Lithium Salts Research Articles

A Super-Ionic Solid-State Block Copolymer Electrolyte.

Polymer solid-state electrolytes offer great promise for battery materials with high energy density, mechanical stability, and improved safety. However, their low ion conductivities have so far limited their potential applications. Here, it is shown for poly(ethylene oxide) block copolymers that the super-stoichiometric addition of lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) as lithium salt leads to the formation of a crystalline PEO block copolymer phase with exceptionally high ion conductivities and low activation energies. The addition of LiTFSI further induces block copolymer phase transitions into bi-continuous Fddd and gyroid network morphologies, providing continuous 3D conduction pathways. Both effects lead to solid-state block copolymer electrolyte membranes with ion conductivities of up to 1·10-1Scm-1 at 90°C, decreasing only moderately to 4·10-2Scm-1 at room temperature, and to >1·10-3Scm-1 at -20°C, corresponding to activation energies as low as 0.19eV. The co-crystallization of PEO and LiTFSI with ether and carbonate solvents is observed to play a key role to realize a super-ionic conduction mechanism. The discovery of PEO super-ionic conductivity at high lithium concentrations opens a new pathway for fabrication of solid polymer electrolyte membranes with sufficiently high ion conductivities over a broad temperature range with widespread applications in electrical devices.

Synergistic Enhancement of Biaxial Stretching and Multilayer Composites in All-Solid-State Polymer Electrolytes.

As an important component of lithium-ion batteries, all-solid-state electrolytes should possess high ionic conductivity, excellent flexibility, and relatively high mechanical strength. All-solid-state polymer electrolytes (ASSPEs) based on polymers seem to be able to meet these requirements. However, pure ASSPEs have relatively low ionic conductivity, and the addition of inorganic fillers such as lithium salts will reduce their flexibility and mechanical strength. To address the above issues, in this paper, the solvent-free method was used to prepare a poly(vinylidenefluoride-co-hexafluoropropylene)/lithium bis(trifluoromethanesulfonyl) imide/poly(ethylene oxide) all-solid-state polymer electrolyte, which was then subjected to 4 × 4 magnification synchronous bidirectional stretching. Subsequently, it was multilayered with PEO-based composite polymer electrolytes to obtain multilayered composite polymer electrolytes (MCPEs). Bidirectional stretching provides superior in-plane and out-of-plane mechanical properties to MCPEs by inducing molecular chain orientation, which suppresses the growth of lithium dendrites. Concurrently, it facilitates the formation of the β-crystal form of PVDF-HFP, thereby weakening the ion solvation effect and reducing the lithium-ion migration energy barrier. Multilayered compounding improves the interfacial contact between MCPEs and electrodes, thereby reducing the interfacial impedance. Experiments have demonstrated that the MCPEs prepared in this paper exhibit high ionic conductivity at room temperature (1.83 × 10-4 S cm-1), low interfacial resistance (547 Ω cm-2), excellent mechanical properties (26 MPa), and excellent cycling rate performance (a capacity retention rate of 90% after 110 cycles at 0.1 C), which can meet the performance requirements of lithium-ion batteries for ASSPEs.

A method for deriving oligomers from sulfamide monomer and their application as electrolytes

This paper describes the development of a method of catalytic polymerization that was then applied to synthesize sulfate-based oligomers from sulfamide. Two molecules, copper triflate and copper acetate, catalyzed the formation of oligomers with diol monomers. Two oligomers were identified as products of the reactions. Oligomers with sulfate incorporated in the backbone proved to have an ability for ion diffusion. When the oligomers were doped with lithium salt, anion transportation was predominant, as shown by solid-state NMR. The lithium ion was found to be strongly bonded to the backbone, while the anion was highly mobile. To corroborate this finding, we conducted molecular dynamics (MD) simulations, which revealed the structural characteristics and static properties of two electrolytes containing LiTFSI and two different polyethylene oxide oligomers. Interactions between the anion and cation were analyzed through computation of the radial distribution function (RDF) and the spatial distribution function (SDF). Our findings indicate that while the anion presents weak interactions with the polymer chain, the cation interacts strongly with the oligomer backbone.

