Solid-state Lithium Research Articles

Mechanisms of the Accelerated Li+ Conduction in MOF-Based Solid-State Polymer Electrolytes for All-Solid-State Lithium Metal Batteries.

Solid polymer electrolytes (SPEs) for lithium metal batteries have garnered considerable interests owing to their low cost, flexibility, lightweight, and favorable interfacial compatibility with battery electrodes. Their soft mechanical nature compared to solid inorganic electrolytes give them a large advantage to be used in low pressure solid-state lithium metal batteries, which can avoid the cost and weight of the pressure cages. However, the application of SPEs is hindered by their relatively low ionic conductivity. In addressing this limitation, enormous efforts are devoted to the experimental investigation and theoretical calculations/simulation of new polymer classes. Recently, metal-organic frameworks (MOFs) have been shown to be effective in enhancing ion transport in SPEs. However, the mechanisms in enhancing Li+ conductivity have rarely been systematically and comprehensively analyzed. Therefore, this review provides an in-depth summary of the mechanisms of MOF-enhanced Li+ transport in MOF-based solid polymer electrolytes (MSPEs) in terms of polymer, MOF, MOF/polymer interface, and solid electrolyte interface aspects, respectively. Moreover, the understanding of Li+ conduction mechanisms through employing advanced characterization tools, theoretical calculations, and simulations are also reviewed in this review. Finally, the main challenges in developing MSPEs are deeply analyzed and the corresponding future research directions are also proposed.

Design Principles of Quinone Redox Systems for Advanced Sulfide Solid-State Organic Lithium Metal Batteries.

The emergence of solid-state battery technology presents a potential solution to the dissolution challenges of high-capacity small molecule quinone redox systems. Nonetheless, the successful integration of argyrodite-type Li6PS5Cl, the most promising solid-state electrolyte system,and quinone redox systems remains elusive due to their inherent reactivity. Here, a library of quinone derivatives is selected as model electrode materials to ascertain the critical descriptors governing the (electro)chemical compatibility and subsequently the performances of Li6PS5Cl-based solid-state organic lithium metal batteries (LMBs). Compatibility is attained if the lowest unoccupied molecular orbital level of the quinone derivative is sufficiently higher than the highest occupied molecular orbital level of Li6PS5Cl. The energy difference is demonstrated to be critical in ensuring chemical compatibility during composite electrode preparation and enable high-efficiency operation of solid-state organic LMBs. Considering these findings, a general principle is proposed for the selection of quinone derivatives to be integrated with Li6PS5Cl, and two solid-state organic LMBs, based on 2,5-diamino-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone, are successfully developed and tested for the first time. Validating critical factors for the design of organic battery electrode materials is expected to pave the way for advancing the development of high-efficiency and long cycle life solid-state organic batteries based on sulfides electrolytes.

Carboxymethyl chitosan composited poly(ethylene oxide) electrolyte with high ion conductivity and interfacial stability for lithium metal batteries

Low ionic conductivity and poor interface stability of poly(ethylene oxide) (PEO) restrict the practical application as polymeric electrolyte films to prepare solid-state lithium (Li) metal batteries. In this work, biomass-based carboxymethyl chitosan (CMCS) is designed and developed as organic fillers into PEO matrix to form composite electrolytes (PEO@CMCS). Carboxymethyl groups of CMCS fillers can promote the decomposition of Lithium bis(trifluoromethane sulfonimide) (LiTFSI) to generate more lithium fluoride (LiF) at CMCS/PEO interface, which not only forms ionic conductive network to promote the rapid transfer of Li+ but also effectively enhances the interface stability between polymeric electrolyte and Li metal. The enrichment of carboxyl, hydroxyl, and amidogen functional groups within CMCS fillers can form hydrogen bonds with ethylene oxide (EO) chains to improve the tensile properties of PEO-based electrolyte. In addition, the high hardness of CMCS additives can also strengthen mechanical properties of PEO-based electrolyte to resist penetration of Li dendrites. LiLi symmetric batteries can achieve stable cycle for 2500 h and lithium iron phosphate full batteries can maintain 135.5 mAh g−1 after 400 cycles. This work provides a strategy for the enhancement of ion conductivity and interface stability of PEO-based electrolyte, as well as realizes the resource utilization of biomass-based CMCS.

