Li-ion Transport Research Articles

Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte

AbstractLi‐rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all‐solid‐state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling‐up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF4−) ion doped LiRAP Li2OHCl. Assisted by first‐principles calculation, powder X‐ray diffraction, solid‐state magnetic resonance and electrochemical impedance spectra, it is confirmed that Li ion transport in BF4− ion doped Li2OHCl is strongly associated with the rotational coupling among OH−, BF4− and Li2−O−H octahedrons, which enhances the Li ion conductivity for more than 1.8 times with the activation energy lowering 0.03 eV. This work provides a new perspective to design high‐performance superionic conductors with multi‐polyanions.

Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte.

Li-rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all-solid-state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling-up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy to fasten the Li ion conduction in tetrafluoroborate (BF4-) ion doped LiRAP Li2OHCl. Assisted by first-principles calculation, powder X-ray diffraction, solid-state magnetic resonance and electrochemical impedance spectra, it is confirmed that Li ion transport in BF4- ion doped Li2OHCl is strongly associated with the rotational coupling among OH-, BF4- and Li2-O-H octahedrons, which enhances the Li ion conductivity for more than 1.8 times with the activation energy lowering 0.03 eV. This work provides a new perspective to design high-performance superionic conductors with multi-polyanions.

One-pot Synthesis of High-capacity Sulfur Cathodes via In-situ Polymerization of a Porous Imine-based Polymer.

Lithium-ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur-based cathodes, offering a high theoretical capacity of 1675mAhg-1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state-of-the-art sulfur-based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur's mobility leads to battery degradation - an effect known as the "sulfur-shuttle". This study introduces a solution by developing a microporous, covalently-bonded, imine-based polymer network grown in-situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li-ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1C (1360mAhg-1) to 3C (807mAhg-1). Demonstrating a high-performance, sustainable sulfur cathode produced via a simple one-pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal-based cathodes.

Enhancing Li-ion transport by creating continuous channels and improving the decomposition of lithium salts in composite polymer electrolytes

Enhancing Li-ion transport by creating continuous channels and improving the decomposition of lithium salts in composite polymer electrolytes

An all-solid-state electrochemical four-electrode cell–Application to Li-ion transport between two sulfide solid electrolytes

Understanding Li-ion transport at the solid | solid interface is crucial to improving the performance of all-solid-state Li-ion batteries. Electrochemical four-electrode cells have been widely used for electrochemical measurements of ion transports at liquid | liquid and solid | liquid interfaces. However, there is no report of the application to the Li-ion transport at the solid | solid interface, and the electrochemistry of Li-ion transport at the solid | solid interface has not been understood well. In this study, we develop an all-solid-state electrochemical four-electrode cell and investigate the Li-ion transports at the interfaces between two sulfide solid electrolytes. The Li-ion transport resistances at the solid | solid interfaces are successfully evaluated by AC impedance measurement. The activation energy of the Li-ion transports at the solid | solid interfaces is similar to that of the Li-ion transports in the solid electrolytes with lower ionic conductivities.

Solid polymer electrolytes with fragment-separated microphase for advanced Li ion transport and highly stable lithium metal batteries

Solid polymer electrolytes (SPEs) with high ionic conductivity and good interfacial compatibility are one of the main factors constraining the performance of lithium metal batteries. However, the most common PEO (Polyethylene oxide)-based SPEs always lack of considerable relaxation of PEO segments, and therefore fail to apply into practical situations. Herein a novel method to prepare fragment-separated epoxy polymer electrolytes (FSEEs) characterized with fragment-separated microphase patterns via a rigid-and flexible monomers cross-link reaction is presented to enhance the overall SPE performance. The fragment-separated microphase can separate the PEO chains in framework and improve the relaxation of PEO chains, optimize the Li+ transport, where the ionic conductivity can be up to 0.56 mS cm−1 at 25 °C. The fragment-separated Li+ transport mechanism in FSEEs also provide better interfacial compatibility than that of PEO due to the even Li+ distribution at interface. The utilization of FSEE-S in Li/Li symmetric cells demonstrated a stable voltage plateau after cycling for 2000 h. Additionally, Li/LFP batteries exhibit favorable 0.5 C performance under 45 °C, lasting over 600 h and exceeding 150 cycles. This study offers a promising approach to SPE design, which may catalyze further exploration of the role of microphase in SPE performance.

