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209 records · Page 7

Polycarbonate‐Based Solid‐Polymer Electrolytes for Solid‐State Sodium Batteries

Solid-polymer electrolytes comprised of polypropylene carbonate (PPC) and varied sodium bis(fluorosulfonyl)imide (NaFSI) salt concentrations are investigated for implementation as a conductive solid polymer electrolyte into solid-state cathode composites utilizing a sodium-layered oxide active material. The ionic conductivity generally increases with NaFSI salt content, reaching ≈1 mS cm −1 at 80 °C at the highest salt concentration (PPC:NaFSI = 0.5:1). Through an all-in-one slurry casting method, Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode composites are fabricated in which the dispersed PPC electrolyte acts as the primary binder. Enabled by a bilayer polymer electrolyte system, cycling performance with the PPC cathode electrolyte is optimized with respect to salt concentration and anode material. The best cyclability is achieved with a moderate salt concentration electrolyte (PPC:NaFSI = 5:1), showcasing an initial capacity of 83 mA h g −1 with a remarkable 80% capacity retention after 150 cycles at C/5 rate and 60 °C. The superior performance of the lower salt concentration electrolyte is attributed to better electrochemical stability, as confirmed by linear sweep voltammetry and online electrochemical mass spectrometry measurements. In conclusion, these results underscore the potential of carbonate-based polymer electrolytes and the importance of balancing electrolyte conductivity and stability in cell design.

25 ENERGY STORAGE

Cation-Diffusive Carbon Interlayers Stabilize Na Metal and Double the Current in Na-S Redox-Flow Batteries for Grid-Scale Energy Storage

The sodium-sulfur nonaqueous redox-flow batteries (Na-S NARFBs) using earth-abundant elements are highly attractive due to the low material cost and improved energy density for grid-scale energy storage. However, the low current performance, poor Na0/Na+ redox kinetics, and Na dendrite growth pose severe challenges. We introduce cation-diffusive layers (CDLs): thin and Na+ affinitive interlayers at the Na anode that direct Na+ transport and stabilize Na deposition. Benchmarking three archetypal materials—carbon paper (CP), glass microfiber paper (GF), and foam—across Na-Na and Na-Cu, and Na-S cells identifies CP as the optimum. CP reduces symmetric cell overpotential by more than 70%, achieves 98% Na plating-stripping efficiency, and doubles the Na-S cell current density from 0.5 to 1.0 mA cm−2 without sacrificing capacity or efficiency. Ex situ electrochemical and SEM/XPS analysis, combined with molecular dynamics (MD) studies, reveal that electron-rich carbon fibers disperse supporting salt aggregates, enrich near-surface Na+ density, and create ion transport pathways for fast Na0/Na+ exchange while mitigating membrane degradation. Because of the ion-centric mechanism, CDLs can be generalized to other metal-anode designs. Further, this work establishes CDL design rules—cationic affinity and appropriate micro/nanostructure—as a simple, scalable route to high-current, durable metal-anode flow batteries.

Wu, Wenda [ORNL] (ORCID:000900033307687X)

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Electrochemistry

Electrostatic‐Attraction‐Driven Self‐Assembled Graphene‐Disordered Rocksalt Composite Cathode for Lithium‐Ion Batteries

Disordered rocksalt cathodes hold promise for achieving high-capacity lithium-ion batteries while using low-cost, earth-abundant elements. However, their electrochemical performance remains critically limited by their poor electronic conductivity. Conventional strategies such as high-energy ball milling with excess carbon additives can improve conductivity but remain challenging to scale and often produce defects and increase surface area, thereby accelerating capacity degradation. Herein, we report an alternative approach of electrostatic-attraction-driven self-assembly to fabricate Li 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 (LMTOF) particles uniformly wrapped with electronically conductive graphene sheets without associated materials degradation. The graphene-wrapped LMTOF demonstrates significantly improved cycling stability (89% capacity retention after 100 cycles) and superior rate capability compared with an LMTOF-carbon composite electrode fabricated using the conventional high-energy ball-milling process. Post-cycling analysis reveals reduced oxygen evolution, suppressed unwanted side reactions, and improved structural integrity for the graphene-LMTOF composite. This work highlights the advantages of solution-based carbon wrapping and offers a scalable strategy to prepare high-performance DRX cathodes for lithium-ion batteries.

carbon composite

A Cross‐Linked Flexible Metaferroelectrolyte Regulated by 2D/2D Perovskite Heterostructures for High‐Performance Compact Solid‐State Sodium Batteries