In situ coordinated ultrathin MOF-polymer electrolyte membrane with vertically aligned transfer channels for solid lithium metal batteries

Metal organic framework (MOF)-polymer composite solid electrolyte membrane with novel microstructure is expected to show attractive prospect for solid state lithium metal batteries. But the reported MOF were usually regarded as an entirety in composite solid electrolyte resulting in tradeoff between ionic conductivity and lithium dendrite inhibition ability. Herein, MOF-polymer composite membrane with vertically aligned channels and ultrathin MOF layer is proposed to decrease lithium ion transportation resistance obtained by simple phase inversion and in situ coordinated growth methods. The vertically aligned highways can decrease tortuous pathways and intensify ion conduction. The embedded ultrathin MOF layer on membrane surface leads to homogeneous plating/stripping of lithium. This novel structured MOF-polymer composite solid electrolyte exhibits improved ionic conductivity of 0.55 mS cm−1 at 22 ° C and lithium ion transference number of 0.87. Furthermore, the Li/Li symmetrical cell shows stable lithium plating/stripping performance for 1100 h at 0.1 mA cm−2 and 0.1 mA h cm−2. LiFePO4/MOF-polymer/Li coin battery demonstrates good rate capability and cycling performance with capacity retention of 82 % after 100 cycles at 0.2C and the pouch cell can light up the “DLUT” blue light lamp under folding and cutting states. This work encourages a new avenue to develop composite solid electrolytes with ion transportation highways and uniform distribution plane for solid lithium metal batteries.

LiTa2PO8-Based Polymer–Ceramic Electrolyte Paved the Way to High-Performance Solid-State Lithium Metal Batteries

LiTa₂PO₈-Based Polymer–Ceramic Electrolyte Paved the Way to High-Performance Solid-State Lithium Metal Batteries

Fluorine-Doped Li7La3Zr2O12 Fiber-Based Composite Electrolyte for Solid-State Lithium Batteries with Enhanced Electrochemical Performance.

Garnet-based electrolytes with high ionic conductivity and excellent stability against lithium metal anodes are promising for commercial applications in solid-state lithium batteries (SSLBs). However, the further development of SSLBs is inhibited by issues such as low ionic conductivity and uncontrolled lithium dendrite growth. Herein, we report the synthesis of fluorine-doped Li7La3Zr2O12 (LLZO-F0.2) fibers by electrospinning and the subsequent calcination at high temperatures. The solid composite electrolyte with LLZO-F0.2 exhibits an ionic conductivity of 5.37 × 10-4 S cm-1 and a high lithium-ion transference number of 0.61 at room temperature. Meanwhile, it exhibits lower resistance and more uniform lithium metal stripping and deposition in symmetric cells. The full cell with LiFePO4 cathode exhibits excellent rate capability and cycling stability for 800 cycles at 0.5 C with a discharge specific capacity retention of 97.7%. This fluorine-doped fibrous garnet-type electrolyte provides a viable option for preparing high-performance SSLBs.

Review: Application of Bionic-Structured Materials in Solid-State Electrolytes for High-Performance Lithium Metal Batteries.

Solid-state lithium metal batteries (SSLMBs) have gained significant attention in energy storage research due to their high energy density and significantly improved safety. But there are still certain problems with lithium dendrite growth, interface stability, and room-temperature practicality. Nature continually inspires human development and intricate design strategies to achieve optimal structural applications. Innovative solid-state electrolytes (SSEs), inspired by diverse natural species, have demonstrated exceptional physical, chemical, and mechanical properties. This review provides an overview of typical bionic-structured materials in SSEs, particularly those mimicking plant and animal structures, with a focus on their latest advancements in applications of solid-state lithium metal batteries. Commencing from plant structures encompassing roots, trunks, leaves, flowers, fruits, and cellular levels, the detailed influence of biomimetic strategies on SSE design and electrochemical performance are presented in this review. Subsequently, the recent progress of animal-inspired nanostructures in SSEs is summarized, including layered structures, surface morphologies, and interface compatibility in both two-dimensional (2D) and three-dimensional (3D) aspects. Finally, we also evaluate the current challenges and provide a concise outlook on future research directions. We anticipate that the review will provide useful information for future reference regarding the design of bionic-structured materials in SSEs.

