Li-ion Conductivity Research Articles

Improving Bulk and Interfacial Lithium Transport in Garnet-Type Solid Electrolytes through Microstructure Optimization for High-Performance All-Solid-State Batteries.

Garnet-type Li6.4La3Zr1.4Ta0.6O7 (LLZTO) is regarded as a highly competitive next-generation solid-state electrolyte for all-solid-state lithium batteries owing to reliable safety, a wide electrochemical operation window of 0-6 V versus Li+/Li, and a superior stability against Li metal. Nevertheless, insufficient interface contacts caused by pores, along with Li dendrite growth at these voids and grain boundary regions, have hindered their commercial application. Herein, we suggest a method to produce high-quality LLZTO using LiAlO2 (LAO) as a chemical additive that leads to an improved microstructure with larger grain size (∼25 μm), a high relative density (∼96%), lower porosity (∼3.7%), and continuous secondary phases in grain boundary regions. This improved structure results in (i) improved Li-ion conductivity and enhanced interfacial resistance between Li metal and LLZTO by a denser structure with fewer pores and (ii) suppression of Li dendrite penetration in the electrolyte by secondary phases in grain boundary regions.

High-throughput screening of halide solid-state electrolytes for all-solid-state Li-ion batteries through structural descriptor

All-solid-state Li-ion batteries (ASSLIBs) have attracted great attention due to their intrinsic safety and high potential energy density. To realize ASSLIBs, the development of solid-state electrolytes (SSEs) with favorable electrochemical stability and high Li-ion conductivity is of utmost significance. Compared to trial-and-error searches, theoretical computation-based methods are recognized as a powerful tool for accelerating the exploration of SSEs. However, the development of appropriate descriptors is often the first hurdle toward implementing accurate and meaningful screening process. Here we quantified the structural properties pertaining to low Li-ion migration barriers and performed a high-throughput screening of 3119 Li-containing halides obtained from the Materials Project (MP) database to search for promising SSEs. After excluding previously reported SSEs, three candidate materials, Li4ZrF8, Li3ErBr6, and Li2ZnI4 with crystal structure exhibiting 3D diffusion pathway were obtained. Subsequent theoretical calculations of these materials were performed to evaluate their thermodynamic stability, chemical/electrochemical stability, and ionic conductivity. The three halide materials appeared to be promising SSE candidates due to their robust thermodynamical stability against cathodes, and high ionic conductivity. This research provides a new insight and a systematic quantitative understanding of the relationship between the structural properties and Li-ion migration barriers, which can motivate future computational studies on new fast-ion conductors and accelerate the discovery of high ionic conductivity SSEs for the use in ASSLIBs.

In Situ Alloying Enabled by Active Liquid Metal Filler for Self-Healing Composite Polymer Electrolytes.

Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self-healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li-ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li-LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid-state Li/LiFePO4 battery achieves promising full-cell functionality with notable rate performance and stable cycle life. This active filler-mediated self-healing approach could bring new insights into the battery design in versatile solid-state systems.

Boosting Li-Ion Conductivity of Fluoride Solid Electrolyte by Low-Temperature Molten Salt Ablation and Particle Boundary Doping.

Halide solid electrolytes (SEs) are attracting great attention, owing to their high ionic conductivity and excellent high-voltage compatibility. However, severe moisture sensitivity, poor thermal stability, and instability at the lithium metal anode interface with chloride and bromide SEs retard their applications in solid-state lithium metal batteries. Fluoride SEs are expected to solve these problems, but they are now plagued by inadequate room-temperature (RT) ionic conductivity. Herein, a low-temperature molten salt (LiCl+1.33AlCl3) ablation method is proposed to enhance the ionic conductivity of monoclinic Li3GaF6 by particle boundary doping. The RT ionic conductivity of Li3GaF6 is correspondingly increased by 2 orders of magnitude, and the conductivity reaches 10-4 S cm-1 at 60 °C. The improved ionic conductivity benefits from the enhancement of interfacial ion transport, with the formation of more conductive chlorine-doped Li3GaF6-xClx and in situ binder LiAlCl4 to cement surrounding nanoparticles. The as-synthesized Li3GaF6 demonstrates outstanding humidity tolerance without conductivity degradation after exposure to a relative humidity of up to 35%. It also exhibits the widest electrochemical stability window experimentally (close to 6 V) compared with other state-of-the-art SEs. The solid-state Li/Li3GaF6/LiFePO4 cell with a stable Li+-conductive polymer interface is successfully driven for at least 200 cycles at 0.5C. Our study provides a solution to various chemical and electrochemical stability issues encountered by the halide SE family.

