Electrolytes For Li-ion Batteries Research Articles

Exploring the capabilities and limitations of the Van Hove function to understand directional correlations in ion movements within Li-ion battery electrolytes.

Understanding microscopic directional correlations in ion movements within lithium-ion battery (LIB) electrolytes is important because these correlations directly affect the ionic conductivity. Onsager transport coefficients are widely used to understand these correlations. On the other hand, the Van Hove function (VHF) is also capable of determining correlated motions. However, identifying various types of ion correlated motions in LIB electrolytes using VHF is not well explored. Here, we have conducted molecular dynamics simulations of a representative experimental LIB electrolyte system-lithium hexafluorophosphate (LiPF6)-at different concentrations in a (9:1 wt. %) mixture of ethyl methyl carbonate and fluoroethylene carbonate in order to explore the capabilities and limitations of using VHF to understand different types of ion correlations. We conclude that analysis of VHF can qualitatively describe both the positive correlation between cation-anion at different salt concentrations and the negative correlation between cation-cation and anion-anion present in high salt concentration, but it cannot foretell which correlation is dominating at any given electrolyte concentration. This type of quantitative information can be obtained only via Onsager's approach. This could be seen as a limitation of relying solely on VHF to fully understand ion correlation in electrolyte media.

Using Three-Dimensional Carbon and Boron Nitride to Improve the Properties of Polyethylene Oxide-Based Solid-State Electrolytes for Li Ion Batteries

Polyethylene oxide (PEO)-based solid-state electrolyte (SSE) is attractive due to its excellent adhesion with electrodes and good processability. However, lithium dendrites easily penetrate PEO because of their soft nature, which results in inferior battery performance and safety issues. In this talk, we will discuss the development of 3D (insulating) amorphous carbon and 3D amorphous BN to improve the properties of polyethylene oxide (PEO)-based solid-state electrolytes for Li ion batteries.For the 3D amorphous carbon, we developed a novel self-healing PEO-based SSE is prepared by incorporating 2 wt% amorphous three-dimensional carbon (3DC). This SSE possesses suitably low electronic conductivity for battery applications (on the order of 10^−9 S/cm), which is five orders of magnitude lower than its ionic conductivity (10−4 S/cm) at 60 °C. In addition, the improved fluidity and strong adhesion between the 3DC and the PEO matrix contribute to the self-healing ability of SSE, which will repair the cracks of SSE formed during battery cycling. Moreover, this SSE shows enhanced ionic and thermal conductivities and mechanical strength, suppressing the formation and growth of lithium dendrites. As a result, this SSE exhibits excellent electrochemical stability, achieving 5000 h of stable cycles in lithium symmetric cell (0.1 mA cm−2, 0.1 mAh cm−2) and 850 long-term stable cycles for the LFP//Li full cell at 1 C (0.31 mA cm−2).For the 3D amorphous BN, we have developed the first synthesis of powdery hexagonal boron nitride (h-BN). This synthesis introduces a novel NaCl-glucose assisted strategy to synthesize micron-sized 3D h-BN with a honeycomb-like structure. When incorporated into polyethylene oxide-based electrolytes for Li-ion batteries, 5 wt% of 3D h-BN significantly enhances ionic conductivity and mechanical strength. Consequently, this composite electrolyte demonstrates superior electrochemical stability; it delivers 300 h of stable cycles in the lithium symmetric cell at 0.1 mA cm-2 and retains 89 % of discharge capacity (138.9 mAh/g) after 100 cycles at 1 C in the LFP//Li full cell.These two approaches reveal that 3DC and 3D h-BN can be used to improve the properties of PEO-based electrolytes of Li-ion batteries.

The Effect of Structural Disorder on Li-Ion Transport in the Inorganic Components of the Electrode-Electrolyte Interfaces of Li-Ion Batteries

Conventional organic electrolytes in Li-ion batteries have an electrochemical window that is too narrow, leading to a decomposition at the cathode and anode surfaces, especially at high voltages. The breakdown of the electrolyte leads to the formation of cathode-electrolyte interphase (CEI) and solid-electrolyte interface (SEI) at the anode. These interfaces are a multicomponent, 3-dimensional heterogeneous structures that span from a few nanometers to micrometers. To understand the atomic-scale impact of the interfaces’ structure and chemistry on function we have run molecular dynamics simulations of the Li-ion diffusivity in the most likely components: LiF, Li2CO3, and Li2O. Our work focuses on identifying the effect of local chemistry and lattice structure in disordered or amorphous component materials on Li-diffusivity. We extract Li-ion diffusivity and the activation energy for Li-ion transport from both machine learning force fields and ab-initio molecular dynamics from the individual components of the interface and explicit interfaces. Post analysis establishes the local correlation between atomic structure, chemistry, and Li-ion migration. If well designed, the SEI and CEI can protect the electrolyte and cathode to prevent further degradation during cycling and thus optimization of battery performance.This work was sponsored by the Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office and was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Novel Electrochemical Methodology for the Removal of HF from Carbonate-Based LiPF6-Containing Li-Ion Battery Electrolytes