Robust asymmetric gel polymer electrolytes with 2D h-BN as protective layer for highly stable solid-state lithium metal batteries

Gel polymer electrolytes (GPEs) have emerged as a highly promising alternative to conventional liquid electrolytes for stable lithium-metal batteries (LIBs). However, their inherent poor mechanical properties and limited interfacial compatibility with lithium metal usually lead to unexpected growth of lithium dendrites, hindering commercial viability. Herein, an asymmetric polymer electrolyte with h-BN (HGPE) as protective layer was fabricated via a facile one-step coating strategy. Compared to pure GPE, the asymmetric polymer electrolytes exhibit significantly enhanced mechanical strength from 4.4 MPa to 7.4 MPa, effectively suppressing lithium dendrite growth. Furthermore, the HGPE improves interfacial compatibility with the anodes by preventing direct contact between GPE and lithium metals. The addition of h-BN also enhances the lithium-ion transfer number (tLi+), reaching 0.87 compared to 0.53 for pure GPE, attributed to the hindrance of anion movement by the protective layer. Consequently, the Li symmetric battery assembled with HGPE demonstrate exceptional long-term stability, maintaining performance over 1600 h at 0.1 mA cm−2. Furthermore, the assembled Li|LiFePO4 battery can deliver a high-capacity retention rate of 93.8 % after 500 cycles at room temperature, showcasing the promising potential of asymmetric polymer electrolytes for high-performance LMBs.

Percolating coordinated ion transport cells in polymer electrolytes to realize room-temperature solid-state lithium metal batteries

Polymer electrolytes, notable for their good mechanical properties, superior processability, and high electrochemical stability, are promising for high-energy-density lithium metal batteries. However, the ionic conduction of polymer electrolytes is seriously constrained by either the entanglement of polymer chains or binding of anions, particularly at ambient temperatures, making their practical application impossible. Herein, we employ a high-salt-concentration strategy with poly(vinylene carbonate) to construct a percolating network by linking coordinated ion transport cells. The cells, consisting of lithium-ion at the core surrounded by coordinated poly(vinylene carbonate), N,N-dimethylformamide, or incompletely bonded bis(trifluoromethanesulfonyl)imide, ensure an efficient coordination and de-coordination process for ion transport. Thus, a high rate of Li+ transport is realized, achieving an ionic conductivity of 0.82 mS cm−1 at 30 °C. Consequently, the formulated solid-state lithium metal batteries with the poly(vinylene carbonate) electrolyte enable superior stability in cycling under a wide temperature range (0–60 °C), high working voltage (4.5 V), and high mass load (>10 mg cm−2). This simple strategy for creating an ion-percolating network by linking coordinated ion transport cells not only offers new insights into understanding the mechanism for ion transport in polymer electrolytes but also paves the way for the application of solid-state lithium metal batteries.

Solid-state electrolytes: a way to increase the power of lithium-ion batteries

Currently, all-solid-state lithium metal batteries are considered among the most promising energy storage devices, due to their safety and high energy density. Solid-state electrolytes, the key components of the batteries, are attracting increasing attention. This review presents an analysis of important recent advances in the field of lithium conducting solid-state electrolytes, including the mechanisms of conductivity, the main approaches to increase the conductivity, optimization of interfaces and ways to improve the stability for the main types of electrolytes, <i>i.e.</i>, inorganic, polymer and composite materials. For solid inorganic electrolytes, high conductivity and stability have been achieved; however, the problems related the formation of dense thin films and formation of a reliable contact with electrode materials are still unsolved. Polymer electrolytes are characterized by lower conductivity, which is improved upon plasticization with aprotic solvents. Composite electrolytes, for which it is possible to achieve a combination of high conductivity and good mechanical properties along with stability, are considered as the most promising. The main problems in the field of solid electrolytes for all-solid-state lithium metal batteries and possible ways to solve them are outlined.<Br>The bibliography includes 661 references.<Br> Key words: solid-state lithium battery, inorganic electrolyte, polymer electrolyte, composite electrolyte, ionic conductivity, lithium conductivity, transference numbers

