Reliable Fabrication of All-solid-state Lithium Batteries with High Cell-level Specific Energy (SOLIFAB)
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Liang, Yanliang↗
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A Fluoride-Rich Solid-Like Electrolyte Stabilizing Lithium Metal Batteries
To address the problems associated with Li metal anodes, a fluoride-rich solid-like electrolyte (SLE) that combines the benefits of solid-state and liquid electrolytes is presented. Its unique triflate-group-enhanced frame channels facilitate the formation of a functional inorganic-rich solid electrolyte interphase (SEI), which not only improves the reversibility and interfacial charge transfer of Li anodes but also ensures uniform and compact Li deposition. Furthermore, these triflate groups contribute to the decoupling of Li + and provide hopping sites for rapid Li + transport, enabling a high room-temperature ionic conductivity of 1.1 mS cm -1 and a low activation energy of 0.17 eV, making it comparable to conventional liquid electrolytes. Consequently, Li symmetric cells using such SLE achieve extremely stable plating/stripping cycling over 3500 h at 0.5 mA cm -2 and support a high critical current up to 2 mA cm -2 . Here, the assembled Li||LiFePO 4 solid-like batteries exhibit exceptional cyclability for over 1 year and a half, even outperforming liquid cells. Additionally, high-voltage cylindrical cells and high-capacity pouch cells are demonstrated, corroborating much simpler processibility in battery assembly compared to all-solid-state batteries.
25 ENERGY STORAGE↗
Broadening solid ionic conductor selection for sustainable and earth-abundant solid-state lithium metal batteries
We propose a universal solid electrolyte design that broadens the selection of ceramic LICs for solid-state lithium metal batteries, without requirements of electronic insulation or (electro)chemical stability.
Chemistry↗
All-Solid-State Lithium–Sulfur Batteries Enhanced by Redox Mediators
We report redox mediators (RMs) play a vital role in some liquid electrolyte-based electrochemical energy storage systems. However, the concept of redox mediator in solid-state batteries remains unexplored. Here, we selected a group of RM candidates and investigated their behaviors and roles in all-solid-state lithium-sulfur batteries (ASSLSBs). The soluble-type quinone-based RM (AQT) shows the most favorable redox potential and the best redox reversibility that functions well for lithium sulfide (Li 2 S) oxidation in solid polymer electrolytes. Accordingly, Li 2 S cathodes with AQT RMs present a significantly reduced energy barrier (average oxidation potential of 2.4 V) during initial charging at 0.1 C at 60 °C and the following discharge capacity of 1133 mAh g s -1 . Using operando sulfur K-edge X-ray absorption spectroscopy, we directly tracked the sulfur speciation in ASSLSBs and proved that the solid-polysulfide-solid reaction of Li 2 S cathodes with RMs facilitated Li 2 S oxidation. In contrast, for bare Li 2 S cathodes, the solid-solid Li 2 S-sulfur direct conversion in the first charge cycle results in a high energy barrier for activation (charge to ~4 V) and low sulfur utilization. The Li 2 S@AQT cell demonstrates superior cycling stability (average Coulombic efficiency 98.9% for 150 cycles) and rate capability owing to the effective AQT-enhanced Li-S reaction kinetics. This work reveals the evolution of sulfur species in ASSLSBs and realizes the fast Li-S reaction kinetics by designing an effective sulfur speciation pathway
25 ENERGY STORAGE↗
A review of composite polymer-ceramic electrolytes for lithium batteries
All solid-state lithium batteries are garnering attention in both academia and industry. Lithium-ion conductive polymers and lithium-ion conductive ceramics are the two major classes of solid electrolytes that have prevalently been pursued for many years. However, each of them has its own advantages and disadvantages. One approach to overcome the disadvantages and get the best out of each of those materials is a solid composite electrolyte that combines the advantages of inorganic ceramic electrolytes and solid polymer electrolytes. Such composite electrolytes can offer acceptable ionic conductivity, high mechanical strength, and favorable interfacial contact with electrodes, which can greatly improve the electrochemical performance of all-solid-state batteries compared to cells based on a polymer electrolyte alone or a ceramic electrolyte alone. We present in this review the state-of-the-art composite polymer-ceramic electrolytes in view of their electrochemical and physical properties for the applications in lithium batteries. The review mainly encompasses the polymer matrices, various ceramic filler materials, and the polymer/ceramics composite systems. Specifically, the structures, ionic conductivities, electrochemical/chemical stabilities, and fabrications of solid composite electrolytes are discussed in-depth. On the basis of previous work, a perspective on future research directions is highlighted for developing high-performance composite polymer-ceramic electrolytes.