Coupling of ion-conducting interphase with lithiophilic-solid-oxide-electrolyte interlayer toward fast-charging lithium metal batteries

The uncontrollable dendritic Li growth and limited Coulombic efficiency have long impeded the implementation of fast-charging lithium metal batteries. Contrary to the widely accepted attempt of using a sintering dense ceramic electrolyte to realize dendrite-free deposition, we report a coupling architecture of ion-conducting-Li3PO4-Li3N interphase with lithiophilic-solid-oxide-electrolyte interlayer for Li-metal anode using a reactive lithiophilic solid oxide electrolyte (RLSE) rather than dense ceramics. The synergistic interphase and protection layer can facilitate the Li-ion transport and enhance the lithiophilicity. As a result, an ultrahigh Li plating/stripping current density of 10 mA cm−2 and areal capacity of 10 mAh cm−2 for over 1000 h, and a remarkable Coulombic efficiency of 99.8 % are achieved simultaneously. Moreover, the use of interphase-interlayer synergistic protection enables a stable long-term 3000-cycling of Li||Li4Ti5O12 cell at 2C rate. More importantly, high-current–density (e.g. 1.8 mA cm−2) cycling of Li||LiNi0.8Co0.1Mn0.1O2 batteries with a practical area capacity of 3.6 mAh cm−2 is achieved in both carbonate and quasi-solid electrolytes. This study demonstrates an alternative approach of solid oxide electrolytes to stabilize Li-metal anode and enable fast-charging lithium metal batteries.

Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution.

Traditional cathode chemistry of Li-ion batteries relies on the transport of Li-ions within the solid structures, with the transition metal ions and anions acting as the static components. Here, we demonstrate that a solid solution of F- and PO43- facilitates the reversible conversion of a fine mixture of iron powder, LiF, and Li3PO4 into iron salts. Notably, in its fully lithiated state, we use commercial iron metal powder in this cathode, departing from electrodes that begin with iron salts, such as FeF3. Our results show that Fe-cations and anions of F- and PO43- act as charge carriers in addition to Li-ions during the conversion from iron metal to a solid solution of iron salts. This composite electrode delivers a reversible capacity of up to 368 mAh/g and a specific energy of 940 Wh/kg. Our study underscores the potential of amorphous composites comprising lithium salts as high-energy battery electrodes.

Two-dimensional MXene/MOFs heterojunction nanosheets as confinement hosts for dendrite-free lithium metal anodes

Although metallic lithium is regarded as the most potential anode candidate for next-generation batteries, its applications are greatly restricted by the uncontrollable growth of lithium dendrites and unstable anode/electrolyte interface. Herein, MXene/MOFs heterojunction nanosheets are developed through a convenient self-assembly process by harnessing the chemical interactions between MXene and Ni-MOFs monolayers. In this heterojunction, not only the MXene interlayer induces uniform lithium nucleation, but also MOFs monolayers act as stable interfaces to promote Li ion transport and homogenize the subsequent lithium deposition. Moreover, the MXene/MOFs substrate mitigates the volume change of lithium anodes. Consequently, 2D MXene/MOFs heterojunction nanosheets as confinement hosts effectively suppress lithium dendrites and exhibit enhanced electrochemical performances including a coulombic efficiency of 99 % over 300 cycles at 0.5 mA cm−2 and 1 mAh cm−2, and a long cycling life up to 500 h at 1 mA cm−2 and 1 mAh cm−2. The MXene/MOFs-Li||LiFePO4 cells exhibit a stable cycling performance with a capacity retention of 91 % after 600 cycles.

Improved Mechanical Strength without Sacrificing Li-Ion Transport in Polymer Electrolytes.

Next-generation batteries demand solid polymer electrolytes (SPEs) with rapid ion transport and robust mechanical properties. However, many SPEs with liquid-like Li+ transport mechanisms suffer a fundamental trade-off between conductivity and strength. Dynamic polymer networks can improve bulk mechanics with minimal impact to segmental relaxation or ionic conductivity. This study demonstrates a system where a single polymer-bound ligand simultaneously dissociates Li+ and forms long-lived Ni2+ networks. The polymer comprises an ethylene oxide backbone and imidazole (Im) ligands, blended with Li+ and Ni2+ salts. Ni2+-Im dynamic cross-links result in the formation of a rubbery plateau resulting in, consequently, storage modulus improvement by a factor of 133× with the introduction of Ni2+ at rNi = 0.08, from 0.014 to 1.907 MPa. Even with Ni2+ loading, the high Li+ conductivity of 3.7 × 10-6 S/cm is retained at 90 °C. This work demonstrates that decoupling of ion transport and bulk mechanics can be readily achieved by the addition of multivalent metal cations to polymers with chelating ligands.