Thermodynamic and structural characterization of high-entropy garnet electrolytes for all-solid-state battery

This study explores multi-component garnet-based materials as solid electrolytes for all-solid-state lithium batteries. Through a combination of computational and experimental approaches, we investigate the thermodynamic and structural properties of lithium lanthanum zirconium oxide garnets doped with various elements. Applying density functional theory, the influence of dopants on the thermodynamic stability of these garnets was studied. Probable atomic configurations and their impact on materials’ properties were investigated with the focus on understanding the influence of these configurations on structural stability, phase preference, and ionic conductivity. In addition to the computational study, series of cubic-phase garnet compounds were synthesized and their electrochemical performance was evaluated experimentally. Our findings reveal that the stability of cubic phase in doped Li-garnets is primarily governed by enthalpy, with configurational entropy playing a secondary role. Moreover, we establish that the increased number of doping elements significantly enhances the cubic phase’s stability. This in-depth understanding of materials’ properties at atomic level establishes the basis for optimizing high-entropy ceramics, contributing significantly to the advancement of solid-state lithium batteries and other applications requiring innovative material solutions.

Inorganic fillers tailored Li+ solvation sheath for stable lithium metal batteries

Ionogel electrolytes based on gel scaffolds and ionic liquids (ILs) have garnered widespread attention for their processing compatibility, non-flammability, and exceptional thermal/electrochemical properties. While there have been many studies demonstrating the effectiveness of the bisalt approach in stabilizing lithium metal anode, the precise impact of skeleton-constrained dual-anion ionogels on interface modulation remains somewhat obscured and deserves further attention. Herein, we formulate a Li6.4La3Zr1.4Ta0.6O12 (LLZTO)-incorporated dual-anion ionogel to reveal the solvation chemistry in the presence of LLZTO and detail the Li+ transport mechanism and effect on the interfacial chemistries of Li-metal. The impact of inorganic substances on the solvation structure in IL-based solid electrolytes and their role in forming the SEI layer on lithium metal was unveiled. To be specific, the introduction of fillers exert a selective modulating influence on the anions species in the Li+-solvated shell and fine-tunes the local Li+ environment, thereby fostering a more robust interfacial layer. Modified ion environment in ionogels enables a preferable shift from vehicular to structural Li+ transport, whereby a high Li ion conductivity (1.24×10−3 S/cm) and high Li ion transference number of 0.42 is achieved. The synergistic solvent coordination and adjustment of the electrode-electrolyte interface enable the LiFePO4|PIL-10|Li cells to cycle steadily with capacity retention of 95.4 % after 500 cycles at 1C and 25 °C. The strategy of promoting transport mechanisms holds promise for designing the next-generation solid-state lithium metal batteries with high energy density.

Vitrified Metal-Organic Framework Composite Electrolyte Enabling Dendrite-Free and Long-Lifespan Solid-State Lithium Metal Batteries.

Solid-state lithium metal batteries (LMBs) are still plagued with low ionic conductivity and inferior interfacial contact, which hinder their practical implementation. Herein, a quasi-solid-state composite electrolyte, poly(1,3-dioxolane) (PDOL)/glassy ZIF-62 (PGZ) with fast ion transport and intimate interface contact, is fabricated via in situ polymerization. The in situ polymerization of DOL in an electrolyte matrix not only improves the exterior interface between electrolyte/electrode but also optimizes the inner interfaces among glassy particles, rendering PGZ as an uninterrupted ionic conductor. Moreover, PGZ inherits the superior ionic conductivity and the robust dendrite prohibition of glassy MOFs originating from their grain-boundary-free nature, isotropy, and abundant groups containing N species. As expected, our proposed PGZ exhibits a prominent ionic conductivity of 6.3 × 10-4 S cm-1 at 20 °C. Li|PGZ|LiFePO4 delivers an outstanding rate performance (103 mAh g-1 at 4C) and a stable cycling capacity (118 mAh g-1 at 1C over 1000 cycles). PGZ also presents excellent low-temperature cycling performance with 75 mAh g-1 for 480 cycles at -20 °C and excellent flame retardance. Even at a high loading of 12.1 mg cm-2, it can still discharge at 140 mAh g-1 for 100 cycles. Hence, PGZ prepared via in situ polymerization holds enormous prospects as a solid-state electrolyte for high-performance and safe LMBs.