25 ENERGY STORAGE↗
Li 2 S 6 ‐Integrated PEO‐Based Polymer Electrolytes for All‐Solid‐State Lithium‐Metal Batteries
Abstract The integration of Li 2 S 6 within a poly(ethylene oxide) (PEO)‐based polymer electrolyte is demonstrated to improve the polymer electrolyte's ionic conductivity because the strong interplay between O 2− (PEO) and Li + from Li 2 S 6 reduces the crystalline volume within the PEO. The Li/electrolyte interface is stabilized by the in situ formation of an ultra‐thin Li 2 S/Li 2 S 2 layer via the reaction between Li 2 S 6 and lithium metal, which increases the ionic transport at the interface and suppresses lithium dendrite growth. A symmetric Li/Li cell with the Li 2 S 6 ‐integrated composite electrolyte has excellent cyclability and a high critical current density of 0.9 mA cm −2 at 40 °C. Impressive electrochemical performance is demonstrated with all‐solid‐state Li/LiFePO 4 and high‐voltage Li/LiNi 0.8 Mn 0.1 Co 0.1 O 2 cells at 40 °C.
Fang, Ruyi↗
Elastic NaxMoS2-carbon-BASE triple interface direct robust solid-solid interface for all-solid-state Na-S batteries
The promises of all-solid-state (ASS) sodium batteries for the next generation energy storage are widely recognized but their developments have been severely constrained by the difficulties to design favorable solid-solid interfaces for unhindered Na-ion transport. Using the most promising ß?-Al2O3 solid state electrolyte (BASE) as a platform, we demonstrate here a triple nanojunction strategy that provides simultaneous strong Na adhesion and continuous Na-ions diffusion at solid-solid interface. Such triple junctions (NaxMoS2-carbon-BASE) were constructed by adhering ternary composite Na anodes containing dispersed 3 wt% MoS2 and 3 wt% carbon on BASE, and provide nearly complete adhesion of Na on BASE with a much smaller contact angle (~ 45o vs. 120o of pristine Na). The composite Na anodes exhibited ~ 3 times improved elastic property and the synergy of NaxMoS2 and carbon provides the required ionic and electronic diffusion channels at solid-solid interface, which significantly improve Na utilization and resist premature failure due to loss of solid-solid contact as Na shrink during high capacity stripping. As a result, Na metal at the triple junction exhibited more than five time reduced charge transfer resistance and at least 200 hours stable battery cycling at practical current densities. The novel anode architecture also enabled high capacity cycling of prototype ASS sodium sulfur batteries when coupled with advanced sulfur cathodes containing intrinsic Na-ions diffusion channels and redox catalytic mediators, leading to stable cycling with specific capacity of 1110 mAh g-1.