Understanding the improved performances of Lithium–Sulfur batteries containing oxidized microporous carbon with an affinity-controlled interphase as a sulfur host

Li–S batteries (LSBs) based on the solid-phase conversion reaction that contain microporous carbon (MC) materials as their S hosts exhibit high cycling stabilities. Oxidized MC with O-containing functional groups increases the capacity of LSBs and lowers their internal resistance. Although these polar functional groups should improve the electrolyte affinities of electrode materials, their effects on the MC–S cathode/electrolyte interface have not yet been clarified. Herein, we report the affinity between the MC–S cathode and electrolyte. Contrary to conventional wisdom, the O-containing functional groups form affinity-controlled interphases on the MC–S cathodes, alleviating electrolyte decomposition and the formation of a cathode–electrolyte interphase during LSB cycling. This lowers the internal resistance of the LSB by facilitating unhindered Li-ion conduction, which stabilizes cycling at a low electrolyte [μL]/S [mg] ratio of 2.0, with an improved capacity (from 6.58 to 309.4 mAh g−1) in the second cycle. Thus, the use of an affinity-controlled interphase should improve the energy densities of LSBs and other energy storage devices.

Stabilization of single crystal LiNi0.90Mn0.05Co0.05O2 via ZrO2 dual-functional coating enables superior performance for solid-state lithium battery

Chlorine-rich argyrodites with ultrafast Li-ion conductivities exhibits great potential as solid electrolytes for all-solid-state lithium batteries. However, the poor interfacial stability and slow ion dynamics between Li5.5PS4.5Cl1.5 (Cl1.5) and high nickel layered cathode hinder the achievement of superior battery performances. Here, the prepared ZrO2 coating film was found to perform two functions: enhancing the bulk and interfacial stability of single crystal LiNi0.90Mn0.05Co0.05O2 (NCM911) towards sulfide, and facilitating Li-ion transport rates across the interface. A Li2ZrO3 phase with fast Li-ion diffusion rate generates during cycling and further improve the layered-structure integrity of NCM911 and interfacial stability toward the Cl1.5 electrolyte, which are due to the reduction of lattice oxygen release from NCM911 and the isolation of direct contact between the two materials. As a result, these effects enable superior electrochemical performances for the ZrO2-coated NCM911 than the bare sample in Cl1.5-based all-solid-state lithium batteries at varying C-rates and different operating temperatures. It delivers high initial discharge capacities of 156.6 mAh g−1 at 2C and retains 86.0 % of its capacity after 1000 cycles at room temperature, and displays an initial discharge capacity of 172.6 mAh g−1 at 0.5C under 60 °C and 142.4 mAh g−1 at 0.1C under –20 °C, respectively. This dual-functional surface modification strategy provides guidelines to stabilize high-nickel cathode in sulfide-based all-solid-state lithium batteries.

Tin-based dual-modification enabling enhanced air stability and electrochemical performance for Li5.5PS4.5Cl1.5 in all-solid-state lithium metal batteries