Abstract To address the issues of limited ionic conductivity and poor interface stability at room and low temperatures in solid‐state electrolytes, a robust intrinsic ferroelectrolyte or nanoferroelectrolyte strategy for engineering solid‐state flexible ferroelectric composite electrolytes utilizing strongly coupled intrinsic ion conducting 2D/2D sodium‐rich anti‐perovskite (NaRAP)/ferroelectric perovskite heterostructures is introduced. Herein, highly scalable PVDF‐based metaferroelectrolytes with Na 2.99 Ba 0.005 OCl/Ca 2 Na 2 Nb 5 O 16 − (CNNO − ) nanosheets into a ferroelectric poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) matrix, through an in situ cross‐linking and spontaneous bridging method, for compact solid‐state sodium batteries (SSBs), are reported. Benefiting from unique well‐dispersed 3D ferroelectric coupled network and the Na 2.99 Ba 0.005 OCl/CNNO − ‐induced PVDF‐HFP ferroelectric β phase, the Na + flux is regulated, thereby inhibiting Na dendrite growth at the interface. Notably, the optimized PH‐5% NC metaferroelectrolyte exhibits rapid ion transport (1.11 × 10 −4 S cm −1 at 25 °C), a wide electrochemical window (> 4.8V), superior conformal mechanical compatibility, improved flexibility, good elasticity and flame retardancy. The solid‐state Na 3 V 2 (PO 4 ) 3 /PH‐5% NC/Na batteries present a stable cycling performance (remaining 56.4 mAh g −1 after 500 cycles at 1 C) even at 0 °C, potential for cost‐effective, safe, stable and compact SSB energy storage over 600 Wh L −1 , vastly surpassing 365 Wh L −1 of the current commercial sodium‐ion liquid‐electrolyte batteries.

Chemistry

Advanced LiFSI-LiPF6 Electrolyte for Wide-Temperature and Thermally Stable Lithium-Ion Batteries

A new optimized LiFSI–LiPF6 dual-salt controlled-solvation electrolyte (E-DS) is demonstrated to enable practical graphite||LiNi0.8Mn0.1Co0.1O2 cells (˜4.0 mAh cm?²) to achieve exceptional performance and safety under extreme conditions. By optimizing anion coordination with the smaller, more dissociating FSI? anion, the E-DS forms ultrathin, dense, and inorganic-rich electrode/electrolyte interphases that dramatically suppress solvent decomposition, transition-metal dissolution, and surface reconstruction compared to the conventional LiPF6/carbonate electrolyte. Consequently, E-DS cells deliver >78% capacity retention after 300 cycles at 60 °C, retain fast discharging capacity at 30 °C, and operate effectively at -20 °C. Most strikingly, fully charged full cells with E-DS, even under overcharging to 4.8 V, show a lower heat evolution in stable formulations — transforming a traditionally unstable high-voltage/high-temperature configuration into an intrinsically safe state. This work establishes a new benchmark for carbonate-containing electrolytes, simultaneously achieving high energy density, fast-discharging capability, wide-temperature operation (-20 to 60 °C), and outstanding thermal safety in nickel-rich lithium-ion batteries.

electrode/electrolyte interphase

Crack‐Free Single‐Crystalline LiNiO 2 for High Energy Density All‐Solid‐State Batteries

Abstract Single‐crystalline layered oxide (LiNi 1‐ x ‐ y Mn x Co y O 2 ) cathodes have been found to exhibit exceptional electrochemical properties when coupled with various inorganic solid electrolytes (ISEs) in all‐solid‐state batteries (ASSBs). Their advantages stem from the robust morphological integrity with the absence of grain boundaries and the high electrochemical oxidative stability. Here, ASSBs featuring single‐crystalline LiNiO 2 (LNO) with the highest Ni content are reported, offering a high theoretical specific capacity of 275 mAh g ‐1 alongside a high average discharge voltage (3.7 V vs Li + /Li). Through a careful investigation, it is demonstrated that micron‐sized single‐crystalline LNO (µSC‐LNO) composite cathodes with a halide ISE exhibit a high initial discharge capacity of 205 mAh g ‐1 with an outstanding cycle performance over 200 cycles in room‐temperature ASSBs. The significance of engineering parameters is emphasized, such as particle size and specific density, in promoting a homogeneous and fast Li + transport within the composite cathodes. Furthermore, the formation of undesirable interphase between the halide ISE in the cathode and sulfide ISE separator is elucidated, which may be a critical factor impeding long‐term cyclability of ASSBs. This work provides insights into the design of composite cathodes for high‐energy‐density ASSBs.