Baseline Li-ion battery (LIB) electrolytes typically consist of LiPF6 salt dissolved in carbonate solvents. Due to trace amounts of water and the hydrolysis of PF6 - in carbonate solvents, these electrolytes always contain trace amounts of HF. [1] On the cathode, HF has negative effects, including transition metal dissolution and capacity fading. [2] On the anode, HF is involved in the formation and evolution of the solid electrolyte interphase (SEI). [3] The SEI originates in the thermodynamic instability of electrolyte moieties (salt, solvent, impurities) on the anode surface. As a result, electrolyte moieties are reduced and may then react with Li+ ions to form solid, insoluble products on the anode surface. This limits electron and solvent transport while permitting Li+ transport, kinetically stabilizing the interface. [4] The mechanism of nucleation and growth remains poorly understood despite their significance. The formation of LiF is one example. Although it is believed that direct PF6 - anion reduction is important, it is difficult to observe this reaction unambiguously because it frequently coexists with electrochemical signatures of electrocatalytic HF reduction or even acts in concert with one another. [5]The objective of this work is to remove ppm-levels of HF from carbonate-based LiPF6-containing electrolytes to enable foundational studies of SEI nucleation (e.g., direct PF6 - anionic direction) without interfering HF effects. We propose an electrochemical purification approach, which is complementary to conventional approaches using scavenging molecules. [6] Utilizing the knowledge that all other electrolyte moieties in baseline carbonate LiPF6-containing LIB electrolyte remain intact at relatively high potentials (significantly > 1.5 V vs. Li/Li+), we postulate to solely and selectively electrocatalytically reduce HF on metal electrodes. Therefore, our basic hypothesis is that all the HF in the electrolyte will be electrocatalytically reduced when an appropriate potential is applied to a high-surface area catalytically active electrode, while all other moieties essentially stay unchanged. To achieve this, we employed a porous Cu-foam working electrode that is integrated into a Teflon cone-type cell that has a second Pt working electrode. This allows us to use cyclic voltammetry (CV) to electrochemically test the HF concentration in the electrolyte. We report on the successful removal of HF to levels below a few ppm. Additionally, we observe CV features which we tentatively assign to direct anion reduction. Investigations are underway to gain deeper insight into the specifics of this reaction. We anticipate that the developed electrochemical method could lead to new opportunities for HF removal and basic research on the SEI reaction in electrolytes containing LiPF6.Literatur:[1] S.F. Lux, J. Chevalier, I.T. Lucas, R. Kostecki, HF Formation in LiPF6-Based Organic Carbonate Electrolytes, ECS Electrochemistry Letters, 2 (2013) A121.[2] C. Ye, W. Tu, L. Yin, Q. Zheng, C. Wang, Y. Zhong, Y. Zhang, Q. Huang, K. Xu, W. Li, Converting detrimental HF in electrolytes into a highly fluorinated interphase on cathodes, Journal of Materials Chemistry A, 6 (2018) 17642-17652.[3] D. Strmcnik, I.E. Castelli, J.G. Connell, D. Haering, M. Zorko, P. Martins, P.P. Lopes, B. Genorio, T. Østergaard, H.A. Gasteiger, F. Maglia, B.K. Antonopoulos, V.R. Stamenkovic, J. Rossmeisl, N.M. Markovic, Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries, Nature Catalysis, 1 (2018) 255-262.[4] A. Wang, S. Kadam, H. Li, S. Shi, Y. Qi, Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries, npj Computational Materials, 4 (2018) 15.[5] C. Cao, T.P. Pollard, O. Borodin, J.E. Mars, Y. Tsao, M.R. Lukatskaya, R.M. Kasse, M.A. Schroeder, K. Xu, M.F. Toney, H.-G. Steinrück, Toward Unraveling the Origin of Lithium Fluoride in the Solid Electrolyte Interphase, Chemistry of Materials, 33 (2021) 7315-7336.[6] J.-G. Han, M.-Y. Jeong, K. Kim, C. Park, C.H. Sung, D.W. Bak, K.H. Kim, K.-M. Jeong, N.-S. Choi, An electrolyte additive capable of scavenging HF and PF5 enables fast charging of lithium-ion batteries in LiPF6-based electrolytes, Journal of Power Sources, 446 (2020) 227366.