Pyrrolidinium-Based Ionic Liquids as Advanced Non-Aqueous Electrolytes for Safer Next Generation Lithium Batteries

In the current context of increasing energy demand, ionic liquids (ILs) are presented as possible candidates to replace conventional electrolytes and to develop more efficient energy storage devices. The IL 1-Methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide has been selected for this work, due to the good thermal and chemical stabilities and good electrochemical performance of the pyrrolidinium cation based ILs. Binary mixtures of this IL and lithium salt with the same anion, [TFSI], have been prepared with the aim of assessing them, as possible electrolytes for lithium batteries. These mixtures were thermally and electrochemically characterised through DSC and dielectric spectroscopy studies. The ionic conductivity decreases as the salt concentration increases, finding values ranging between 0.4 S/m and 0.1 S/m at room temperature. Additionally, a wide liquid range was found for the mixtures, which would reduce or even eliminate some of the most common problems of current electrolytes, such as their crystallisation at low temperatures and flammability. Finally, the toxicity of pure IL and the intermediate salt concentration was also evaluated in terms of the bioluminescence inhibition of the Alivibrio Fischeri bacteria, observing that, although the toxicity increases with the salt addition, both samples can be classified as practically harmless.

Experimental study of radioprotective properties of lithium pyruvate in vitro

Radiotoxicity is a serious problem for patients undergoing radiotherapy, so the search for new radioprotective drugs to mitigate its effects is highly relevant. Radioprotectors should have a number of properties, including direct antioxidant action, reduction of oxidative stress, ability to induce DNA repair or inhibit apoptosis, and at the same time not cause their own side effects. Antioxidants based on lithium salts look promising in terms of their properties. The aim of study was to study the radioprotective properties of lithium pyruvate in vitro. Material and Methods. Relatively radiosensitive blood mononuclear cells and relatively radioresistant fibroblasts of 3T3L1 line were used as biomodels for x-ray exposure. Cells were incubated and irradiated in 96-well plates. Lithium pyruvate was used at a final concentration of 1.2 mM. Cells were irradiated at a dose rate of 15 mGy/s in the absorbed-dose range from 0 to 5 Gy using an x-ray unit (anode voltage: 160 kV, average current: 3.5 mA). Cell viability was assessed by MTT test and resazurin test. The evaluation of cell death variants and the level of oxidative stress were determined by cytofluorimetric method. Results. The cytoprotective effect of lithium pyruvate was established. Cytoprotection was manifested in the increased cell survival and decreased oxidative stress level under lithium pyruvate after x-ray in a wide range of absorbed doses. Relatively high efficiency was shown in relation to blood mononuclear cells with an increase in the viable fraction by 5–7 % and a decrease in oxidative stress level during irradiation in the range of 1.0–3.0 Gy. Apoptosis was found to be the main mechanism of cell death after irradiation. Lithium pyruvate reduced the level of apoptosis in cell population under irradiation and chemically induced oxidative stress. Conclusion. Radioprotective effect of lithium pyruvate under x-ray irradiation in vitro has been shown. Reduction of oxidative stress under the action of pyruvate provides a pathogenetic basis for the potential use of this compound as a radioprotector, which requires further studies on in vivo models.

Rare Gold-Catalyzed 4-exo-dig Cyclization for Ring Expansion of Propargylic Aziridines toward Stereoselective (Z)-Alkylidene Azetidines, via Diborylalkyl Homopropargyl Amines.

We report an uncommon 4-exo-dig cyclization of N-tosyl homopropargyl amines, catalyzed by [AuCl(PEt3)]/AgOTf, to prepare stereoselective (Z)-2-alkylidene-1-tosylazetidine compounds. The reaction outcome contrasts with the gold-catalyzed cyclization of N-tosyl homopropargyl amines containing a methyl group at the propargylic position that provides substituted 2,3-dihydropyrroles via a 5-endo-dig mechanism. The access to N-tosyl homopropargyl amines is possible by the regioselective nucleophilic attack of α-diboryl alkylidene lithium salts to propargylic aziridines.