ß”-Al2O3 solid electrolyte, solid state batteries,↗
In Situ Visualization of Li-Whisker with Grating-Interferometry-Based Tricontrast X-ray Microtomography
The lithium-ion battery has demonstrated tremendous economic and social impacts. Upon battery operation under different conditions, lithium changes its chemical state and physical formation, leading to undesired side reactions, e.g., lithium dendrite growth that degrades the cell performance and causes safety concerns. In situ detection and visualization of lithium metal in functional batteries could offer insights with both scientific and industrial significance but remain a frontier challenge. In this work, we demonstrate in situ three-dimensional imaging of lithium whisker using a grating-interferometry-based tricontrast X-ray microtomography method. Our approach explicitly reveals the micromorphology of the electrochemically developed porous lithium whisker with micrometer-level spatial resolution while offering sensitivity to the nanoporosity that is smaller than the nominal resolution limit. Our result reveals valuable structural information on the lithium whisker that is otherwise inaccessible. This method is also readily applicable to a broad range of battery research, including all-solid-state batteries.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Organic-Inorganic Reaction of Li-Containing thin film: Structure of Lithium Propane Dioxide via MLD
In combining organometallic with organic precursors, molecular layer deposition (MLD) offers not only an expanded portfolio of molecular combinations but specifically the possibility of tuning mechanical properties for more robust functionality. This is appealing for applications in energy storage, where ion transport in and out of electrodes causes significant stress/strain cycling. It is particularly opportune for Li-ion solid state batteries (LISSBs), where electrode and solid electrolyte structures are usually arranged densely for high power and energy. Despite diverse MLD applications to date, little prior research has been aimed at Li-containing MLD materials and processes. Here, we report the MLD growth and process for a lithium-containing organic thin film using lithium tert-butoxide (LiO t Bu) and 1,3-propanediol, leading to an MLD film of lithium propane dioxide, Li 2 O 2 C 3 H 6 (LPDO), identified through X-ray photoelectron spectroscopy (XPS) and ab initio calculations. The growth showed self-limiting behavior for both precursors, with significant nucleation delay before linear growth at 0.23 Å/cycle at 150 °C, and 0.15 Å/cycle at 200 °C. XPS-determined stoichiometry was Li 1.6 O 2.2 C 3 H 6 at both 150 and 200 °C, while additional species, presumably from incomplete reaction, were found at 100 °C, leading to a notably higher (0.84 Å/cycle) growth rate. The LPDO film showed crystallinity and high surface roughness when grown on the crystalline substrate, while on the amorphous substrate, an amorphous LPDO film with low surface roughness was observed. In addition, high air sensitivity of LPDO film was observed, with Li propyl carbonate and Li carbonate formation under air exposure. Further modification strategies were proposed in order to achieve a MLD or atomic layer deposition-/MLD-based solid electrolyte material.
25 ENERGY STORAGE↗
Electrochemical Healing of Dendrites in Garnet-Based Solid Electrolytes
Garnet oxides are a promising material family for solid-state batteries (SSBs). Dendrite formation in solid electrolytes critically limits the applicability of SSBs because of limiting Coulombic efficiency and power capability. In this study, the authors report operando electrochemical healing of dendrites in a garnet-based solid electrolyte (SE). Dendrites were deliberately formed at high operational current density (2 mA cm –2 ) beyond the critical current density (0.55 mA cm –2 ) of the used garnet SE. Electrochemical impedance spectroscopy and scanning electron microscopy were used to confirm dendrite growth in the SE. Dendrites were subsequently healed electrochemically via plating and stripping at 20 and 1 μA cm –2 current densities. Removal of dendrites was shown by an increase in bulk and interfacial resistance and a progressive increase in polarization during galvanostatic plating and stripping. High local current density at the dendrite tips was identified as the mechanism for preferentially removing dendrites electrochemically. The dendrite detection and healing methods discussed here are crucial for extending the life of SSBs.
25 ENERGY STORAGE↗
Electro-Chemo-Mechanical Evolution at the Garnet Solid Electrolyte–Cathode Interface
Solid-state batteries promise higher energy density and improved safety compared with lithium-ion batteries. However, electro-chemomechanical instabilities at the solid electrolyte interface with the cathode and the anode hinder their large scale implementation. Here, in this study, we focus on resolving electro-chemo-mechanical instability mechanisms and their onset conditions between a state-of-the-art cathode, LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622), and the garnet Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte. We used thin-film NMC622 on LLZO pellets to place the interfacial region within the detection depth of the X-ray characterization techniques. The experimental probes of the near-interface region included in operando X-ray absorption spectroscopy and ex situ focused ion beam scanning electron microscopy. Electrochemical degradation was not observable during cycling at room temperature with 4.3 V versus Li/Li + charge voltage cutoff, or with stepwise potentiostatic hold up to 4.1 V versus Li/Li + . In contrast, secondary phases including reduced transition metal species (Ni 2+ , Co 2+ ) were found after cycling up to 4.3 V versus Li/Li + at 80 °C and during potentiostatic hold at 4.3 V versus Li/Li + (Ni 2+ ). Intergranular cracks between NMC622 grains and delamination at the NMC622|LLZO interface occurred readily after the first charge. These interface reaction products and mechanical failure lowered the capacity and cell efficiency due to partial loss of the NMC622 phase, partial loss of contact at the interface, and a higher polarization resistance. Electrochemical instability between delithiated NMC622 and LLZO could be mitigated by using a low charge voltage cutoff or cycling at lower temperature. Ways to engineer the mechanical properties to avoid crack deflection and delamination at the interface are also discussed for enhancing mechanical stability.
