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DOE OSTI2025

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↗
DOE OSTI2026

From Cation Order to Disorder: Unlocking Ion Transport Pathways in Li–Zn–Zr–Cl Halospinels

Lithium metal chloride halospinels of the general formula Li 2 MCl 4 are a promising class of earth-abundant ion conductors for all-solid-state batteries. However, poor roomtemperature ionic conductivity has historically limited their use in practical applications. Here, we substitute Zr 4+ into Li 2 ZnCl 4 along the series Li 2−2x/3 Zn 1−x Zr 2x/3 Cl 4 (x = 0, 0.1, 0.3, 0.4, 0.6, 0.9, and 1.0) to understand how cation disorder and vacancy tuning impact ion transport in “normal” halospinels. Aliovalent Zr 4+ substitution increases ionic conductivity by nearly 5 orders of magnitude, from 1.320(3) × 10 −9 S cm −1 in Li 2 ZnCl 4 to 6.74(1)× 10 −5 S cm −1 for x = 0.6. Average and local structure characterization through synchrotron X-ray diffraction (SXRD) and neutron pair distribution function (nPDF) analysis reveal that Zr 4+ redistributes the Zn 2+ and Li + sublattices into previously unoccupied interstitial sites, which form new low-energy hopping pathways that facilitate ion transport. We rationalize the dramatic rearrangement of the cation local structure by considering the coordination preferences of the cations and the potential electrostatic penalties incurred by the higher-valent Zr 4+ cations. This work delivers an atomistic understanding of substitution-induced cation disorder and ion transport properties in a new family of earth-abundant halospinels.

Cardoza, Abby M. [Colorado School of Mines, Golden↗
DOE OSTI2025

Unveiling the lithium-ion transport mechanism in Li{sub 2}ZrCl{sub 6} Solid-State Electrolyte {ital via} deep learning-accelerated molecular dynamics simulations.

Lithium zirconium chlorides (LZCs) present a promising class of cost-effective solid electrolytes for next-generation all-solid-state batteries. The unique crystal structure of LZCs plays a crucial role in facilitating lithium-ion mobility, which further affects the electrochemical performance. To understand the underlying mechanism governing ion transport, we employed deep learning-accelerated molecular dynamics simulation on Li2ZrCl6 (trigonal alpha- and monoclinic beta-LZC), focusing specifically on the zirconium coordination environment. Our results reveal that disordered alpha-LZC exhibits the highest ionic conductivity, while beta-LZC demonstrates significantly lower conductivity, closely aligning with experimental findings. The study confirms that across all phases, lithium migration proceeds via the site-to-site hopping mechanism, where variations in site residence times critically impact the overall ionic conductivity. In alpha-LZCs, lithium ions prefer to anisotropically diffuse across interlayers as the result of a lower energy barrier, driven primarily by collective diffusion. In contrast, lithium ions in beta-LZC primarily isotropically diffuse within the intralayer, hindered by higher energy barriers and determined by individual diffusion. The variation in ZrCl6 2- octahedral unit softening, induced by the specific layered arrangement of zirconium atoms, emerges as a critical determinant of the energy barriers across the LZC phases. These atomic-scale insights into the transport processes provide valuable guidance for the rational design and optimization of LZCs-based electrolytes, accelerating their practical application in advanced energy storage technologies.

Guo, Hanzeng↗
DOE OSTI2025

A Unique Case of the “Goldilocks Rule” in Solid-State Electrolytes: Two Are Good, Four Are Too Many