A Supramolecular Deep Eutectic Electrolyte Enhancing Interfacial Stability and Solution Phase Discharge in Li-O2 Batteries.

Li-O2 batteries (LOBs) have gained widespread recognition for their exceptional energy densities. However, a major challenge faced by LOBs is the lack of appropriate electrolytes that can effectively balance reactant transport, interfacial compatibility, and non-volatility. To address this issue, a novel supramolecular deep eutectic electrolyte (DEE) has been developed, based on synergistic interaction between Li-bonds and H-bonds through a combination of lithium salt (LiTFSI), acetamide (Ace) and boric acid (BA). The incorporation of BA serves as an interface modification additive, acting as both Li-bonds acceptor and H-bonds donor/acceptor, thereby enhancing the redox stability of the electrolyte, facilitating a solution phase discharge process and improving compatibility with the Li anode. Our proposed DEE demonstrates a high oxidation voltage of 4.5 V, an ultrahigh discharge capacity of 15225 mAh g-1 and stable cycling performance of 196 cycles in LOBs. Additionally, the intrinsic non-flammability and successful operation of a Li-O2 pouch cell indicate promising practical applications of this electrolyte. This research broadens the design possibilities for LOBs electrolytes and provides theoretical insights for future studies.

A Supramolecular Deep Eutectic Electrolyte Enhancing Interfacial Stability and Solution Phase Discharge in Li‐O2 Batteries

Li‐O2 batteries (LOBs) have gained widespread recognition for their exceptional energy densities. However, a major challenge faced by LOBs is the lack of appropriate electrolytes that can effectively balance reactant transport, interfacial compatibility, and non‐volatility. To address this issue, a novel supramolecular deep eutectic electrolyte (DEE) has been developed, based on synergistic interaction between Li‐bonds and H‐bonds through a combination of lithium salt (LiTFSI), acetamide (Ace) and boric acid (BA). The incorporation of BA serves as an interface modification additive, acting as both Li‐bonds acceptor and H‐bonds donor/acceptor, thereby enhancing the redox stability of the electrolyte, facilitating a solution phase discharge process and improving compatibility with the Li anode. Our proposed DEE demonstrates a high oxidation voltage of 4.5 V, an ultrahigh discharge capacity of 15225 mAh g−1 and stable cycling performance of 196 cycles in LOBs. Additionally, the intrinsic non‐flammability and successful operation of a Li‐O2 pouch cell indicate promising practical applications of this electrolyte. This research broadens the design possibilities for LOBs electrolytes and provides theoretical insights for future studies.

A novel technology for lithium extraction through low-temperature synergistic roasting of α-spodumene with lepidolite

α-Spodumene and lepidolite have garnered significant attention because of the booming market of lithium (Li) salts. However, α-spodumene requires a high-temperature phase transition step at ≥1050 °C, and lepidolite needs a large amount of sulfate to extract Li. The economic and environmental benefits of these processes need to be improved. Herein, an innovative scheme, low-temperature synergistic roasting of α-spodumene with lepidolite, was proposed to efficiently extract Li. The conditions for phase transition roasting, acid baking, and water leaching were sequentially optimized. The mechanisms underlying the synchronous phase transition of α-spodumene and lepidolite were studied using various characterization methods. Results indicated that lepidolite lowers the transition temperature of spodumene from the α-phase to the β-phase by 150 °C. During the synergistic roasting, fluorine escapes from the lepidolite lattice and attacks SiO, AlO, and LiO bonds within the α-spodumene lattice. Under optimal conditions, 97.60 % of the Li was extracted, while the leaching ratios of Na, K, Al, and Si were only 50.96 %, 10.96 %, 5.75 %, and 0.30 %, respectively. Current scheme is a promising low-carbon technology that synchronously achieves the low-temperature phase transition of α-spodumene and additive-free Li extraction from lepidolite, offering superior economics, environmental benefits, and practicality compared with the existing methods.