Mg-Composition Dependent Cycle Stability in Zn<sub>1-x</sub>Mg<sub>x</sub>O Li-ion Battery: Transition from Electronic Transport-Limited to Ionic Transport Limited Cycles

This study explores Mg-composition dependent cycle stability in a Zn<sub>1-x</sub>Mg<sub>x</sub>O Li-ion battery, where battery cycles transition from an electronic transport-limited to an ionic transport limited regime. We investigated the impact of Mg doping in Zn<sub>1-x</sub>Mg<sub>x</sub>O nanocrystals on Li-ion battery performance, focusing on Mg compositions between x=0.05 and x=0.15. Mg composition dependent structural and electrical properties were explored using field effect transistors (FETs) and various microscopic/spectroscopic methods. The electronic conductivity was found to be sensitive to changes in Mg composition. Consistently, the initial capacity decreased with an increase in Mg composition, aligning with the reduction in electronic conductivity due to Mg doping. However, with successive cycles, the capacity became independent of the electronic conductivity, an outcome attributed to the formation of a solid-electrolyte interphase (SEI) and the conversion reactions. Initially, Mg doping reduces electronic conductivity due to increased carrier trapping, leading to lower discharge capacity. However, as cycling progresses, the impact of Mg doping diminishes. The formation of the SEI layer becomes more influential, significantly affecting Li-ion transport. Over time, factors like SEI formation, conversion reaction dynamics, and structural changes within the electrode start to dominate the battery's capacity, rather than the initial electronic conductivity influenced by Mg doping. This understanding can guide the development of materials with lower resistance, facilitating faster charging and discharging rates. More importantly, this study indicates that the initial capacity is closely tied to the conductivity of the Zn<sub>1-x</sub>Mg<sub>x</sub>O material.

Exploring Li-Ion Transport Properties of Li3TiCl6: A Machine Learning Molecular Dynamics Study

We performed large-scale molecular dynamics simulations based on a machine-learning force field (MLFF) to investigate the Li-ion transport mechanism in cation-disordered Li3TiCl6 cathode at six different temperatures, ranging from 25°C to 100°C. In this work, deep neural network method and data generated by ab − initio molecular dynamics (AIMD) simulations were deployed to build a high-fidelity MLFF. Radial distribution functions, Li-ion mean square displacements (MSD), diffusion coefficients, ionic conductivity, activation energy, and crystallographic direction-dependent migration barriers were calculated and compared with corresponding AIMD and experimental data to benchmark the accuracy of the MLFF. From MSD analysis, we captured both the self and distinct parts of Li-ion dynamics. The latter reveals that the Li-ions are involved in anti-correlation motion that was rarely reported for solid-state materials. Similarly, the self and distinct parts of Li-ion dynamics were used to determine Haven’s ratio to describe the Li-ion transport mechanism in Li3TiCl6. Obtained trajectory from molecular dynamics infers that the Li-ion transportation is mainly through interstitial hopping which was confirmed by intra- and inter-layer Li-ion displacement with respect to simulation time. Ionic conductivity (1.06 mS/cm) and activation energy (0.29eV) calculated by our simulation are highly comparable with that of experimental values. Overall, the combination of machine-learning methods and AIMD simulations explains the intricate electrochemical properties of the Li3TiCl6 cathode with remarkably reduced computational time. Thus, our work strongly suggests that the deep neural network-based MLFF could be a promising method for large-scale complex materials.

Asymmetric Solid-State Lithium-Metal-Battery Electrolytes Featuring Na Superionic Conductor-Type Ceramic and Garnet-Type Ceramic Filled Composite Polymer

In this study, Li1.3Al0.3Ti1.7(PO4)3 (LATP)-based lithium metal battery (LMB) cells are prepared using two different protection layers against Li metal: a solid polymer electrolyte (SPE) containing polyethylene oxide and lithium bis(fluorosulfonyl)imide (LiTFSI), and a composite polymer electrolyte (CPE) filled with a 14 wt% Li6.4La3Zr1.4Ta0.6O12 (LLZTO). The CPE-containing symmetric cell exhibits a smaller overvoltage than that of its SPE-containing counterpart, which is maintained for ∼1000 h at 0.1 mA·cm−2 at 60 °C, owing to enhanced Li-ion transport in the CPE and at the LATP–CPE interface as well as the uniform Li deposition induced by the CPE with a higher Li+ transference number. Post-material analyses reveal that the CPE imparts long-term (∼1000 h) protection to the LATP against Li metal, whereas the SPE is effective over a shorter period (∼100 h). The CPE-based full cell exhibits a higher capacity (∼141 mAh·g−1; with a LiFePO4) and capacity retention (∼95%) than those of the SPE-based full cell (∼130 mAh·g−1 and ∼55%, respectively), for 310 cycles at 60 °C. This study recommends utilizing asymmetric solid electrolytes containing a ceramic (LATP at the cathode) and composite polymer (PEO + LLZTO at the anode) to improve cyclability and suppress Li dendrite growth in solid-state LMBs.