Chemistry

Mechanistic origin of solvent-dependent thermal stability in sodiated Sn anodes for sodium-ion batteries

Understanding the thermal stability of high-energy density alloy anodes is critical for the safe deployment of sodium-ion batteries (SIBs). Here, accelerating rate calorimetry (ARC), post-mortem characterizations, and density functional theory (DFT) calculations are combined to understand the thermal reactivity of fully sodiated Sn, Sn-hard carbon (HC) blends, and HC anodes in carbonate- and ether-based electrolytes. ARC measurements show that propylene carbonate (PC) causes earlier self-heating rate (SHR) onset and higher reactivity than tetraethylene glycol dimethyl ether (TEGDME), indicating inferior thermal stability. Sodiated Sn exhibits better thermal stability than sodiated HC, while Sn-HC blends show intermediate behavior that improves with increasing Sn content. Post-ARC analyses reveal desodiation of Na15Sn4 to metallic Sn with particle coalescence, whereas Sn-HC blends and HC retain finer morphologies. PC promotes Sn oxidation to SnO, while TEGDME suppresses oxide formation; NaPF6-containing electrolytes additionally form NaF. DFT calculations show that PC adsorption lowers Na extraction energy and enhances interfacial electronic interactions, facilitating Na release and reductive decomposition. These results establish a direct correlation between solvent-dependent reaction pathways and thermal stability in SIB alloy anodes.

Accelerating rate calorimetry

An integrated in-situ coordination strategy enabling high-performance layered cathodes for sodium-ion batteries

O3-type layered transition metal oxide cathodes hold tremendous potential in sodium-ion batteries (SIBs) due to their low cost and high energy density. However, the structure instability associated with detrimental phase transitions and severe interface parasitic reactions exacerbate the material's electrochemical performance degradation. Herein, we develop an integrated in-situ coordination strategy via heteroatomic modulation inducing coherent epitaxial layer to collaboratively enhance the overall framework robustness from surface to bulk. The theoretical calculation and multiple in/ex-situ characterizations demonstrate the charge density around oxygen is redistributed, which promotes the electron localization, thus widening the NaO 2 lattice space and accelerating the Na + transport dynamics. Furthermore, the formed strengthened oxygen bond energy effectively distributes the long-range coordination of Mn 3+ O 6 octahedron, thereby alleviating Jahn-Teller distortion and local stress. Importantly, the in-situ formed conformal buffer layer dramatically relieves the adverse interface side reactions, facilitating the construction of robust cathode-electrolyte interface, which ameliorate the whole structure stability of designed materials. Consequently, the optimized NFMZ@NZO-1.0 exhibits the excellent cycling stability with 80.2% capacity retention after 300 cycles at 1C, and delivers a high discharge capacity of 107.1 mAh g −1 at 10C. In conclusion, this distinctive coupling strategy provides valuable insights for developing high-performance layered cathode materials in SIBs.

Coherent epitaxial layer

First Principles Study of Aluminum Doped Polycrystalline Silicon as a Potential Anode Candidate in Li‐ion Batteries

Addressing sustainable energy storage remains crucial for transitioning to renewable sources. While Li‐ion batteries have made significant contributions, enhancing their capacity through alternative materials remains a key challenge. Micro‐sized silicon is a promising anode material due to its tenfold higher theoretical capacity compared to conventional graphite. However, its substantial volumetric expansion during cycling impedes practical application due to mechanical failure and rapid capacity fading. A novel approach is proposed to mitigate this issue by incorporating trace amounts of aluminum into the micro‐sized silicon electrode using ball milling. Density functional theory (DFT) is employed to establish a theoretical framework elucidating how grain boundary sliding, a key mechanism involved in preventing mechanical failure is facilitated by the presence of trace aluminum at grain boundaries. This, in turn, reduces stress accumulation within the material, reducing the likelihood of failure. To validate the theoretical predictions, capacity retention experiments are conducted on undoped and Al‐doped micro‐sized silicon samples. In conclusion, the results demonstrate significantly reduced capacity fading in the doped sample, corroborating the theoretical framework and showcasing the potential of aluminum doping for improved Li‐ion battery performance.