Investigating the electrochemical properties of poly(vinylidene fluoride)/polyaniline blends doped with lithium-based salt

Conductive polymers have attracted much attention in various applications, owing to their excellent chemical, thermal, and oxidative stability. However, they have low dielectric constant, which limits their performance in electrochemical devices. To overcome this drawback, blending with other polymers helps improving their electrochemical properties. Herein, we investigate structural and electrochemical properties of poly(vinylidene fluoride) (PVDF)/polyaniline (PANI) blends doped with lithium-based salt. Results showed that the blends exhibit phase separation of PANI and PVDF, which is confirmed by the thermodynamic interaction parameter. We found that the interaction between the two polymers enhanced the ionic conductivity from 4.9×10-5 S.cm-1 for neat PVDF to 5.3×10-4 S.cm-1 for composition of 50:50 (PANI50), whereas the ionic conductivity was inversely proportional to the temperature. Moreover, by adding lithium salt to the blend, the thermal stability increased from 376.6 to 478.5 °C for PANI50. The ionic conductivity of the blends depends on the PVDF content, which affects the interaction between the two polymers.

High-surface area active boron nitride nanofiber rich in oxygen vacancies enhanced the interface stability of all-solid-state composite electrolytes

Solid electrolytes are the most promising candidate for replacing liquid electrolytes due to their safety and chemical stability advantages. However, a single inorganic or organic solid electrolyte cannot meet the requirements of commercial all-solid-state batteries (ASSBs), which motivates the composite polymer electrolyte (CPE). Herein, a CPE of boron nitride nanofiber (BNNF) with a high specific surface area, rich pore structure, and poly (ethylene oxide) (PEO) are reported. Anions strongly adsorb on the surface of BNNF through electrostatic interactions based on oxygen vacancies, promoting the dissociation of lithium salts at the two-phase interface. The three-dimensional (3D) BNNF network provides three advantages in the CPE, including (i) improving ionic conductivity through strong interaction between polymers and fillers, (ii) improving mechanical properties through weaving a robust skeleton, and (iii) improving stability through a rapid and uniform thermal dispersion pathway. Therefore, the CPE with BNNF delivers high ionic conduction of 4.21 × 10−4 S cm−1 at 60°C and excellent cycling stability (plating/stripping cycles for 2000 h with a low overpotential of ∼40 mV), which results in excellent electrochemical performance of LiFePO4 (LFP) full cell assembled with CPE-5BNNF-1300 (152.7 mAh g−1 after 200 cycles at 0.5 C, and 134.8 mAh g−1 at 2.0 C). Furthermore, when matched with high-voltage LiNi0.6Co0.2Mn0.2O2 (NCM622), it also exhibits an outstanding rate capacity of 120.4 mAh g−1 at 1.0 C. This work provides insight into the BNNF composite electrolyte and promotes its practical application for ASSBs.

PEO kaolinite intercalation interface accelerates lithium-ion transfer for all-solid-state lithium metal batteries

The improvement of ionic conductivity and Li dendrite inhibition capability of poly(ethylene oxide)(PEO)-based solid polymer electrolytes(SPEs) is urgent for the development of all-solid-state lithium metal batteries (ASSLMBs). Here, intercalated composite consisted with PEO polymer chains inserted into the clay gallery of the formamide intercalated kaolinite (KM) is formed. Due to this alternating organic-inorganic layered structure, the crystallinity of PEO decreases to 26.2% and the ion conductivity of SPE with 3% KM of PEO mass added(PEO+KM-3) increased to 1.43 × 10−3 S cm−1 at 60 °C. Besides, bis (trifluoromethane) sulfonimide lithium salt (LiTFSI) interacts with formamide to form a complex, making the local solvated Li+ transports close to a quasi-solid model. PEO+KM-3 SPE exhibits a good inhibition effect on lithium dendrites due to the formation of organic silicon at lithium anode side, and Li/ PEO+KM-3/Li cell works steadily for more than 1600 h at 60 °C with 0.1 mA cm−2. The assembled Li//LiFePO4 cell provides a capacity of 118 mAh g−1 after 500 cycles at 0.5 C at 60 °C.

