + , in contrast to the case of added salts where the anion contribution dominates. Herein, electrochemical impedance spectroscopy shows the ionic conductivity of PEO thin films increases up to three orders of magnitude (from 10 –7 to 10 –4 S cm –1 ) when contacted with Li at elevated temperature. This is due to the reduction of ether bonds, which produces lithium alkoxides that are responsible for Li + transport. Density functional theory analysis confirms this mechanism as thermodynamically favorable. X-ray photoelectron spectroscopy also shows the presence of organolithium species and Li 2 O, which are responsible for propagating reactions with PEO and forming an electronically insulating layer at the PEO–Li interface that halts further reaction, respectively. The underlying mechanisms of Li–polymer electrolyte reactions is clarified and new pathways for in situ Li + doping of polymer electrolytes is presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improved Stability and Cyclability of Ceramic Solid Electrolyte by Coating Polymer

Rechargeable all-solid-state lithium (Li) metal batteries show better safety and energy density compared to commercial Li-ion batteries using liquid electrolyte. As the key component of Li metal batteries, ceramic solid-state electrolyte has attracted great interest because of its high ion conductivity and great potential in interfacing with Li metal. Ceramic electrolyte has a more stable interface with Li metal than liquid electrolyte, but chemical reaction and Li dendrite growth at the electrolyte/Li interface are still significant, which causes device degradation and failure by cycling of Li plating and stripping. Unlike ceramic electrolyte, polymer electrolyte has a relatively stable interface with Li metal and better mechanical flexibility. Therefore, we introduced a polymer electrolyte coating to protect the ceramic electrolyte from direct contact with Li metal. The galvanotactic cycling Li plating/striping data on the devices with (without) the coating illustrates increased (decreased) overall conductivity and cyclability of the test cell by the cycling. Nanometer-scale ionic-transport imaging, based on atomic force microscopy, shows that cycling degrades the ceramic-only electrolyte by partially blocking ionic transport in areas; in contrast, cycling on the polymer-coated electrolyte improves ionic conductivity. Compared with the ceramic-only electrolyte, this novel polymer electrolyte coating on ceramic electrolyte shows less degradation when in contact with Li metal.

25 ENERGY STORAGE↗

LixNiO/Ni Heterostructure with Strong Basic Lattice Oxygen Enables Electrocatalytic Hydrogen Evolution with Pt-like Activity

The low-cost hydrogen production from water electrolysis is crucial for practical deployment of sustainable hydrogen economy, but is often constrained by the lack of active and robust electrocatalysts from Earth-abundant materials. We describe here an unconventional heterostructure composed of strongly coupled Ni-deficient LixNiO nanoclusters and polycrystalline Ni nanocrystals, and its exceptional activities toward hydrogen evolution reaction (HER) in aqueous electrolytes. The presence of unique lattice oxygen species with strong Brønsted basicity is a significant feature, which spontaneously split water molecules and effectively accelerate the sluggish Volmer H-OH dissociation step in neutral and alkaline HER. In combination with the unpreceded level of intimate LixNiO and Ni interfacial junctions that produces abundant “hotspots” for promoted hydride coupling, the catalyst exhibited kinetic activities almost identical as Pt/C and decent long term stability in universal pH.