36 MATERIALS SCIENCE↗
Silver-carbon interlayers in anode-free solid-state lithium metal batteries: Current development, interfacial issues, and instability challenges
As an interlayer between the anode and the electrolyte of the all-solid-state lithium metal batteries (ASSLMBs), the silver-carbon (Ag-C) nanocomposite has been reported to significantly increase the energy density and cycle rate of solid-state lithium metal batteries. Ag-C interlayers serve as mixed ionic-electronic conductor that conducts both Li+ ions and electrons and lithium storage capacity. Unfortunately, it was unclear how the Ag-C interlayer regulated lithium plating and stripping. Moreover, the structural and chemical instabilities between the interlayer and the electrolyte, within the interlayer, or beneath the interlayer on lithium substrate are likely to cause cell failure. In this review, we discuss interfacial issues and summarize recent progress in solution strategies for ASSLMBs, with a specific focus on the use of a silver-carbon (Ag-C) nanocomposite interlayer in anode-free setups. Based on the Li transport kinetics among the Ag-C interlayers, the interfacial configurations of Ag-C interlayers are classified as either exterior or internal. Furthermore, the review concludes with a discussion of the perspectives and future prospects, allowing for the improvement of interlayer techniques for solid-state batteries.
25 ENERGY STORAGE↗
Understanding slurry formulations to guide solution-processing of solid electrolytes
Scalable processing of thin solid electrolytes is crucial for engineering solid-state batteries with practical energy densities. To leverage existing battery production infrastructure, pathways for solution processing of solid electrolyte films must be investigated. Here, roll-to-roll compatible film preparation of aluminum-doped lithium lanthanum zirconate oxide was studied. Four slurry configurations accounting for different solvent properties and solid loadings were evaluated to investigate the ternary interactions within the dispersions. Rheological and coating stability analyses were carried out on the processed slurries. The analysis and characterization indicated that improved component interactions within the ethanol/toluene system result in homogenized distribution of the particles, binder, and plasticizer, and enable the extraction of free-standing thin films with thicknesses of 20 μm and large area (>15 in. 2 ). The drawbacks and opportunities of several protocols for high temperature sintering of the dried green films were investigated. This study highlights the importance of engineering dispersions during the development of processing protocols for solid electrolytes and provides guidelines for the best practices that can be leveraged for solution processing–based fabrications for a wide range of solid electrolyte materials.
25 ENERGY STORAGE↗
Size-Dependent Chemomechanical Failure of Sulfide Solid Electrolyte Particles during Electrochemical Reaction with Lithium
The very high ionic conductivity of Li 10 GeP 2 S 12 (LGPS) solid electrolyte (SE) makes it a promising candidate SE for solid-state batteries in electrical vehicles. However, chemomechanical failure, whose mechanism remains unclear, has plagued its widespread applications. Here, we report in situ imaging lithiation-induced failure of LGPS SE. In this work, we revealed a strong size effect in the chemomechanical failure of LGPS particles: namely, when the particle size is greater than 3 μm, fracture/pulverization occurred; when the particle size is between 1 and 3 μm, microcracks emerged; when the particle size is less than 1 μm, no chemomechanical failure was observed. This strong size effect is interpreted by the interplay between elastic energy storage and dissipation. Our finding has important implications for the design of high-performance LGPS SE, for example, by reducing the particle size to less than 1 μm the chemomechanical failure of LGPS SE can be mitigated.
25 ENERGY STORAGE↗
Highly disordered amorphous Li-battery electrolytes
"Medium-entropy" highly disordered amorphous Li garnets, with ≥4 unique local bonding units (LBUs), hold promise for use as solid-state electrolytes in hybrid or all-solid-state batteries owing to their grain-boundary-free nature and low-temperature synthesis requirement. Through this work, we resolved the local structure of amorphous Li garnet and understood their implication for Li dynamics. These medium-entropy amorphous structures possess unique characteristics with edge- and face-sharing LBUs, not conforming to the classic Zachariasen glass formation rules, and can be synthesized in a wide but processing-friendly temperature range (<680°C). Within these amorphous structures, Li and Zr are identified as the network formers and La as network modifier, with maxima in Li dynamics observed for smaller Li-O and Zr-O coordination; this structure understanding serves as a baseline for identifying additional network formers to further modulate Li transport. In conclusion, our insight provides fundamental guidelines for the structure and phase design for amorphous Li garnets and paves the way for their integration in next-generation batteries.