A Star-StructuredPolymer Electrolyte for Low-Temperature Solid-State Lithium Batteries.

Solid-state polymer lithium metal batteries (SSLMBs) have attracted considerable attention because of their excellent safety and high energy density. However, the application of SSLMBs is significantly impeded by uneven Li deposition at the interface between solid-state electrolytes and lithium metal anode, especially at a low temperature. Herein, this issue is addressed by designing an agarose-based solid polymer electrolyte containing branched structure. The star-structured polymer is synthesized by grafting poly (ethylene glycol) monomethyl-ether methacrylate and lithium 2-acrylamido-2-methylpropanesulfonate onto tannic acid. The star structure regulates Li-ion flux in the bulk of the electrolyte and at the electrolyte/electrodeinterfaces. This unique omnidirectional Li-ion transportation effectively improves ionic conductivity, facilitates a uniform Li-ion flux, inhibits Li dendrite growth, and alleviates polarization. As a result, a solid-state LiFePO4||Li battery with the electrolyte exhibits outstanding cyclability with a specific capacity of 134 mAh g-1 at 0.5C after 800 cycles. The battery shows a high discharge capacity of 145 mAh g-1 at 0.1 C after 200 cycles, even at 0°C. The study offers a promising strategy to address the uneven Li deposition at the solid-state electrolyte/electrode interface, which has potential applications in long-life solid-state lithium metal batteries at a low temperature.

Can large lattice volume always facilitate ion diffusion in solids?

Large lattice volume is usually expected to expand the bottleneck size and enlarge free volume for fast Li ion transport in solids. But the universality of lattice expansion decreasing activation energy barrier for Li ion migration is still debatable. Herein, our molecular dynamics simulations and density functional theory calculations detect the unconventional phenomenon of lattice expansion increasing activation energy barrier for Li ion migration in β-Li3PS4, Li4SnS4 and Li4GeS4 sulfides with the hcp-type anion sublattice, and discover the underlying mechanism. On one hand, lattice expansion enlarges the relative energies between the octahedral and tetrahedral Li sites, and correspondingly increase activation energy barrier for tetrahedral Li ions migration along the Tet-Oct-Tet migration paths in β-Li3PS4, Li4SnS4 and Li4GeS4. On the other hand, the lattice dynamics calculations show Li energy landscapes of β-Li3PS4, Li4SnS4 and Li4GeS4 are anharmonic and enlarging lattice volume make the local minimum of Li potential energy surface flatter, simultaneously reduce the relative energy of Li occupation site, eventually resulting in the higher activation energy barrier for Li ion migration. Thus, understanding the effect of lattice volume on ion migration in solids should not only consider the factor of bottleneck size and free volume, but also combine the aspects of Li ion occupation type, Li ion migration path and anion sublattice type. These new understandings of the lattice expansion increasing activation energy barrier for ion migration would further promote the further optimization and rational design of superionic conductors by element doping or strain engineering.

Lithium Metal-Compatible Antifluorite Electrolytes for Solid-State Batteries.

Lithium (Li) metal solid-state batteries feature high energy density and improved safety and thus are recognized as promising alternatives to traditional Li-ion batteries. In practice, using Li metal anodes remains challenging because of the lack of a superionic solid electrolyte that has good stability against reduction decomposition at the anode side. Here, we propose a new electrolyte design with an antistructure (compared to conventional inorganic structures) to achieve intrinsic thermodynamic stability with a Li metal anode. Li-rich antifluorite solid electrolytes are designed and synthesized, which give a high ionic conductivity of 2.1 × 10-4 S cm-1 at room temperature with three-dimensional fast Li-ion transport pathways and demonstrate high stability in Li-Li symmetric batteries. Reversible full cells with a Li metal anode and LiCoO2 cathode are also presented, showing the potential of Li-rich antifluorites as Li metal-compatible solid electrolytes for high-energy-density solid-state batteries.

Wide Temperature Electrolytes for Lithium Batteries: Solvation Chemistry and Interfacial Reactions.