We report the syntheses of two new series of methacrylate monomers with different backbones: ureidopyrimidinone (PU) and boron-substituted urea pyrimidine (U), which enhance both the mechanical and electrochemical properties of the solid-state electrolyte (SSE) while improving the cycle life of lithium iron phosphate (LiFePO 4 , LFP) cathodes. The PU backbone is characterized by four hydrogen bonds (H-bonds), while the U backbone bears only two. Importantly, our research reveals that two H-bonds in these monomers are optimal; in contrast, four are excessive. The exceptional mechanical properties and processability of the SSE with the U series additives, resulting from the optimal H-bonds, were unexpectedly achieved. This leads to the establishment of a “Goldilocks rule” for additive design. The key strategies include: 1) reducing hydrogen-bonding (H-bonding) sites by changing pyrimidinone to pyrimidine and 2) shifting from intermolecular to intramolecular H-bonding and π−π bonding. Furthermore, this reduction in H-bonding also offers significant advantages in processability. The advancement can be extended to electrode fabrication, making the manufacturing of all-solid-state batteries more practical and efficient.

hydrogen bonding↗
DOE OSTI2026

Aliovalent Anion Incorporation in Halide Na-ion Conductors for Enhanced Ionic Conductivity

Halide-based solid electrolytes (SEs), particularly zirconium (Zr)-centered halides, are attractive from a material cost perspective. Nevertheless, Zr-centered halide SEs are hindered by their low ionic conductivity. Here, in this study, we report on the cubic Na 3 ZrCl 5 S superionic conductor through strategic sulfur anion incorporation, achieving 10 times higher ionic conductivity than that of Na 2 ZrCl 6 . With the optimal composition, the highest ionic conductivity of 0.753 mS cm –1 is obtained for the 0.6Na 2 S–1.4NaCl–ZrCl 4 compound. When paired with a NaCrO 2 cathode, the assembled all-solid-state batteries (ASSBs) achieve a specific discharge capacity of 110 mA h g –1 at 0.1C and exhibit long-term cycling stability at 0.3C at room temperature over 1000 cycles (with 83% capacity retention). Moreover, in situ electrochemical impedance spectroscopy combined with distribution of relaxation times analysis reveal the dynamically interfacial stability between Na halide with electrodes. In conclusion, this work highlights the design and synthesis of advanced halide electrolytes through anion incorporation, paving the way for the development of next-generation ASSBs.

Guo, Xiaolin [Univ. of Louisville, KY (United Stat↗
DOE OSTI2026

Amorphous ZrCl 4 -Based Superionic Conductor as a Cost-Effective Solid Electrolyte for Batteries

Developing highly conductive and cost-effective solid electrolytes is essential for the commercialization of all-solid-state batteries (ASSBs). Zr-based halide electrolytes hold great promise due to their low estimated cost and high oxidation stability. However, the ionic conductivities of most of them are not high enough to enable moderate- and high-rate cycling of ASSBs. Here, fast ion transport is achieved in a group of cost-effective ZrCl 4 -based electrolytes via a design strategy to create highly disordered amorphous structures. Amorphous Li 0.8 ZrCl 4 (SO 4 ) 0.4 , with a low estimated cost of $21 kg –1 , achieves an ionic conductivity of 1.86 mS cm –1 at 25 °C. It also shows a high oxidation limit of 4.5 V vs Li/Li + and good compatibility with high-voltage cathodes, as demonstrated by the stable cycling of ASSBs (73.7% capacity retention after 1000 cycles at 1 C). Synchrotron X-ray diffraction, pair distribution function analysis, and electrochemical impedance spectroscopy reveal that the outstanding conductivity of these amorphous electrolytes is closely related to their short-range and medium-range ordering, revealing new insights for designing high-performance, cost-effective solid electrolytes.