As one of sulfide electrolytes, chlorine-rich lithium argyrodites (Li5.5PS4.5Cl1.5) have significant advantages as solid state electrolytes (SSEs) in all-solid-state batteries (ASSBs) due to their ultra-high conductivity. However, their practical application is limited by poor air stability and weak compatibility with Li metals. Herein, we enhance the performance of Li5.5PS4.5Cl1.5 by doping it with SnO2, resulting in the formation of the Li5.58P0.92Sn0.08S4.34O0.16Cl1.5 electrolyte. The introduction of Sn and O dopants forms strong Sn-S and P-O bonds in the electrolyte, replacing the sensitive P-S bonds and suppressing H2S release. Additionally, this doped electrolyte demonstrates an impressive Li-ion conductivity of 5.71 mS cm−1, a high critical current density of 2.9 mA cm−2, and significantly improved air and moisture stability. Moreover, the Sn dopant produces a Li-Sn alloy layer on the bare Li metal anode, endowing the ASSB with an initial discharge capacity of 146.7mAh/g at 0.2C and a capacity retention of 86.2 % after 200 cycles at 0.5C. Combining with a 10 wt% SnF2-treated Li metal anode to further strengthen the electrode interfacial stability by the in-situ formed Li-Sn and LiF derivatives, the resultant full cell delivers a promoted initial discharge capacity of 179.5mAh/g at 0.2C and a high discharge capacity of 112.2mAh/g after 300 cycles at 0.5C. The dual strategy of electrolyte doping and Li anode modification achieves a synergistic effect that enables the ASSB to exhibit superior electrochemical performance, providing an effective way of preparing stable sulfide-based SSEs for large-scale applications.

Enhanced electrochemical performance of garnet Li7La3Zr2O12 electrolyte by efficient incorporation of LiCl

Garnet-type Ta-doped Li7La3Zr2O12 (LLZO) lithium-ion-conducting ceramic electrolytes has become the promising and critical candidate for developing the high-energy-density all-solid-state lithium batteries, due to the satisfied Li+ conductivity, stability against metallic lithium anode, and the feasible preparation under ambient air. Here, to further increase the lithium-ion conductivity of LLZO comparable to that of the commercial organic liquid electrolytes, lithium chloride (LiCl) is effectively introduced to synthesize the garnet-type ceramic electrolytes with the nominal composition (Li6.5La3Zr1.5Ta0.5O12)1-x–(LiCl)x (x = 0, 5mol%, 10mol%, 15mol%, 20mol%, and 25mol%) via high-temperature calcination process. The cubic structure with highly conductive performance is confirmed from X-ray diffraction measurement as well as Raman spectra analysis. Structural information is observed according to field emission scanning electron microscope equipped with energy dispersive spectrometer and density measurements. Among above investigated ceramic compositions, the prepared (Li6.5La3Zr1.5Ta0.5O12)0.85–(LiCl)0.15 ceramic electrolyte sheet sintered at 1200 °C for 12h presents the room-temperature Li-ion conductivity of 1.22 × 10−3 S·cm−1 by alternating current (AC) impedance analysis along with the corresponding activation energy of 0.262eV through Arrhenius equation calculation. The electronic conductivity measurements are also done by direct-current polarization to confirm the ionic nature for all investigated ceramics. Furthermore, the Li|(Li6.5La3Zr1.5Ta0.5O12)0.85–(LiCl)0.15 |Li symmetric batteries can possess the small interfacial resistance of 92.3 Ω cm2 and stably run for 1000 h at 0.1 mA cm−2 without a short circuit at room temperature. The hybridized lithium-sulfur battery with (Li6.5La3Zr1.5Ta0.5O12)0.85–(LiCl)0.15 electrolyte delivered excellent initial room-temperature discharge capacity of 1204mAh·g−1 and 1152 mAh·g−1 under the current density of 0.1C and 0.2C respectively, large coulombic efficiency, and great cycling stability. Moreover, the lithium-sulfur batteries also can show excellent cycling performances under different current densities and a good capacity recoverability. The above investigation results suggest that the low-melting-point LiCl incorporation in Li6.5La3Zr1.5Ta0.5O12 electrolyte is an effective measurement to synthesize the cubic and dense Li-stuff garnet ceramic sheets for the high-performance rechargeable next-generation solid-state batteries.

Transient Phase-Mediated Li+ Transportation in the Lithium Lanthanum Titanate Solid-State Electrolyte.

