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At least 145 records · Page 8

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DOE OSTI2023

Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods

A lithium ion-conductive solid electrolyte including a freestanding inorganic vitreous sheet of sulfide-based lithium ion conducting glass is capable of high performance in a lithium metal battery by providing a high degree of lithium ion conductivity while being highly resistant to the initiation and/or propagation of lithium dendrites. Such an electrolyte is also itself manufacturable, and readily adaptable for battery cell and cell component manufacture, in a cost-effective, scalable manner.

Visco, Steven J.↗

DOE OSTI2024

Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods

Visco, Steven J.↗

DOE OSTI2021

Interconnected cathode-electrolyte double-layer enabling continuous Li-ion conduction throughout solid-state Li-S battery

All-solid-state lithium (Li) batteries with high energy density are a promising solution for the next-generation energy storage systems in large-scale devices. To simultaneously overcome the challenges of poor ionic conduction of solid electrolytes and shuttling of active materials, here we introduce a functional electrolyte-cathode bilayer framework with interconnected LLAZO channels from the electrolyte into the cathode for advanced solid-state Li-S batteries. Differing from the traditional solid-state batteries with separated layer compositions, the introduced bilayer framework provides ultrafast and continuous ion/electron conduction. Instead of transferring Li+ across the polymer and garnet phases which involve huge interfacial resistance, Li+ is directly conducted through the LLAZO channels created continuously from the cathode layer to the solid electrolyte layer, significantly shortening the diffusion distance and facilitating the redox reaction of sulfur and sulfides. A stable cycle life is demonstrated in the prototype Li-S solid-state batteries assembled with the introduced LLAZO-LLAZO@CNF interconnected bilayer framework. High capacity is obtained at room temperature, indicating the superior electrochemical properties of the bilayer framework that result from the unique design of the interconnected LLAZO garnet phase.

25 ENERGY STORAGE↗

DOE OSTI2020

High-Energy All-Solid-State Organic–Lithium Batteries Based on Ceramic Electrolytes

Recent studies have identified unique properties of organic battery electrode materials such as moderate redox potentials and mechanical softness which are uniquely beneficial for all-solid-state batteries based on ceramic electrolytes. Here, we further explore the promise of organic materials and demonstrate a sulfide electrolyte- based organic-lithium battery with a specific energy of 828 Wh kg –1 , rivaling the state-of- the-art of all-solid-state batteries. Two innovation steps are responsible for the accomplishment. First, the combination of lithium anode and the high-capacity cathode material pyrene-4,5,9,10-tetraone ensures a high theoretical specific energy. Second, the microstructure of the organic cathode is optimized with the introduction of cryomilling, a technique common to processing soft materials but not familiar to electrode fabrication. The cathode material utilization increases to 99.5% as a result, up from the 55–89% previously reported for ceramic electrolyte-based solid-state organic batteries. In conclusion, the improvement highlights the special requirements of solid-state organic electrodes for microstructural engineering while preserving the chemical integrity of components.

25 ENERGY STORAGE↗

DOE OSTI2024

Decoupling first-cycle capacity loss mechanisms in sulfide solid-state batteries

Solid-state batteries (SSBs) promise more energy-dense storage than liquid electrolyte lithium-ion batteries (LIBs). However, first-cycle capacity loss is higher in SSBs than in LIBs due to interfacial reactions. The chemical evolution of key interfaces in SSBs has been extensively characterized. Electrochemically, however, we lack a versatile strategy for quantifying the reversibility of solid electrolyte (SE) redox for established and next-generation SSB electrolytes. In this work, we perform tailored electrochemical tests and operando X-ray diffraction to disentangle reversible and irreversible sources of capacity loss in positive electrodes composed of Li 6 PS 5 Cl SE, Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (NMC), and carbon conductive additives. We leverage an atypically low voltage cutoff (2.0 V vs. Li/Li + ) to quantify the reversibility of SE redox. Using slow (5.5 mA g NMC −1 ) cycling paired with >100 h low-voltage holds, our cells achieve a surprising 96.2% first-cycle coulombic efficiency, which is higher than previously reported (mean: 72%, maximum: 91.6% across surveyed literature). We clarify that sluggish NMC relithiation kinetics have been historically mistaken for permanently irreversible capacity loss. In conclusion, through systematic decoupling of loss mechanisms, we uncover the unexpected reversibility of SE redox and isolate the major contributors to capacity loss, outlining a strategy for accurate assessment of next-generation SE materials and interface modifications.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1973

Residual water bactericide monitor development program

A silver-ion bactericidal monitor is considered for the Space Shuttle Potable Water System. Potentiometric measurement using an ion-selective electrode is concluded to be the most feasible of available techniques. Four commercially available electrodes and a specially designed, solid-state, silver-sulfide electrode were evaluated for their response characteristics and suitability for space use. The configuration of the solid-state electrode with its Nernstian response of 10 to 10,000 ppb silver shows promise for use in space. A pressurized double-junction reference electrode with a quartz-fiber junction and a replaceable bellows electrolyte reservoir was designed verification-tested, and paired with a solid-state silver-sulfide electrode in a test fixture.