Zhang, Guangxing [Georgia Institute of Technology,↗
DOE OSTI2025

Operando neutron imaging-guided gradient design of Li-ion solid conductor for high-mass-loading cathodes

High-mass-loading cathodes are crucial for achieving high energy density in all-solid-state batteries from the lab scale to industry. However, as mass-loading increases, electrochemical performance is significantly compromised due to sluggish kinetics. In this work, operando neutron imaging is deployed on a high-mass-loading NMC 811 cathode of 33 mg/cm 2 (5.0 mAh/cm 2 ) and directly visualizes the lithiation prioritization of the cathode active material (CAM) from the solid electrolyte membrane side to the current collector side. In addition to the tortuosity, another key limitation on ion transfer in the cathode arises from the mismatch between the uniform distribution of the solid electrolyte (catholyte) in the conventional composite cathode and the non-uniform Li + flux generated by the faradaic reaction of CAMs. Therefore, we engineer a gradient in the catholyte concentration to match the Li + flux distribution as a means of eliminating the ion transfer obstacle. This approach demonstrates enhanced rate performance, even with high-mass-loading cathodes. A LiCoO 2 composite cathode with 100 mg/cm 2 high-mass-loading exhibits an areal capacity of 10.4 mAh/cm 2 at a current density of 2.25 mA/cm 2 . This work provides insight into the ion-transport limitation in thick cathodes and demonstrates an effective gradient design to overcome the kinetic barrier and achieve high battery performance.

Batteries↗
DOE OSTI2025

Mechanistic insights into superionic thioarsenate argyrodite solid electrolytes via machine learning interatomic potentials

The lithium argyrodite sulfide solid electrolyte Li 6 PS 5 Cl has attracted considerable interest for all-solid-state batteries owing to its high ionic conductivity, which can be further enhanced through ionic substitution. Although a variety of substitutions have been investigated, thioarsenate argyrodites remain comparatively underexplored. Here, we systematically investigate the phase stability and Li-ion conduction mechanisms in superionic Br-incorporated thioarsenate argyrodites using first-principles calculations and molecular dynamics simulations based on machine learning interatomic potentials (MLIPs). Systematic variation of S/Br site inversion reveals that an optimal degree of anion disorder significantly enhances inter-cage connectivity and facilitates long-range Li-ion diffusion. Configurational entropy serves as an effective quantitative descriptor of anion disorder, exhibiting a strong correlation with ionic conductivity. While greater anion disorder induced by site inversion and higher Br content enhances ionic conductivity up to 50 mS cm −1 , it simultaneously reduces structural stability. This trade-off results in an optimal window in which a moderate level of disorder yields conductivities exceeding 20 mS cm −1 while maintaining synthetic feasibility. In conclusion, this work highlights the reliability and efficiency of MLIPs for elucidating ion-transport mechanisms and accelerating the design of novel superionic argyrodites.

Jang, Myeongcho [Korea Institute of Science and Te↗
DOE OSTI2025

Anion sublattice design enables superionic conductivity in crystalline oxyhalides

Solid-state batteries are attractive energy storage systems as a result of their inherent safety, but their development hinges on advanced solid-state electrolytes (SSEs). Most SSEs remain largely confined to single-anion systems (e.g., sulfides, oxides, halides, and polymers). Through mixed-anion design strategy, we develop crystalline Li 3 Ta 3 O 4 Cl 10 (LTOC) and its derivatives with excellent ionic conductivities (up to 13.7 millisiemens per centimeter at 25°C) and electrochemical stability. The LTOC structure features mixed-anion spiral chains, consisting of corner-shared oxygen and terminal chlorine atoms, which induces continuous “tetrahedron-tetrahedron” Li-ion migration pathways with low energy barriers. Additionally, LTOC demonstrates holistic cathode compatibility, enabling solid-state batteries operation at 4.9 volts versus Li/Li + and low temperature, down to −50°C. In conclusion, these findings describe a promising class of superionic conductors for high-performance solid-state batteries.