The lithium lanthanum titanium oxide (LLTO) perovskite is one type of superior lithium (Li)-ion conductor that is of great interest as a solid-state electrolyte for all-solid-state lithium batteries. Structural defects and impurity phases formed during the synthesis of LLTO largely affect its Li-ion conductivity, yet the underlying Li+ diffusion mechanism at the atomic scale is still under scrutiny. Herein, we use aberration-corrected transmission electron microscopy to perform a thorough structural characterization of the LLTO ceramic pellet. We reveal a prevalent transient phase transition of (La, Ti)2O3 existing at the antiphase boundaries between single-crystalline LLTO domains. This transient phase exhibits a specific crystal orientation with the LLTO phase and shows a gradual structural transition to a tetragonal LLTO structure, which enables detailed crystallographic analysis to correlate their formation to the sintering process of LLTO powders into ceramic pellets. We also find that Li diffusion is retarded by this phase and correlated with the excess amount of La, which is corroborated by the theoretical evaluation of the atomistic mechanisms of Li diffusion across this phase.

The role of crystallographic orientation on surface properties and ion transport in lithium germanate (Li2GeO3) anodes: A computational approach

The performance of lithium-ion batteries (LIBs) hinges on the surface properties of their anodes. Compared to the bulk material, the anode surface is more susceptible to environmental changes during lithium (Li) intake and release, directly impacting factors like capacity, cycling stability, and charge/discharge rates. Lithium germanate (Li2GeO3, LGO) has emerged as a promising anode material due to its fast Li-ion conduction. While numerous studies have explored performance improvements through various methods, including defect engineering. However, there is currently a lack of atomistic-level understanding of the surface structure. Consequently, despite the importance of precisely understanding the surface to manipulate its different properties, specific surface details of LGO remain unclear. This knowledge gap hinders precise manipulation of surface properties for optimal performance.This study addresses this critical need by employing theoretical calculations to predict the structural, electrochemical characteristics, and Li-ion transport behavior in LGO surfaces. Our results indicate that polar surfaces exhibit lower formation energies compared to non-polar surfaces. Further investigation revealed that Li-terminated surfaces possess the lowest surface energy among various surface terminations. Interestingly, the work function calculations displayed an opposite trend to surface formation energy, with polar surfaces exhibiting the lowest work function values.To explore Li-ion transport, we employed ab initio molecular dynamics simulations. Notably, the (003) surface displayed the highest Li-ion diffusion rate among all considered surfaces.Further analysis of the (001) surface, which exhibited similar diffusion pathways to the (003) surface, revealed a lower diffusion rate.To understand this disparity, nudged elastic band (NEB) simulations were used to estimate the energy barriers for Li-ion migration along each pathway in both structures. Despite sharing similar pathways, the energy barriers in the (003) surface were significantly lower than those in the (001) surface. This finding suggests that the intrinsic energy landscape of the surface plays a crucial role in dictating Li-ion transport behavior.

Influence of Ga-Ge doping on the structural and electrical properties of Li7La3Zr2O12 solid electrolytes

In order to replace the conventional liquid electrolytes by solid electrolytes, high room temperature ionic conductivity is required. To achieve such high ionic conductivity, the series Li7-3xGaxLa3Zr1.9Ge0.1O12 was prepared by solid-state reaction method. The content of Ge was kept constant at 0.10 atoms per formula unit (a.p.f.u), and the Ga has been varied from 0 to 0.40 a.p.f.u. The conducting cubic phase was identified using X-ray diffraction study, whereas the physical and structural studies were performed using density measurements and scanning electron microscopy (SEM) analysis, respectively. Electrical conductivity results revealed that the 0.20 Ga ceramic sample possessed the highest room temperature Li ion conductivity of 5.09 × 10-4 S/cm with minimum activation energy of 0.25 eV. The high room temperature ionic conductivity makes the 0.20 Ga ceramic sample a suitable solid electrolyte for all-solid-state lithium-ion batteries (ASSLIBs).

Boron Surface Treatment of Li7La3Zr2O12 Enabling Solid Composite Electrolytes for Li-Metal Battery Applications.