Impact of functional groups on lithium salt dispersion and mobility in polymer electrolytes

AbstractSolid Polymer electrolytes are versatile, highly processible and electrochemically compatible with solid electrode materials. The versatility of these materials is a result of the existence of many possible conductive polymer‐salt, polymer‐polymer and salt‐salt combinations. Despite the wide array of available lithium salts, most polymer electrolyte materials are made using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) due to its long history of achieving relatively high ionic conductivities in polymer electrolyte systems with the most famous being poly(ethylene oxide) (PEO). It is however possible that better ionic conductivities can be achieved with different salts and/or in polymer matrices containing different functional groups. This is because ionic conductivity in polymer electrolytes is partially based on the ability of the polymer matrix to dissolve and bond to the salt. These interactions impact local‐scale ion mobility which can be measured via NMR spectroscopy using pulsed field gradient experiments. In this work, polymer electrolytes are prepared using PEO, hydrogenated nitrile butadiene rubber and poly(propylene) carbonate. Ion mobility, lithium conductivity and salt‐polymer interactions are investigated to compare interactions between LiTFSI and lithium cyano(trifluorosulfonyl)imide in polymers with common salt‐dissociating functional groups such as ethyl, nitrile and carbonate to determine the impact of these interactions on ionic conductivity.

Polymer Composite Electrolytes Membrane Consisted of Polyacrylonitrile Nanofibers Containing Lithium Salts: Improved Ion Conductive Characteristics and All‐Solid‐State Battery Performance

AbstractPolymer electrolyte membranes with superior lithium‐ion (Li+) conductivity and sufficient electrochemical stability are desired for all‐solid‐state lithium‐ion batteries (ASS‐LIBs). This paper reports novel polymer composite membranes consisting of polyacrylonitrile (PAN) nanofibers (Nfs) containing lithium salts. It is first revealed that the lithium salt addition increases polar surface groups on the PAN nanofibers. Subsequently, the lithium salts‐containing PAN nanofiber (PAN/Li Nf) composite membrane affects the matrix poly(ethylene oxide) (PEO)/lithium bis(trifluoromethyl sulfonylimide) (LiTFSI) electrolyte to increase the numbers of Li+ with high mobility. Consequently, the PAN/Li Nf composite membrane shows relatively good ion conductivity (σ = 9.0 × 10−5 S cm−1) and a considerably large Li+ transference number (tLi+ = 0.41) at 60 °C, compared to the PEO/LiTFSI membrane without nanofibers. The 6Li solid‐state NMR study supports that the PAN/Li Nf bearing abundant polar nitrile groups at their surface enhances Li+ diffusion in the PEO‐based electrolyte membranes. The galvanostatic constant current cycling tests reveal that the PAN/Li Nf composite membrane possesses good electrochemical and mechanical stabilities. The ASS‐LIB consisting of the PAN/Li Nf composite membrane shows significantly improved charge and discharge cycling performances, promising future all‐solid‐state batteries.

Metal-organic frameworks Derived frustrated Lewis acid-base pairs accelerate ion dynamics to dendrite-free solid-state lithium batteries

The Poly(ethylene oxide) (PEO)-based polymer electrolytes exhibit the drawbacks of high crystallinity and low ionic conductivity (<10−5 S m−1), which significantly restrict their application in solid-state lithium metal batteries. This study presents the bismuth metal-organic frameworks (MOFs) as a PEO-based electrolyte filler, incorporating frustrated Lewis acid-base pairs, which is formed in-situ through the coordination of ellagic acid (EA) and bismuth ions (Bi3+). The simultaneous presence of Lewis acids (unsaturated Bi3+) and bases (free nitrate, NO3−) in the MOFs, which effectively transfers and transports the lithium ions through the synergistic interaction based on the polymer matrix and the lithium salts, resulting in the high durable solid-state lithium batteries. Meanwhile, NO3− can further promote the dissociation of lithium ion (Li+) and the formation of inorganic solid electrolyte interfaces (SEIs) with lithium metal, which is conducive to the dynamic repair of SEIs. Characterizations and calculations show that Bi-MOFs promote the increase of composite ionic conductivity (6.4 × 10−4 S cm−1, 60 °C) and lithium transference number (0.52, 60 °C). At a current density of 0.4 mA cm−2, the assembled Li–Li symmetric battery can be continuously cycled for more than 500 h. This strategy opens a new window for improvement of solid-state electrolyte performance.