Neuron-Like Silicone Nanofilaments@Montmorillonite Nanofillers of PEO-Based Solid-State Electrolytes for Lithium Metal Batteries with Wide Operation Temperature.

Poly(ethylene oxide) (PEO)-based composite solid electrolytes (CSEs) are promising to accelerate commercialization of solid-state lithium metal batteries (SSLMBs). Nonetheless, this is hindered by the CSEs' limited ion conductivity at room temperature. Here, we propose design, synthesis, and application of the bioinspired neuron-like nanofillers for PEO-based CSEs. The neuron-like superhydrophobic nanofillers are synthesized by controllably grafting silicone nanofilaments onto montmorillonite nanosheets. Compared to various reported fillers, the nanofillers can greatly improve ionic conductivity (4.9×10-4 S cm-1, 30 °C), Li+ transference number (0.63), oxidation stability (5.3 V) and mechanical properties of the PEO-based CSEs because of the following facts. The distinctive neuron-like structure and the resulting synaptic-like connections establish numerous long-distance continuous channels over various directions in the PEO-based CSEs for fast and uniform Li+ transport. Consequently, the assembled SSLMBs with the CSEs and LiFePO4 or NCM811 cathodes display superior cycling stability over a wide temperature range of 50 °C to 0 °C. Surprisingly, the pouch batteries with the large-scale prepared CSEs kept working after being repeatedly bent, folded, cut or even punched in air. We believe that design of neuron-like nanofillers is a viable approach to produce CSEs with high room temperature ionic conductivity for SSLMBs.

Inhibiting Residual Solvent Induced Side Reactions in Vinylidene Fluoride-Based Polymer Electrolytes Enables Ultra-Stable Solid-State Lithium Metal Batteries.

Residual solvents in vinylidene fluoride (VDF)-based solid polymer electrolytes (SPEs) have been recognized as responsible for their high ionic conductivity. However, side reactions by the residual solvents with the lithium (Li) metal induce poor stability, which has been long neglected. This study proposes a strategy to achieve a delicate equilibrium between ion conduction and electrode stability for VDF-based SPEs. Specifically, 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA) is developed as the nonside reaction solvent for poly(vinylidene fluoride-co-hexafluoropropylene) (PVHF)-based SPEs, achieving both high ionic conductivity and significantly improved electrochemical stability. The developed FDMA solvent fosters the formation of a stable solid electrolyte interphase (SEI) through interface reactions with Li metal, effectively mitigating side reactions and dendrite growth on the Li metal electrode. Consequently, the Li||Li symmetric cells and Li||LiFePO4 cells demonstrate excellent cycling performance, even under limited Li (20µm thick) supply and high-loading cathodes (>10mg cm-2, capacity >1 mAh cm-2) conditions. The stable Li||LiCoO2 cells operation with a cutoff voltage of 4.48V indicates the high-voltage stability of the developed SPE. This study offers valuable insights into the development of advanced VDF-based SPEs for enhanced lithium metal battery performance and longevity.

Polymer-based electrolytes for high-voltage solid-state lithium batteries

Increasing the charging cut-off voltage of lithium batteries is a feasible method to enhance the energy density. However, when batteries operate at high voltages (> 4.3 V), the degradation of liquid organic carbonate electrolyte is accelerated and may cause safety hazards. Polymer-based electrolytes with inherently high safety and good electrochemical stability can prevent the electrolyte degradation in high-voltage solid-state lithium batteries. This paper provides a comprehensive and in-depth review of the design strategies, recent developments, and scientific challenges associated with polymer-based electrolytes for high-voltage applications. Emphases are placed on the interfacial compatibility between electrolytes and cathodes, such as mechanical contacts and interface chemical stability, which are critical to the lifespan of high-voltage lithium batteries. Moreover, guidelines for the future development of high-voltage solid-state lithium batteries are also discussed.