Despite being promoted as a superior Li-ion conductor, lithium lanthanum zirconium oxide (LLZO) still suffers from a number of shortcomings when employed as an active ceramic filler in composite polymer-ceramic solid electrolytes for rechargeable all-solid-state lithium metal batteries. One of the main limitations is the detrimental presence of Li2CO3 on the surface of LLZO particles, restricting Li-ion transport at the polymer-ceramic interfaces. In this work, a facile way to improve this interface is presented, by purposely engineering the LLZO particle surfaces for a better compatibility with a PEO:LiTFSI solid polymer electrolyte matrix. It is shown that a surface treatment based on immersing LLZO particles in a boric acid solution can improve the LLZO surface chemistry, resulting in an enhancement in the ionic conductivity and cation transference number of the CPE with 20 wt % of boron-treated LLZO particles compared to the analogous CPE with non-treated LLZO. Ultimately, an improved cycling performance and stability in Li//LiFePO4 cells was also demonstrated for the modified material.

A Review of Nanocarbon-Based Anode Materials for Lithium-Ion Batteries

Renewable and non-renewable energy harvesting and its storage are important components of our everyday economic processes. Lithium-ion batteries (LIBs), with their rechargeable features, high open-circuit voltage, and potential large energy capacities, are one of the ideal alternatives for addressing that endeavor. Despite their widespread use, improving LIBs’ performance, such as increasing energy density demand, stability, and safety, remains a significant problem. The anode is an important component in LIBs and determines battery performance. To achieve high-performance batteries, anode subsystems must have a high capacity for ion intercalation/adsorption, high efficiency during charging and discharging operations, minimal reactivity to the electrolyte, excellent cyclability, and non-toxic operation. Group IV elements (Si, Ge, and Sn), transition-metal oxides, nitrides, sulfides, and transition-metal carbonates have all been tested as LIB anode materials. However, these materials have low rate capability due to weak conductivity, dismal cyclability, and fast capacity fading owing to large volume expansion and severe electrode collapse during the cycle operations. Contrarily, carbon nanostructures (1D, 2D, and 3D) have the potential to be employed as anode materials for LIBs due to their large buffer space and Li-ion conductivity. However, their capacity is limited. Blending these two material types to create a conductive and flexible carbon supporting nanocomposite framework as an anode material for LIBs is regarded as one of the most beneficial techniques for improving stability, conductivity, and capacity. This review begins with a quick overview of LIB operations and performance measurement indexes. It then examines the recently reported synthesis methods of carbon-based nanostructured materials and the effects of their properties on high-performance anode materials for LIBs. These include composites made of 1D, 2D, and 3D nanocarbon structures and much higher Li storage-capacity nanostructured compounds (metals, transitional metal oxides, transition-metal sulfides, and other inorganic materials). The strategies employed to improve anode performance by leveraging the intrinsic features of individual constituents and their structural designs are examined. The review concludes with a summary and an outlook for future advancements in this research field.

Surface modification of LiFePO4 cathode enabled by highly Li+ mobility wrapping layer towards high energy and power density

Surface-modified cathode materials have been developed to achieve high-performance lithium secondary batteries with higher capacity, rate capability, and longer cycle performance than bulk active materials. In this study, a new surface-modified active material was explored through a low-temperature in situ-solution wrapping method (LiFePO4@Li4SiO4 composite). In addition, high Li-ion and electronic conductivity materials with amorphous nanostructures, in which the bulk LiFePO4 nanoparticles were covered with a Li4SiO4 layer, were demonstrated. In lithium-ion batteries, the LiFePO4@Li4SiO4 composite demonstrated enhanced charge transfer kinetics, which lowered the interfacial resistance between electrode and electrolyte and resulted in enhanced electrochemical performance when compared to that of bulk LiFePO4. Furthermore, Li4SiO4 is introduced as a surface stabilizer and effective Li-ion conductor to avoid side reactions and prevent the dissolution of active materials into the electrolyte. The designed cathode delivers a high specific discharge capacity of 171.8 mAh g-1 at 0.1 C with 99.76 % capacity retention after 150 cycles and a high capacity of 121.2 mAh g-1 at 10 C. Moreover, Li-ion full batteries employing LiFePO4@Li4SiO4 and graphite displayed a high specific energy density of 416.078 Wh kg-1 at a power density of 69.34 W kg-1 at 5 C. In summary, this paper reports a new strategy based on low-temperature in situ solution phase wrapping materials for developing active materials for high energy-power density energy storage devices.