Aqueous lithium-ion battery of dual electrolytes separated by cation-exchange membrane with enhanced rate capability for thick electrodes

Aqueous lithium-ion batteries (ALIBs) have received increasing attention because of their high safety. An aqueous electrolyte system compatible with a wider electrochemical window and high ionic conductivity is desired to increase the industrial potential of ALIBs. In this study, a dual-electrolyte system separated by a perfluorosulfonated cation-exchange membrane (CEM) was designed to demonstrate a 2 V-class ALIB. The specific compositions of the cathode and anode electrolytes to be stable in facing via the CEM were experimentally determined, where each electrolyte pH was adjusted for the lithiation/delithiation of LiMn2O4 and TiO2, together with a high ionic conductivity of >70 mS/cm. The pH difference successfully suppressed water splitting, which enabled stable battery operation in the 1.5–2.8 V range with >99 % Coulombic efficiency. The optimized cathode and anode electrolytes also exhibited better rate performances even in a thick electrode layer over 50 mg/cm2 of the active material loading than a conventional concentrated electrolyte of 21 mol/kg LiTFSI (9 mS/cm). The present system, which employs the aqueous electrolytes with smaller lithium salts and favorable ionic conductivities should increase the industrial potential of low-cost aqueous lithium-ion batteries.

Thermal transport of alkali halide aqueous solutions: a non-equilibrium molecular dynamics investigation

Electrolyte solutions are essential in various physical, chemical, and biological processes. Thermal fields induce ion mass fluxes in electrolyte solutions, creating stable salt concentration gradients at stationary conditions. The response of the salt to the thermal field is quite complex, as the ions move towards hot or cold regions depending on the composition of the solution. While these phenomena are well-known, the microscopic mechanism determining thermodiffusion is still poorly understood. In this study, we used non-equilibrium molecular dynamics simulations and the Madrid 2019 forcefield to investigate the thermal transport properties of several electrolyte solutions: {Li + , Na + , K + }Cl − and {Li + , Na + , K + }I − . We show that the reduction of the thermal conductivity with salt concentration is correlated with the modification of the isothermal compressibility and the molar mass of the solution. We also calculate the Soret coefficient of the solutions and compare our results with those of existing experiments. The Madrid 2019 forcefield reproduces the main experimental trends of chloride solutions and the stronger thermophilic response of lithium salts. Our results suggest a connection between the ability of cations (Na + , K + ) to disturb oxygen-oxygen correlations within the 0.35–0.5 nm inter-oxygen distance range and the thermophobicity of the solutions.

Lithium salt preprocessing calcination strategy for a more stable layered structure of lithium-rich manganese-based cathodes

The poor cycling performance of lithium-rich manganese-based (LMR) cathodes limits their practical applications. The stability of the layered structure is closely related to the cycling performance. The high-temperature solid-state reaction between transition metal oxides (TMOs) and lithium salts promotes the formation of the layered structure, which determines the quality of the layered structure. Considering the influence of physicochemical changes of the lithium salt on the formed layered structural stability, in this work, the calcination strategy includes a short period of holding time near the melting point of Li2CO3, referred to as the lithium salt preprocessing calcination strategy, which allows the molten Li2CO3 to be fully contacted with TMOs at relatively low temperatures, alleviating the problem of Li in the thermal decomposition products of Li2CO3 not easily further reacting with TMOs. Compared to the conventional calcination procedure, this new calcination strategy reduces the oxygen vacancy concentration as well as the relative Mn3+ content on the surface of the cathodes, which significantly improves the cycling performance. In addition, the shortening of the constant high temperature calcination time effectively reduces the production energy consumption, which provides a reference for the future efficient and low-cost synthesis of electrode materials with excellent cycling performance.