25 ENERGY STORAGE↗
Achieving stable all-solid-state lithium-metal batteries by tuning the cathode-electrolyte interface and ionic/electronic transport within the cathode
All-solid-state batteries with sulfide electrolytes and high-nickel layered oxide cathodes attract much interest due to their high specific energy. However, their cycling performance is primarily influenced by the interface between the sulfide electrolyte and the high-Ni layered oxide particles, which requires the use of composite cathodes with high ionic and electronic conductivities to achieve a kinetically stable interface inside the cathode. Here, we apply Ti 2 O 3 particles to the high-Ni cathode LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811), where Ti 2 O 3 not only acts as an electronic conductor to provide a fast diffusion path for electrons in the composite cathode, but also absorbs the lattice oxygen released from NCM811 cathode during cycling, stabilizing the Li 6 PS 5 Cl/NCM811 interface and suppressing electrolyte oxidation. The as-modified cathode exhibits an initial specific capacity of 192 mAh g -1 and retains 166 mAh g -1 after 140 cycles at 0.1C rate with a good capacity retention of 86.5%. Furthermore, the composite cathode displays high rate capability even at 1C rate. By contrast, the unmodified Li 6 PS 5 Cl/NCM811 cathode shows poor cycling performance with only 130 mAh g -1 remaining after 130 cycles. This work provides a new direction for the design of cathodes for all-solid-state batteries that can deliver high specific energy with long cycle life.
25 ENERGY STORAGE↗
The effect of aspect ratio on the mechanical behavior of Li metal in solid-state cells
The Li metal anode is necessary for solid-state batteries to dramatically exceed the energy density of state-of-the-art conventional Li-ion batteries. To enable the Li metal anode, the mechanical properties of Li metal under compression in a commercially relevant cell configuration must be determined. This work examines the compression creep behavior of Li metal coupled with a relevant model solid-state electrolyte (Li 6.5 La 3 Ta 0.5 Zr 1.5 O 12 ) and current collector (Ni) as a function of applied stress (1–10 MPa) and Li foil thickness (100–700 μm). At 1 MPa applied stress, the strain rate of all Li foil thicknesses under compression was almost four orders of magnitude lower than what is predicted from tensile creep tests. Steady-state creep behavior was observed for Li foil ≥350 μm at 5 MPa and ≥250 μm at 10 MPa. Conversely, sustained creep deformation was not observed for 100 and 150 μm Li foils at any applied stress. It is suggested that friction at the Li/LLZO and Li/Ni interfaces leads to the formation of hydrostatic stress that controls Li deformation at low aspect ratios. Finally, these results have implications for battery pack stack pressure requirements, particularly relating to void formation during stripping and Li metal filament penetration during plating.
25 ENERGY STORAGE↗
Electroanalytical Exploration of Li Loss at the Solid Electrolyte-Anode Interface in Anode-Free Batteries with Polymer Electrolytes
Li loss during cycling at the solid electrolyte|anode interface strongly determines the cycle life of anode-free solid-state batteries (SSBs). Here, this loss is probed electroanalytically for polymer electrolyte (PE)-based SSBs in anode-free coin cells with practical pressures. A wide range of parameters expected to impact the measured average coulombic efficiency (CE) were explored to estimate the expected range of performance. These factors include PE type, cycling profiles, current collector type, and the presence of a thin Li seed layer. Further, low CE values in the ~50%–85% range are observed for all electrolytes and test conditions. Other than the electrolyte type, a strong dependence of the CE on the electrochemical cycling profile and the type of metallic current collector is observed. Compared to the anode-free setup, the presence of a thin (5 μ m) Li seed layer did not improve the average CE for two out of three PEs, suggesting its presence to be a weak contributor in minimizing the Li loss. This work provides baseline data on the Li losses in low-pressure anode-free configuration cells with PEs.
25 ENERGY STORAGE↗