Fostering Li-ion conduction in Zr-Sn-Al-based mid-entropy NASICON electrolyte

NASICON (Na Super Ionic CONductor) type materials are an important class of solid-state electrolytes due to their high ionic conductivity along with decent chemical and electrochemical stability. In this study, a medium-entropy Li1.5Zr1.0Sn0.5Al0.5(PO4)3 (LZSAP) ceramic electrolyte was prepared via a solid-state synthesis method. Rietveld refinement confirmed the rhombohedral structure of the conventionally sintered sample (LZSAP-CS) at 1000 °C. The spark plasma sintering (SPS) technique was used for the densification of the pellet and resulted in ∼2.64 times higher room temperature conductivity (∼4.42 × 10−5 S cm−1) than that of the LZSAP-CS. The activation energy, calculated in the 30–100 °C range, decreased from 0.37 ± 0.01 eV for LZSAP-CS to 0.31 ± 0.01 eV for spark plasma sintered LZSAP pellet. The transference number of Li+ was ∼0.98, indicating that Li+ is the predominant charge carrier in this electrolyte. Further investigation of the lithium metal-electrolyte interface was conducted using a symmetric Li|LZSAP-SPS|Li cell configuration, demonstrating stability for over 500 h at 5 μA cm−2. LZSAP extends the list of suitable solid-state electrolytes for all-solid-state lithium batteries.

Influence of compositional variation of Li3InCl6 on the solid-electrolyte property

Li3InCl6 (LIC) is a promising halogen-based solid electrolyte. This study investigates the influence of compositional variations in LIC on its properties as a solid electrolyte using deep-learning-assisted computational simulations. Introducing vacancies to create LIC compositions with elemental deficiencies enhances the mobility of Li ions. However, while Cl deficiency increases Li-ion mobility, it also induces instability in the crystal structure by facilitating Cl ion movement. In contrast, generating vacancies exclusively for Li ions significantly boosts Li-ion conductivity while maintaining a stable anionic superlattice structure. Therefore, minimizing Cl vacancies while promoting a Li-deficient state is recommended as an effective compositional design strategy to enhance the solid electrolyte performance of LIC while ensuring crystal structure stability.

Disorder-Dependent Li Diffusion in Li6PS5Cl Investigated by Machine-Learning Potential.

Solid-state electrolytes with argyrodite structures, such as Li6PS5Cl, have attracted considerable attention due to their superior safety compared to liquid electrolytes and higher ionic conductivity than other solid electrolytes. Although experimental efforts have been made to enhance conductivity by controlling the degree of disorder, the underlying diffusion mechanism is not yet fully understood. Moreover, existing theoretical analyses based on ab initio molecular dynamics (MD) simulations have limitations in addressing various types of disorder at room temperature. In this study, we directly investigate Li-ion diffusion in Li6PS5Cl at 300 K using large-scale, long-term MD simulations empowered by machine-learning potentials (MLPs). To ensure the convergence of conductivity values within an error range of 10%, we employ a 25 ns simulation using a 5 × 5 × 5 supercell containing 6500 atoms. The computed Li-ion conductivity, activation energies, and equilibrium site occupancies align well with experimental observations. Notably, Li-ion conductivity peaks when Cl ions occupy 25% of the 4c sites rather than at 50% where the disorder is maximized. In addition, Li-ion diffusion shows non-Arrhenius behavior, leading to different activation energies at high temperatures (>400 K). These phenomena are explained by the interplay between inter- and intracage jumps. By elucidation of the key factors affecting Li-ion diffusion in Li6PS5Cl, this work paves the way for optimizing ionic conductivity in the argyrodite family.