25 ENERGY STORAGE

Eliminating chemo-mechanical degradation of lithium solid-state battery cathodes during >4.5 V cycling using amorphous Nb2O5 coatings

Abstract Lithium solid-state batteries offer improved safety and energy density. However, the limited stability of solid electrolytes (SEs), as well as irreversible structural and chemical changes in the cathode active material, can result in inferior electrochemical performance, particularly during high-voltage cycling (>4.3 V vs Li/Li + ). Therefore, new materials and strategies are needed to stabilize the cathode/SE interface and preserve the cathode material structure during high-voltage cycling. Here, we introduce a thin (~5 nm) conformal coating of amorphous Nb 2 O 5 on single-crystal LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathode particles using rotary-bed atomic layer deposition (ALD). Full cells with Li 4 Ti 5 O 12 anodes and Nb 2 O 5 -coated cathodes demonstrate a higher initial Coulombic efficiency of 91.6% ± 0.5% compared to 82.2% ± 0.3% for the uncoated samples, along with improved rate capability (10x higher accessible capacity at 2C rate) and remarkable capacity retention during extended cycling (99.4% after 500 cycles at 4.7 V vs Li/Li + ). These improvements are associated with reduced cell polarization and interfacial impedance for the coated samples. Post-cycling electron microscopy analysis reveals that the Nb 2 O 5 coating remains intact and prevents the formation of spinel and rock-salt phases, which eliminates intra-particle cracking of the single-crystal cathode material. These findings demonstrate a potential pathway towards stable and high-performance solid-state batteries during high-voltage operation.

Science & Technology - Other Topics

Manganese‐Based Spinel Cathodes: A Promising Frontier for Solid‐State Lithium‐Ion Batteries

Recently, all-solid-state lithium-ion batteries (ASSLIBs), which exhibit improved safety and enhanced energy density compared to conventional commercialized lithium-ion batteries (LIBs), thereby have garnered extensive research interest. Among the promising cathode candidates, Mn-based spinel cathodes LiMn 2 O 4 (LMO) and LiNi 0.5 Mn 1.5 O 4 (LNMO), with the unique characteristics of low cost, structural stability, and 3D Li-ion diffusion channels, have demonstrated excellent performance in LIBs and presented great potential in ASSLIBs applications. However, several challenges, including structural degradations, poor interfacial contact, large interfacial resistance, and Mn-dissolution/diffusion during the electrochemical cycling, hinder their practical applications and commercialization in the ASSLIBs. Particularly, the high-voltage LNMO cathodes suffer from the challenge of electrochemical incompatibility with most of the solid-state electrolytes (SSEs). Herein, the spinel structure, the electrochemical behavior, and the structural degradation of the LMO/LNMO are explored. The characteristics and recent progress of the mitigating strategies to the challenges of various SSEs, including polymer-, oxide-, composite-, sulfide-, halide-, and LiPON-based SSEs, are introduced when paired with LMO/LNMO. Finally, the directions for future research to advance Mn-based spinel cathodes and fulfill the requirements of the next-generation ASSLIBs are also discussed.

Dou, Yu [Concordia University, Montreal, QC (Canad

Mechanical, Electrochemical & Thermal Models - Training (CRADA CRD-19-00798 Final Report)

Under the proposed effort in partnership with Hyundai Motor Company (HMC), the National Renewable Energy Laboratory (NLR) will host Dr. Jaeyoung Lim from HMC for a period of one year to jointly develop mathematical models for battery cells and modules subject to mechanical crush. NLR will assist with the development of mathematical models that Dr. Lim will incorporate into his research effort on new concepts of mobility with electric vehicles.

33 ADVANCED PROPULSION SYSTEMS

Catalytic disproportionation on carbon superstructures enables long-life, high-loading Li–S batteries

Electrocatalysis has been widely explored as an effective strategy to accelerate polysulfide (PS) conversion and suppress the shuttle effect in lithium–sulfur (Li–S) batteries. However, the underlying mechanisms remain elusive, and electrocatalytic reactions are inactive during cell resting. In this work, we reveal and quantitatively analyze a previously unrecognized sulfur reduction route (SRR) driven by catalytic disproportionation at the carbon cathode surface—fundamentally distinct from conventional electrocatalysis. Unlike conventional stepwise pathways, this SRR enables high-order polysulfides (Sₓ²⁻, x = 5–8) to directly convert into S₈ and Li₂S₂, bypassing low-order intermediates. This sulfur-reduction shortcut is systematically elucidated through high-performance liquid chromatography, revealing the intrinsic catalytic contribution of carbon frameworks and the dynamic evolution of PS species. We demonstrate that carbon superstructures (CSS-0.5), assembled from nanosheet subunits with abundant N/O functionalities and interconnected charge-migration channels, synergistically promote this catalytic process. Benefiting from these features, CSS-0.5 delivers superior electrochemical performance under practical conditions, enabling high sulfur loading (6.0 mg cm⁻²) pouch cells with 80.5% capacity retention over 210 cycles. This study provides the first quantitative evidence of electrocatalytic disproportionation in Li–S batteries, offering mechanistic insights and design principles for advanced sulfur cathodes.