In situ construction of ether-based composite electrolyte with stable electrode interphase for high-performance solid state lithium metal battery

Ether-based polymer electrolyte shows promising potential for application in solid-state lithium batteries owing to its cost-effectiveness, excellent flexibility, and above all, remarkable stability to lithium metal anode. However, it still suffers from challenges related to low ionic conductivity and inferior oxidation resistance. Herein, an ether-based gel composite electrolyte containing Li6.5La3Zr1.5Ta0.5O12 (LLZTO) ceramics (LL-GCE) is fabricated via an in-situ polymerization method which can guarantee good interface contact with electrodes. The ceramics not only activate the interaction between polymers and lithium salts, resulting in significantly enhanced ionic conductivity (7.9 × 10−4 S cm−1), but also collaborate with poly(1,3-dioxolane) (PDOL) to construct favorable anion-rich solvation configurations, which effectively restrict the anion migration with Li+ transference number significantly increased to 0.83. Furthermore, the regulated solvation structures can passivate the electrode surface with a high content of robust LiF components formed on the electrolyte/electrode interphase. Consequently, the composite electrolyte demonstrates excellent abilities to inhibit Li dendrite growth and match with high-voltage cathodes. For instance, the LiFePO4||Li cell using such electrolyte conveys a capacity of 135.4mAh/g and the capacity retention is 99.3 % after 250 cycles at 1C. The LiCoO2||Li full cell also shows excellent cycling performance. This work provides an effective strategy to modify ether-based polymer electrolytes and can boost their development in high-performance solid state lithium metal batteries.

Theoretical Study on the Dynamics of Lithium-Ion Transport in PPS-Based Polymer Electrolytes

The development of solid-state lithium-ion batteries (LIBs) is a key advancement in energy storage technology. Solid electrolytes are important in this development because they are safer and more stable than liquid electrolytes, and they have higher energy density. Among the various types of solid electrolytes, Polyphenylene Sulfide (PPS)-based solid-state polymer electrolytes (SPEs) are notable for their ability to conduct ions as well as liquid electrolytes across a wide range of temperatures. This ability is particularly important because other solid polymer electrolytes, like those based on polyethylene oxide (PEO), struggle with ion conduction at different temperatures. PPS-based SPEs are different because their ion transport does not depend on the movement of the polymer chains, which means their ion conduction remains steady from high to low temperatures.The previous study conducted a series of first-principle calculations, revealing that the introduction of neutral molecules, referred to as agent molecules, can significantly enhance the movement of lithium ions within a solid matrix when these are mixed with lithium salts. This is because the intermolecular interactions within a binary system comprising an agent molecule and lithium salt are governed by a strong bond formation between lithium and oxygen atoms. When these agent molecules are introduced, they replace the anionic species around lithium in the salts, leading to a weakened Coulomb force between lithium and oxygen. This reduction is essential for rapid lithium-ion movement through the easy separation of lithium salts and the subsequent generation of ion-hopping sites characterized as lithium-free oxygen cages. According to the previous study, the strategic selection of neutral molecules with functional groups that bolster chemical resonance is imperative. Such molecules have been identified as promising candidates for agent molecules.Our study builds upon previous research by directly incorporating PPS polymers into our computational simulations. We utilized molecular dynamics and quantum mechanics to examine the role of neutral molecules in PPS in facilitating lithium-ion mobility. We parameterized our system with quantum mechanics calculations, which were crucial in informing our molecular dynamics simulations. Using VASP program for interaction assessment and LAMMPS program for energy and structure analysis, we refined our models to understand the interactions between PPS polymers, Li+ ions, TFSI- ions, and Chloranil molecules. Our simulations explored the structural dynamics and the effects of fillers and PPS polymer layers on ion transport.Our work enhances the basic understanding of SPEs and helps in the creation of new lithium-ion batteries that perform better and are safer. We've pinpointed important factors that control how lithium ions move in PPS-based electrolytes, laying the groundwork for future improvements in solid-state electrolytes and leading to lithium-ion batteries that are more effective and safer.Reference:[1] Jiwon Yu, Myungsuk Lee, Yeonseo Kim, Hyung-Kyu Lim, Jonghyun Chae, Gyeong S. Hwang, Sangheon Lee, “Agent molecule modulated low-temperature activation of solid-state lithium-ion transport for polymer electrolytes”, Journal of Power Sources 505, 229917 (2021).