Source record↗

DOE OSTI2020

Review of Emerging Potassium–Sulfur Batteries

Abstract This is the first review on potassium–sulfur (K–S) batteries (KSBs), which are emerging metal battery (MB) systems. Since KSBs are quite new, there are fundamental questions regarding the electrochemistry of S‐based cathode and of K metal anode, as well as the holistic aspects of full‐cell performance. The manuscript begins with a critical discussion regarding the potassium–sulfur electrochemistry and on how it differs from the much better‐known lithium–sulfur. Cathodes are discussed next, focusing on the role of sulfur structure, carbon host chemistry and porosity, and electrolytes in establishing the reversible potassium sulfide K 2 S n phase sequence, the parasitic polysulfide shuttle, pulverization‐driven capacity fade, etc. Following is a discussion of solid‐state electrolytes (SSEs), including of hybrid solid–liquid systems that show much promise. Potassium metal anodes are then critically reviewed, emphasizing electrolyte reactions to form stable versus unstable solid electrolyte interphase (SEI), covering the current understanding of potassium dendrites, and highlighting the deep‐eutectic K–Na alloying approaches for room temperature liquid anodes. The manuscript concludes with K–S batteries, focusing on cell architectures and providing quantitative performance comparisons as master plots. Unanswered scientific/technological questions are identified, emerging research opportunities are discussed, and potential experimental and simulation‐based studies that can unravel these unknowns are proposed.

Ding, Jia↗

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 OSTI2022

Enabling Conversion-Type Iron Fluoride Cathode by Halide-Based Solid Electrolyte

The practical application of low-cost and energy-dense iron fluoride cathodes has been hindered by the first cycle electrochemical irreversibility, cycling instability, and large voltage hysteresis. Here, we report that these challenges may be overcome by the utilization of halide-based solid electrolytes (SEs). The excellent electrochemical stability of halide-based SEs enables a complete conversion and deconversion of FeF 2 which cannot be achieved with sulfide-based SEs. Due to restricted and reversible decomposition of SE, prevention of Fe dissolution, mechanical confinement of active material, as well as improved electrode kinetics, solid-state FeF 2 cathode with halide-based SE demonstrated superior electrochemical performance compared with FeF 2 electrodes in liquid electrolytes, with a high 1st cycle coulombic efficiency (~100 %), high specific capacity (~600 mAh/g), long cycle life (>100 cycles) and high-rate performance (up to 2C). In conclusion, our results suggest solidifying the batteries may be a viable approach to addressing the long-standing key challenges of iron fluoride cathodes.

25 ENERGY STORAGE↗

DOE OSTI2022

High-Energy Solid-State Lithium Batteries with Organic Cathode Materials (Final Report)

Organic materials made from abundant elements via low-energy processes are emerging as sustainable and low-cost alternatives to transition metal oxides as the electrode materials for high- energy batteries in the wake of supply chain and environmental issues associated with critical materials during the transition to clean energy. Organic insertion materials (OIMs) offer material- level energy comparable to transition metal oxides, but they have durability difficulties owing to dissolving in common liquid electrolytes. Combining ceramic-based solid electrolytes with organic electrode materials is one intriguing solution. The goal of this project is to design and synthesize high-energy OIMs, to understand the chemical dynamics and mechanical properties at the OIM-sulfide interface during electrochemical cycling, and to develop methods for constructing the optimum cathode microstructure, which will lead to improved electrochemical performance. The project team has accomplished the following over the last four years: (a) demonstrating that the mechanical softness of organic electrode materials is uniquely beneficial in suppressing crack formation at the electrode-electrolyte interface during cell operation; (b) understanding the interaction between cathode microstructure and the mechanical properties of individual components; and (c) establishing predictive control of cathode microstructure by tuning the mechanical properties of solid electrolytes and OIMs; (d) determining the chemical combability of sulfide electrolyte with high-energy OIMs and finally (f) laying out a road map toward a specific energy of 500 Wh kg -1 for solid-state lithium batteries. 14 publications resulted from this project.