Improving the wide-temperature operation of rechargeable batteries is crucial for boosting the adoption of electric vehicles and further advancing their application scope in harsh environments like deep ocean and space probes. Herein, recent advances in electrolyte solvation chemistry are critically summarized, aiming to address the long-standing challenge of notable energy diminution at sub-zero temperatures and rapid capacity degradation at elevated temperatures (>45°C). This review provides an in-depth analysis of the fundamental mechanisms governing the Li-ion transport process, illustrating how these insights have been effectively harnessed to synergize with high-capacity, high-rate electrodes. Another critical part highlights the interplay between solvation chemistry and interfacial reactions, as well as the stability of the resultant interphases, particularly in batteries employing ultrahigh-nickel layered oxides as cathodes and high-capacity Li/Si materials as anodes. The detailed examination reveals how these factors are pivotal in mitigating the rapid capacity fade, thereby ensuring a long cycle life, superior rate capability, and consistent high-/low-temperature performance. In the latter part, a comprehensive summary of insitu/operational analysis is presented. This holistic approach, encompassing innovative electrolyte design, interphase regulation, and advanced characterization, offers a comprehensive roadmap for advancing battery technology in extreme environmental conditions.

Sulfur-containing soft Lewis base polymers for improved lithium-ion conductivity under polymer-in-salt conditions

Abstract Solid polymer electrolytes have been intensively studied to improve the safety and energy density of lithium-ion batteries (LiBs). Although high-rate performance of LiBs has been reported in electrolytes under polymer-in-salt conditions with an excess of lithium salts and polymers, effective conditions for achieving high ionic conductivity remain unresolved. In this study, we elucidate the mechanism and high Li-ion transportability of poly(sulfone-thioether) under polymer-in-salt conditions. In particular, the composition of the polymer with an asymmetric Li salt, lithium(fluorosulfonyl)(trifluoromethane sulfonyl)imide (LiFTFSI), induced a high ionic conductivity above 10−5 S/cm, which is higher than that of the poly(ethylene oxide) (PEO)-Li salt system. Under polymer-in-salt conditions, the enhanced conductivity of poly(sulfone-thioether) contrasts with the conductivity drop observed in the conventional PEO system. These results show the superiority of polymers with soft Lewis bases, such as sulfur donor atoms, for Li-ion transport under polymer-in-salt conditions.

Enhancing CA-based separators with thermo-responsive ionic liquids: A path to eco-friendly membrane production and multifaceted applications

We synthesized a temperature-responsive ionic liquid, [N4444][SS], and incorporated it into an environmentally friendly cellulose acetate (CA)-based battery separator. A pore was formed in the battery separator by [N4444][SS], which pierced a plasticized part due to water pressure. Varying drying temperatures during membrane fabrication revealed that the CA/[N4444][SS] membrane dried at 50 °C exhibited greater thickness and a smaller average pore size, resulting in an asymmetric internal structure. Despite the asymmetry, this membrane demonstrated significantly higher water flux and a lower Gurley value compared to the membrane dried at 25 °C, indicating minimal tortuosity and low resistance within the internal pores. Thermal behavior analysis through TGA and DSC, as well as FT-IR spectroscopy, confirmed that [N4444][SS] remains within the CA matrix, forming coordinative bonds. The findings suggest that the CA/[N4444][SS] membrane, when used as a Li-ion battery separator, could enhance Li-ion transport properties and conductivity. Moreover, the recyclability of the IL in the membrane fabrication process contributes to a more environmentally friendly approach.

Intergranular amorphous film in GeO2-enriched Li1.5Al0.5Ti1.5(PO4)3 composite electrolytes for high-performance solid-state lithium-ion batteries

Solid-state electrolytes have emerged as a key area of development in the field of Li-ion batteries owing to safety concerns surrounding liquid electrolytes. Among solid-state electrolytes, Li1.5Al0.5Ti1.5(PO4)3 (LATP), a NASICON-type material, is a leading candidate owing to its promising ionic conductivity, chemical and environmental stability, and cost-effectiveness. However, its ionic conductivity is limited by grain-boundary scattering, which hinders its broader adoption. Herein, we introduce a novel grain-boundary engineering strategy for the LATP electrolyte system using typical solid-state method, wherein a Ge-rich liquid phase spontaneously forms at the grain boundaries of GeO2-enriched LATP during synthesis, producing an intergranular amorphous film in the final material that significantly enhances Li-ion transport at the grain boundaries. With an optimal content of 4 wt% GeO2, the ionic conductivity reaches 8.92 × 10−4 S cm−1—an eightfold increase compared to that of pristine LATP. This high ionic conductivity also bestows 4 wt% GeO2-LATP with excellent cell performance, with a symmetric Li/4 wt% GeO2-LATP/Li cell exhibiting stable operation for over 500 h with low overpotentials. Our findings underscore the importance of grain-boundary engineering in advancing solid-state electrolytes and pave the way for the commercialization of next-generation all-solid-state Li-ion batteries.