Zhao, Feipeng [Western University, London, ON (Can↗
DOE OSTI2025

In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Halide-based solid-state electrolytes (SSEs) are promising candidates for next-generation all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and chemical stability. However, their poor interfacial compatibility with lithium metal anode and Li-In alloy significantly hinder practical application due to the requirement for a protective interlayer. In this study, a novel approach to overcome this limitation is presented by introducing iron (Fe) doping into Li 3 InCl 6 (LIC), which enables direct and stable contact with lithium-indium (Li-In) metal without a protective interlayer. Thermodynamic and computational analyses identified Fe 3+ as a suitable dopant based on its similar reduction potential to In 3+ and structural compatibility within the halide lattice. The synthesized 10 at. % Fe-doped LIC exhibits high phase purity, retained ionic conductivity, and notably improved interfacial stability. Full-cell tests using Fe-LIC achieve over 300 cycles with 80 % capacity retention. At the same time, symmetric Li-In/ Fe-LIC/ Li-In cells sustain over 500 h of operation, representing the first reported long-term cycling of LIC-based ASSLB without a protective interlayer. In conclusion, this work establishes Fe doping as an effective strategy to stabilize halide SSEs of In system against Li-In alloy, thereby simplifying cell architecture and advancing the development of safer, high-performance halide-based solid-state electrolytes.

Halide-based solid-state electrolytes↗
DOE OSTI2026

Exploring sodium dynamics in the dilute oxygen regime of mixed oxy-sulfide NaPSiSO glasses

All-solid-state‑sodium batteries have great potential to lower the cost of grid-scale energy storage systems. However, they require a low cost, high conductivity solid electrolyte to become a reality. The electrochemical properties of mixed oxy-sulfide glasses NaPSiSO exceed those of either the pure sulfide or the pure oxide glass alone. In this work, we have tested models of sodium ion dynamics in the NaPSiSO series: zNa 2 S+(1-z)[(1-y)[(1-x)SiS 2 + xPS 5/2 ] + yNaPO 3 ] where 0.57 ≤ z ≤ 0.588, 0 ≤ x ≤ 0.35, and 0.15 ≤ y ≤ 0.35 using 23 Na nuclear magnetic resonance to directly probe the local fields and their fluctuations at the nuclear sites. We determined the distribution of activation energies in these materials arising from distributions of local environments and provided quantitative information about the connectivity of the ionic pathways through which the sodium ions move. We found that the sodium ion conduction dynamics were described as an ionic percolation through a Gaussian distribution of energy barriers and that the composition dependence of the ionic conductivity in the dilute oxygen regime is well-described by the Nernst-Einstein relation modified for percolation.

25 ENERGY STORAGE↗
DOE OSTI2025

Fast lithium ion diffusion in brownmillerite Li x Sr 2 Co 2 O 5

Transition metal oxides not only exhibits novel magnetic properties but also provides outstanding ionic transports. Ionic conductors have great potential for interesting tunable physical properties via ionic liquid gating and novel energy storage applications such as all-solid-state lithium batteries. In particular, low migration barriers and high hopping attempt frequency are the keys to achieve fast ion diffusion in solids. Taking advantage of the oxygen-vacancy channel in Li x Sr 2 Co 2 O 5 , we show that migration barriers of lithium ion are as small as 0.28–0.17 eV depending on the lithium concentration rates. Our first-principles calculation also investigated hopping attempt frequency and concluded the room temperature ionic diffusivity and ion conductivity are high as 10 −7 –10 −6 cm 2 s −1 and 10 −3 –10 −2 Scm −1 , respectively, which outperform most of perovskite-type, garnet-type, and sulfide Li-ion solid-state electrolytes. This work proves Li x Sr 2 Co 2 O 5 as a promising super-ionic conductor.

Crystallographic defects↗
DOE OSTI2025

Novel Superionic Na Conductors for Solid‐State Na batteries: Materials and Interface