Enhancing Li-ion diffusivity of Li1.3Al0.3Ti1.7(PO4)3 through liquid-electrolytes-induced secondary crystallization

Solid electrolytes (SEs) offer promising avenues for improving both the energy density and safety of lithium-ion batteries (LIBs). However, the grain boundary resistance remains a significant hurdle that impact the performance of LIBs, particularly when utilizing SEs in powder form. In this study, we introduce a novel approach to reduce grain boundary resistance in Li1.3Al0.3Ti1.7(PO4)3 (LATP) via secondary crystallization induced by liquid electrolytes (LEs). By immersing nano-sized LATP powders in LiPF6/carbonates LEs, rapid aggregation and recrystallization into bulk micrometer-sized particles occur within minutes under ambient conditions. This secondary crystallization process alters the Li distribution within LATP bulk phase, substantially reducing the grain boundary resistance and enhancing Li-ion diffusivity. Consequently, the assembled LATP-modified commercial LiNi0.89Co0.07Mn0.04O2 cathode using LiPF6 electrolyte delivers a remarkable discharge capacity of 105.4 mAh g−1 at 4C, significantly superior to the bare electrode (44.7 mAh g−1). The recrystallized LATP enhances the transport properties and pathways of Li+ ions within the cathode material, especially at high current densities. Multinuclear and multi-dimensional solid-state NMR analysis reveal that active F− ions released from the hydrolysis of LiPF6 electrolytes act as mineralizing agent, facilitating rapid agglomeration and secondary growth of LATP grains. Our findings underscore the efficacy of secondary crystallization using LEs as a promising strategy for eliminating grain boundary resistance and facilitating fast Li-ion conduction of SEs, thereby advancing LIB performance.

Ionic conductivity and dielectric characteristics of a Li incorporated PVA electrolyte membrane and a study of a fully solid-state electrochromic device based on it

The construction and study of a fully solid state electrochromic (EC) device with cathodic coloration exhibiting very fast response times (< 1s) is reported using a WO3 EC layer and a poly (vinyl alcohol) (PVA)- Lithium acetate membrane electrolyte. Broadband dielectric studies on the polymer membranes with different Li concentrations show multiple relaxation mechanisms out of which a segmental relaxation prominent beyond a certain composition is strongly correlated with Li-ion conduction yielding better ionic conductivity and reversible coloration in the EC device. The relatively high Li conductivity in PVA has a direct correspondence with the lowering of the crystallinity of PVA and a decrease of the glass transition temperature, Tg with increasing Li addition. A simple model of the coloration process suggests that the short electrolyte diffusion length coupled with a high electric field and an interfacial emf that varies as ≈t−0.6 results in the swift current response of the film with an optimal performance at 20 wt.% Li in PVA, exceeding which irreversible coloration can occur on the surface. The transient current is crucial for the observed swift switching characteristics. Ageing studies for almost a month indicate potential stability of the EC device for over 150 cycles.

Unlocking fast Li-ion transport in micrometer-sized Mn-based cation-disordered rocksalt cathodes

The development of cation-disordered rocksalt (DRX) cathodes has garnered worldwide attention due to their high capacity, broad chemical space and excellent structural flexibility. However, their low intrinsic Li-ion conductivity necessitates extensive particle pulverization, typically achieved through ball-milling process, which impedes large-scale production. In this work, we present a proton-exchange assisted strategy to activate the Li-ion transport in Mn-based DRX cathodes. Short-range spinel-like ordering is observed to form within the DRX matrix after the post treatment, which significantly enhances the intrinsic Li ion mobility. Notably, more than 280 mAh g−1 discharge capacity can be delivered at a slow rate from micrometer-sized particles with an overall disordered cation arrangement, which retains more than 150 mAh g−1 when cycled at a very high rate of 2000 mA g−1. Furthermore, we also demonstrate that the electrochemical performance of the post-treated cathodes can be further optimized by fine-tuning the reaction parameters.