Li Alloys in All Solid-State Lithium Batteries: A Review of Fundamentals and Applications

Li Alloys in All Solid-State Lithium Batteries: A Review of Fundamentals and Applications

Solid-state lithium batteries composed of hematite and oxide electrolyte

As Li-ion battery anode materials, two types of hematite (Fe2O3(big), Fe2O3(ultrafine)) were evaluated by using liquid electrolyte and oxide-based solid electrolyte. Although the anode using Fe2O3(ultrafine) with larger specific surface area showed a high initial reversible capacity in the liquid-electrolyte cell, there was a steep capacity decay in the cycling test. In the solid-electrolyte cell, we obtained very low reversible capacities of 40 mA h g−1 for the anode using Fe2O3(big) with smaller specific surface area. In contrast, the capacity of Fe2O3(ultrafine) anode was as high as 400 mA h g−1 at the 20th cycle. This is the first demonstration of charge–discharge reactions for Fe2O3 anode in oxide-based solid-state batteries. The Fe2O3(ultrafine) particles were dispersed relatively uniformly between solid electrolyte in the active layer, suggesting that the contact area between Fe2O3 and solid electrolyte becomes large. Consequently, Fe2O3(ultrafine) could benefit from larger contact area delivering the suitable reaction site for Li+ to improve the anode performance.

Design of Fluorinated Elastomeric Electrolyte for Solid-State Lithium Metal Batteries Operating at Low Temperature and High Voltage.

This work demonstrates the low-temperature operation of solid-state lithium metal batteries (LMBs) through the development of a fluorinated and plastic-crystal-embedded elastomeric electrolyte (F-PCEE). The F-PCEE is formed via polymerization-induced phase separation between the polymer matrix and plastic crystal phase, offering a high mechanical strain (≈300%) and ionic conductivity (≈0.23 mS cm-1) at -10°C. Notably, strong phase separation between two phases leads to the selective distribution of lithium (Li) salts within the plastic crystal phase, enabling superior elasticity and high ionic conductivity at low temperatures. The F-PCEE in a Li/LiNi0.8Co0.1Mn0.1O2 full cell maintains 74.4% and 42.5% of discharge capacity at -10°C and -20°C, respectively, compared to that at 25°C. Furthermore, the full cell exhibits 85.3% capacity retention after 150 cycles at -10°C and a high cut-off voltage of 4.5V, representing one of the highest cycling performances among the reported solid polymer electrolytes for low-temperature LMBs. This work attributes the prolonged cycling lifetime of F-PCEE at -10°C to the great mechanical robustness to suppress the Li-dendrite growth and ability to form superior LiF-rich interphases. This study establishes the design strategies of elastomeric electrolytes for developing solid-state LMBs operating at low temperatures and high voltages.

The role of nanoporous carbon materials for thiophosphate-based all solid state lithium sulfur battery performance

Due to their high theoretical energy density, all solid state lithium sulfur batteries (LS-SSB) represent one of the most promising candidates for next-generation energy storage systems. Whilst high sulfur utilizations have been published for several cathode compositions and preparation methods in recent years, there is still a lack of clarity regarding the influence of the used carbon. Furthermore, LS-SSBs face challenges in up-scaling as the common preparation methods including high energy ball milling are time consuming, batch-wise and need high energy impact. In this study, high sulfur utilization >1600 mAh gS−1 and reversibility with 80 % of initial discharge capacity after 60 cycles is achieved, using a more time-efficient preparation method with drastically lowered energy impact by selecting a suitable carbon. Additionally, the influence of the carbon nanostructure on the electrochemical performance is discussed. This study provides guidance in selecting nanostructured carbon materials to enable cost-efficient, up-scalable preparation methods for LS-SSBs without compromising on the excellent electrochemical performance.