This project aims to advance the fundamental understanding on how the cation or anion doping influence on the crystal structure, phase stability and ion transport of novel Na superionic conductors. Specifically, we focus on the Na 3-x A x SbS 4-y X y family solid electrolytes (A: cation dopant, X: anion dopant), a class of promising materials for all-solid-state sodium batteries owing to their high ionic conductivity and compositional tunability. By integrating materials synthesis, neutron scattering, and electrochemical characterization and theoretical simulations, this project sees to elucidate 1) how does the synthesis approaches (solid-state reaction, low-temperature reaction) on the phase purity and doping process; 2) how chemical doping (A: cation dopants such as Sn; X: anion dopants such as Se, F) modulate lattice dynamics and Na+ migration as well as interface stability toward Na metal. Specifically, this project’s proposed technology involves three objectives: (1) synthesize novel Na-ion conductors (anion or cation doped Na 3 SbS 4 ) with high phase purity and examine their structural features (e.g., phase stability); (2) understand Na-ion conductive properties of new Na-ion conductors through a combination of experimental characterizations and theoretical simulations; (3) investigate the interface stability of novel Na superionic conductors with electrode materials in solid-state Na batteries. These objectives will be achieved through combined experimental synthesis/characterizations and computational approaches. The obtained knowledge will provide a comprehensive synthesis-structure-property correlation, enabling the rational design of novel solid-state conductors with excellent conductivity and stability.

25 ENERGY STORAGE↗
DOE OSTI2025

Overcoming misconceptions in lithium metal polymer electrolyte batteries

Uncovering the truth of lithium polymer batteries. Lithium metal is the holy grail of anodes due to its 10-fold higher gravimetric capacity than graphite. All-solid-state lithium polymer electrolyte batteries are receiving significant attention due to their increased flexibility compared to inorganic solid-state electrolytes, which enhances processability, accommodates cell swelling, and enables more homogeneous interphases. However, prototype solid-state lithium polymer electrolyte batteries have been limited in their usage due to the low ionic conductivity of the electrolyte, which limits their ability to cycle lithium metal at high rates. In this opinion, we provide alternative interpretations of high-rate capability lithium metal polymer electrolytes and breakthroughs in highly ionically conductive all-solid-state polymer electrolytes. In addition, we provide guidance on how to characterize and evaluate polymer electrolytes in lithium metal batteries.

Waugh, John B↗
DOE OSTI2026

All‐Solid‐State Batteries With Mechanically Stable Interfaces Consisting of a Zero‐Strain Cation‐Disordered Rocksalt Cathode

Interface stabilization is critical to the development of working all‐solid‐state batteries. Rigid cathode/solid electrolyte interfaces often disintegrate due to anisotropic volume change of cathode‐active materials, resulting in irreversible capacity loss. Herein, we demonstrate that Li 1.211 Mo 0.467 Cr 0.3 O 2 (LMCO), a pioneering cation‐disordered rocksalt oxide (DRX) cathode that has intrinsically small volume change upon lithium intercalation, can be integrated with a thiophosphate‐based solid electrolyte for all‐solid‐state batteries. Interface stability of the all‐solid LMCO cell was investigated by electrochemical impedance spectroscopy, X‐ray micro‐computed tomography, and electron microscopy. Since LMCO was initially synthesized as a layered phase exhibiting a large volume change, interface disintegration can be observable in the early cycles. As layered LMCO phase‐transformed into DRX LMCO in subsequent cycles, reintegration of the interfaces occurs within a pressurized cell as a result of its zero‐stain behavior. Consequently, the DRX LMCO cathode maintains interface integrity, and thus electrical wiring, over an extended number of cycles, leading to improved capacity retention with small internal cell resistance.

DRX↗
DOE OSTI2026

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↗
DOE OSTI2023

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↗
DOE OSTI2026

Operando neutron radiography validates a parameter-free transport–kinetics model for thick solid-state battery cathodes

Tortuosity-weighted interfacial flux for lithium (TWIF-Li) predicts through-thickness Li gradients in thick composite all-solid-state cathodes without fitted parameters. Image-derived microstructures, GITT-derived concentration-dependent solid diffusion, and tortuosity-weighted interfacial kinetics reproduce operando neutron radiography across practical rates, delivering transferable design rules to suppress transport-limited reaction fronts.

Adam, Andre [ORNL] (ORCID:0000000245023033)↗