25 ENERGY STORAGE↗

DOE OSTI2022

Reviving the rock-salt phases in Ni-rich layered cathodes by mechano-electrochemistry in all-solid-state batteries

The rock-salt phase (RSP) formed on the surface of Ni-rich layered cathodes in liquid-electrolyte lithium-ion batteries is conceived to be electrochemically "dead". Here we show massive RSP forms in the interior of LiNi x Mn y Co (1–x-y) O 2 (NMC) crystals in sulfide based all solid state batteries (ASSBs), but the RSP remains electrochemically active even after long cycles. The RSP and the layered structure constitute a two-phase mixture, a material architecture that is distinctly different from the RSP in liquid electrolytes. The tensioned layered phase affords an effective percolation channel into which lithium is squeezed out of the RSPs by compressive stress, rendering the RSPs electrochemically active. Consequently, the ASSBs with predominant RSP in the NMC cathode deliver remarkable long cycle life of 4000 cycles at high areal capacity of 4.3 mAh/cm 2 . Our study unveils distinct mechano-electrochemistry of RSPs in ASSBs that can be harnessed to enable high energy density and durable ASSBs.

25 ENERGY STORAGE↗

DOE OSTI2022

Synthesis of Fluorine-Doped Lithium Argyrodite Solid Electrolytes for Solid-State Lithium Metal Batteries

Solid-state lithium metal batteries (SSLMBs) that utilize novel solid electrolytes (SEs) have garnered much attention because of their potential to yield safe and high-energy-density batteries. Sulfide-based argyrodite-class SEs are an attractive option because of their impressive ionic conductivity. Recent studies have shown that LiF at the interface between Li and SE enhances electrochemical stability. However, the synthesis of F-doped argyrodites has remained challenging because of the high temperatures used in the state-of-the-art solid-state synthesis methods. In this work, for the f irst time, we report F-doped Li 5+y PS 5 F y argyrodites with a tunable doping content and dual dopants (F-/Cl- and F-/Br-) that were synthesized through a solvent-based approach. Among all compositions, Li 6 PS 5 F 0.5 C l0.5 exhibits the highest Li-ion conductivity of 3.5 x 10 -4 S cm -1 at room temperature (RT). Furthermore, Li symmetric cells using Li 6 PS 5 F 0.5 Cl 0.5 show the best cycling performance among the tested cells. X-ray photoelectron spectroscopy and ab initio molecular dynamics simulations revealed that the enhanced interfacial stability of Li 6 PS 5 F 0.5 C l0.5 SE against Li metal can be attributed to the formation of a stable solid electrolyte interphase (SEI)-containing conductive species (Li 3 P), alongside LiCl and LiF. These findings open new opportunities to develop high-performance SSLMBs using a novel class of F-doped argyrodite electrolytes.

25 ENERGY STORAGE↗

DOE OSTI2025

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

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

25 ENERGY STORAGE↗

DOE OSTI2022

High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode

The development of all-solid-state Li–S batteries has been greatly impeded by dendrite growth and dendrite penetration, which are both related to the Li metal anode. As a compromised alternative, we report lithium silicide (Li x Si) as a dendrite-free and high-capacity anode with Li source. Here, the as-synthesized Li x Si is relatively soft, highly electronically conductive, and with a high Li diffusivity. These distinctive properties make Li x Si anode viable as an “all-electrochem-active” electrode (consisted of 100 wt.% Li x Si). Compared with the typical composite electrode, the all-electrochem-active electrode not merely maximizes the electrode-level energy density but also minimizes the electrolyte-related interfacial degradation. Li x Si symmetric cell demonstrates a reversible cycling at 4 mA cm –2 for over 320 h. Stress change and morphological evolution of the Li x Si electrode are investigated upon dealloying/alloying. When paired with a S cathode (active mass loading of 3 mg cm –2 ), Li x Si–S full cell shows a good cycling behavior over 500 cycles and rate performance (69% capacity retained at 1.2C) even at 25 °C.