25 ENERGY STORAGE

Anode-less Solid-State Li–S Batteries Enabled by Fe-Stabilized Polysulfides

Anode-less solid-state lithium-sulfur batteries (SSLSBs) with lithium sulfide (Li 2 S) as the cathode promise a high energy density and ease of manufacturing. However, Li 2 S is plagued by poor conductivity, sluggish activation kinetics, and a poor cycle life. Here, in this study, we report an FeCl 3 -activated Li 2 S (FLS) cathode with solid-state polysulfide intermediates generated through a redox reaction between FeCl 3 and Li 2 S. This strategy is shown to boost the electrical conductivity of Li 2 S by 7 orders of magnitude and lower the activation barrier. During cycling, Fe plays a significant role in stabilizing the highly active polysulfide species, contributing to the exceptional electrochemical performance. The FLS cathode achieves 80% capacity retention over 500 cycles with >99% Li 2 S utilization. Furthermore, a Li-metal-free (anode-less) full cell retained over 80% of its initial capacity after 240 cycles. This work underscores the promise of leveraging Fe-stabilized polysulfides in enabling high-energy, long-lasting, solid-state Li-S batteries.

25 ENERGY STORAGE

Liquified SO 2 induced solid/cathode electrolyte interphase for lithium ion batteries

Formation of robust solid/cathode electrolyte interphases (S/CEI) is vital for long-term stability and high-performance operation of lithium-ion batteries (LIBs), particularly under high voltage regimes. However, engineering electrochemically stable S/CEIs that effectively suppress interfacial side reactions remains a key challenge. Herein, we introduce a liquefied sulfur dioxide (SO 2 )– ionic liquid complex as a fluorine-free multifunctional electrolyte additive for the first time that significantly improves the formation of sulfate/sulfite-rich S/CEI layers at both graphite and NMC811 interfaces. The unique SO 2 -N coordination with a 1,2,4-triazolide-based ionic liquid enables homogeneous SO 2 dissolution, resulting in controlled SO 2 decomposition during the initial electrochemical cycle. This decomposition yields sulfur-rich interphase species that stabilize the electrolyte-electrode interface, reduce impedance growth, and lessen electrolyte decomposition. Electrochemical tests show significantly improved cycle life, reduced polarization, and increased Coulombic efficiency for both anodes and cathodes. XPS confirms the presence of SO 2 -derived surface species that contribute to interfacial stability. In conclusion, this approach highlights a new direction for interphase engineering using liquefied gas additives and opens pathways for sulfur-based S/CEI chemistry in advanced battery systems.

Graphite

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

Composite Lithium Metal Structure to Mitigate Pulverization and Enable Long‐Life Batteries

In lithium metal batteries, non‐uniform stripping of lithium results in pit formation, which promotes subsequent non‐uniform, dendritic deposition. This viscous cycle leads to pulverization of lithium which promotes cell shorting or capacity degradation, symptoms further exaggerated by high electrode areal loading and lean electrolytes. Here, to address this challenge, a composite lithium metal anode is engineered that contains uniformly distributed, nanometer‐sized carbon particles. This composite lithium is shown to strip more uniformly since the growth of non‐uniform pits is intercepted by the carbon particles. This mechanism is corroborated by a continuum electrochemical model. Subsequent lithium deposition on carbon particles is also found to be more uniform than on the surface with irregular pits. Notably, the pulverization rate of composite lithium is 26 times slower than that of commercial lithium. Moreover, in a Li‐S battery with sulfurized polyacrylonitrile cathode, the use of the composite anode extends the cycle life by three times when the areal capacity is 8 mAh cm −2 . The approach of using an engineered lithium composite structure to address challenges during both stripping and plating can inform future designs of lithium metal anodes for high areal capacity operations.

high areal capacity