Lu, Ke↗

Electrochemical Ammonia Compression

An electrochemical (EC) compressor is a solid-state compression device. For decades, researchers have been studying EC compressors for applications for a variety of energy systems. As the world transitions away from fossil fuel energy sources, EC compression emerges as a promising technique for energy storage, specifically energy stored in the form of pressurized ammonia. Ammonia is also a commonly used refrigerant. The present studies examine the viability of EC compression for ammonia storage and refrigeration. EC ammonia compression increases the concentration of an ammonia-hydrogen mixture via the input of electrical energy and a series of chemical reactions. A polymer electrolyte membrane separates the low-concentration side from the high-concentration side of the device. On the low-pressure (anode) side hydrogen atoms oxidize and react with ammonia molecules, forming positively charge ammonium ions. The ions traverse the membrane electrolytically. The ammonium ions are reduced and revert back to hydrogen and ammonia upon reaching the high-pressure (cathode). An external circuit provides the current needed to sustain the reactions. In this project, we studied the performance of the ammonia EC compressor under a variety of different conditions. We replicated preliminary data and using a small cell with 5 cm2 of active area. We demonstrated the operation of larger cells with 100 cm2 of active area. Further, we used a commercially available hydrogen EC compressor stack to analyze the scaled-up compressor performance. While previous experiments examined only the transient EC compressor performance, we developed test facilities that allowed the compressor to reach steady state. We analyzed the effects of pressure and current on the EC compressor performance. We measured the flow rates of gas leaving the compressors and analyzed the composition using gas chromatography. We tested methods of separating ammonia from the effluent vapor, which contained hydrogen and water vapor. We found that back diffusion adversely affected the performance, especially when we maintained high pressure lifts.

25 ENERGY STORAGE↗

Regulating in situ gaseous deposition to construct highly durable Fe–N–C oxygen-reduction fuel cell catalysts

The activity–stability trade-off challenges the design of high-performance atomically dispersed iron–nitrogen–carbon (Fe–N–C) catalysts for the acidic oxygen reduction reaction in polymer electrolyte fuel cells. Here we develop an in situ chemical vapour deposition approach during catalyst synthesis to break the trade-off, producing highly stable Fe–N–C catalysts while maintaining adequate oxygen reduction reaction activity. The optimal catalyst exhibits a half-wave potential of 0.867 V, remaining unchanged after an accelerated stress test (AST) of 100,000 potential cycles in rotating disk electrode tests. In membrane electrode assemblies under H 2 –air conditions, it delivers 93 mA cm −2 at 0.8 V after a standard AST of 30,000 voltage cycles, and shows minimal current density losses (2.9% at 0.6 V; 14.2% at 0.7 V) after an extended AST up to 120,000 cycles. Furthermore, the catalyst’s durability improvement is primarily due to the in situ chemical vapour deposition, which strengthens Fe–N bonds, increases active-site density, mitigates iron aggregates and reduces surface porosity.

Chemical engineering↗

Untapped Potential of Fluoride Ions in Maximizing the Electrochemical Stability of Deep Eutectic Solvents

Advancing the batteries is pivotal to propelling our society toward a sustainable, electrified future. The stability of electrolytes forms the backbone of energy storage systems. This is particularly the case for redox flow batteries (RFBs). Their deployability depends on their longevity and dependability. The presence of unstable electrolytes can trigger undesirable reactions, degrade performance, and lead to battery failure. Aqueous electrolytes, with limited electrochemical stability window (ESW), are prone to hydrogen and oxygen evolution. Conversely, non-aqueous electrolytes offer enhanced stability. In this study, we unveil the ESW of a non-aqueous eutectic solvent, comprising choline fluoride and ethylene glycol—a composition that has eluded experimental investigation until now. Our findings show that the stability window, reduction and oxidation potential limits of deep eutectic solvents, are sensitive to variations in the halide component of the ammonium salt. Furthermore, this work not only highlights the benefits of novel deep eutectic solvents but also sets the stage for their strategic use in future battery electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extreme Fast-Charging of Lithium-Ion Cells: Effect on Anode and Electrolyte

In this study, the effects of charge rate in coin cells containing NMC532/1506-Tgraphite are investigated. The cells are cycled at room temperature using charge rates of 1-, 2-, 4-, and 8-C and discharged at the 1-C rate for 50 cycles. The amounts of lithium and LiF are found to be highly correlated with charge time. Three decomposition products are identified in the organic electrolyte. The proposed, empirical formulae for these compounds are C 14 H 33 O 15 P 3 , C 16 H 37 O 15 P 3 , and C 11 H 22 O 7 PF; all are most likely organophosphates formed by the reaction of organic electrolyte decomposition products with LiPF 6 or P(=O)F 3 . The relative concentrations of these organics do not display sensitivity to charge rate. These results imply that a new performance fade mechanism is not introduced by electrolyte decomposition.

25 ENERGY STORAGE↗