25 ENERGY STORAGE↗

DOE OSTI2022

Novel Co‐Catalytic Activities of Solid and Liquid Phase Catalysts in High‐Rate Li‐Air Batteries

Abstract Li‐air batteries are considered strong candidates for the next‐generation energy storage systems designed for electrical transportation. However, low cyclability and current rates are two major drawbacks that hinder them from further realization. These issues necessitate the discovery of novel materials to significantly enhance the redox process of discharge products. In this study, a novel catalytic system comprised of tin sulfide (SnS) nanoflakes as a solid catalyst and tin iodide (SnI 2 ) as a dual‐functional electrolyte additive is discovered. This system enables operating the battery at high current rates up to 10 000 mA g −1 (corresponding to 1 mA cm −2 ). The SnS catalyst shows outstanding catalytic activity for both oxygen reduction and evolution reactions compared to carbon, noble metals, and other transition metal dichalcogenides. It also exhibits good structural integrity at high rates. The computations indicate numerous possible oxygen reduction sites without oxygen dissociations on the SnS surface through solution mechanism that is likely responsible for the formation of Li 2 O 2 . The calculations also indicate that the role of the SnI 2 is not only reacting with the lithium anode to provide protection but reducing the charge potential by promoting catalytic decomposition of the Li 2 O 2 . This work provides new novel additives for designing high‐rate Li‐air batteries.

25 ENERGY STORAGE↗

DOE OSTI2023

Lithiation Gradients and Tortuosity Factors in Thick NMC111-Argyrodite Solid-State Cathodes

Achieving high energy density in all-solid-state lithium batteries will require the design of thick cathodes, and these will need to operate reversibly under normal use conditions. We use high-energy depth-profiling X-ray diffraction to measure the localized lithium content of Li 1-x Ni 1/3 Mn 1/3 Co 1/3 O 2 (NMC111) through the thickness of 110 μm thick composite cathodes. The composite cathodes consisted of NMC111 of varying mass loadings mixed with argyrodite solid electrolyte Li 6 PS 5 Cl (LPSC). During cycling at C/10, substantial lithiation gradients developed, and varying the NMC111 loading altered the nature of these gradients. Microstructural analysis and cathode modeling showed this was due to high tortuosities in the cathodes. This was particularly true in the solid electrolyte phase, which experienced a marked increase in tortuosity factor during the initial charge. Our results demonstrate that current distributions are observed in sulfide-based composites and that these will be an important consideration for practical design of all-solid-state batteries.

25 ENERGY STORAGE↗

DOE OSTI2024

Phase Field Modeling of Pressure Induced Densification in Solid Electrolytes

Adoption of dense and homogeneous solid electrolytes can possibly mitigate the propagation of lithium dendrites and enable lithium metal anodes. Application of external pressure helps to minimize the sintering temperature in oxide ceramics and can potentially densify softer sulfide electrolytes even under room temperature conditions. Here, a previously developed phase field-based computational scheme for predicting the high-temperature sintering-induced densification of oxide ceramic solid electrolytes is extended in the present context to capture the influence of external pressure for densifying solid electrolytes. Two different bulk deformation mechanisms, namely, "reorganization" and "creep deformation," are dominant under external pressure, which is different from the surface and grain-boundary diffusion-induced densification of solid electrolytes that occurs during high temperature sintering. External pressure also increases the points of contact between the particles, which further enhances the propensity of diffusion-induced sintering process. Results obtained from simulations indicate that densification under external pressure is independent of the solid electrolyte particle morphology. Finally, a phase map is generated between applied pressure and temperature for achieving complete densification of oxide ceramics, which can possibly guide the synthesis of thin and dense solid electrolyte separators.

25 ENERGY STORAGE↗

DOE OSTI2022

K 3 SbS 4 as a Potassium Superionic Conductor with Low Activation Energy for K–S Batteries

Abstract Solid‐state K‐ion conducting electrolytes are key elements to address the current problems in K secondary batteries. Here, we report a sulfide‐based K‐ion conductor K 3 SbS 4 with a low‐activation energy of 0.27 eV. W‐doped K 3− x Sb 1− x W x S 4 ( x =0.04, 0.06, 0.08, 0.10 and 0.12) compounds were also explored for increasing vacancy concentrations and improving ionic conductivity. Among them, K 2.92 Sb 0.92 W 0.08 S 4 exhibits the highest conductivity of 1.4×10 −4 S cm −1 at 40 °C, which is among the best reported potassium‐ion conductors at ambient temperature. In addition, K 2.92 Sb 0.92 W 0.08 S 4 is electrochemically stable with long‐chained potassium polysulfide of K 2 S x . A room‐temperature solid potassium–sulfur (K−S) battery system has therefore been successfully demonstrated, which is the first K−S battery prototype using non‐commercial inorganic‐based electrolyte to block the polysulfide shuttle.

Shao, Jieren↗