Role of Halogen Elements in Conductivity and Electrochemical Stability of Sulfide Based Solid Electrolytes

All-solid-state batteries (ASSBs) are a promising candidate for future energy storage technology with better safety and higher energy density [1]. Safety of solid state batteries come from solid electrolytes used instead of organic liquid electrolytes in conventional Li-ion batteries. The various types of solid electrolytes have already been reported for SSBs which can be divided into oxides, sulfides, halides and polymers based on their properties, advantages and disadvantages [2]. Among them, sulfide based solid electrolytes have advantages over other due to high conductivity and ductile nature of sulfides [3]. The discovery of Li10GeP2S12 solid electrolyte called LGPS structured sulfide electrolyte have shown great potential to replace liquid electrolyte as ionic conductivity of LGPS was found 1.2×10-2 S cm-1 at room temperature comparable to the conductivity of organic liquid electrolyte [4]. However, Li10GeP2S12 electrolyte suffers with poor cyclability in solid state batteries due to reduction of Ge+4 ions to Ge0, and instable against lithium metal anode [5, 6].The solid electrolytes (SEs) with high conductivity and better stability against lithium metal are most important requirements for successful commercialization of solid state battery (SSB) technology. Therefore, in the search for new SEs with above mentioned qualities, halogen elements (Cl, Br, I) are explored in Li-P-S-O system to prepare Li10GeP2S12 (LGPS) structured SEs. In all prepared SEs, LPSOBr and LPSOI compositions show highest conductivities of 0.55 mS cm-1 and 0.67 mS cm-1 at 25 °C. The phase identification of newly synthesized solid electrolytes is done by X-ray diffractometer technique along with Rietveld refinement analysis. The conductivity of prepared solid electrolytes is determined by electrochemical impedance spectroscopy. These similar compounds also show superior stability against lithium metal in symmetric cells (Li/Ses/SE) as well as in full SSB cells (NCA/SEs/graphite) tested with LiNi0.8Co0.15Al0.05O2 cathode and graphite anode. These compounds also show 5 times higher stability in ambient environment conditions as compared to non-doped LPSO compound.

Molecular Photothermal Effect on the 2D-IR Spectroscopy of Acetonitrile-Based Li-Ion Battery Electrolytes.

Advancements in Li-ion battery (LIB) technology hinge on an understanding of Li-ion solvation and charge transport dynamics. Ultrafast two-dimensional infrared (2D-IR) spectroscopy has been used to investigate these dynamics in electrolytes by probing chemical exchange processes through time-dependent cross-peak analysis. However, accurate interpretation is complicated by factors such as vibrational energy transfer and molecular photothermal effect (MPTE), affecting cross-peak evolution. Pinpointing the precise origin of these cross-peaks has posed a significant challenge in time-resolved IR spectroscopic studies of LIB electrolytes. Here, we trace the origin of 2D-IR cross-peaks of LIB electrolytes utilizing acetonitrile as a solvent. Time-dependent analysis of LiSCN and CH3SCN mixtures in CD3CN revealed distinctive MPTE features. Furthermore, direct observation of intermolecular MPTE through two-color IR pump-probe spectroscopy lends support to the findings. Our results emphasize the non-negligible artifacts induced by MPTE and the necessity of considering these effects to accurately observe the ultrafast dynamics within LIB electrolytes.

Investigation of Zn Doped Li1.5Al0.5−xZnxGe1.5(PO4)3 (x = 0, 0.1 & 0.2) as a Solid Electrolyte for Li Ion Batteries

All solid lithium-ion batteries (ASLB) have gained a lot of attention as it could deliver high energy and power density. In order to completely establish ASLB, proper understanding of solid electrolyte is very vital and the research from diverse point is still undergoing. Among them, NASICON-type phosphate based solid electrolytes are one of the promising materials due to good ionic conductivity and atmospheric stability. Addition of proper dopants into the parent material could cause an increment in their ionic conductivity as well as stability, thus fitting the material apt as solid electrolyte. This study aims in understanding the effect of ionic conductivity and stability of Lithium Aluminium Germanium Phosphate (LAGP) material upon adding Zinc as dopant material. We explored the effect of structural, ionic conductivity, stability against Li and Ac conductivity properties of Li1.5Al0.5−xZnxGe1.5(PO4)3 solid electrolyte with x = 0, 0.1 and 0.2. Our study showed that doping of aluminium with slightly bigger Zn ion could enhance the stability and conductivity of the material without changing the crystal structure. When x = 0.1 the ionic conductivity of the material attained is 1 × 10−5 S cm−1 at RT, which reaches 2.57 × 10−5 S cm−1 at 60 °C. Such a change in conductivity arises due to the expansion of ionic pathways which can be further tuned by exploring the limiting concentration 0 ≤ x < 0.1. Moreover, the sample also showed good stability at 0.03 and 0.05 mA cm−2 current densities against Li metal. Present study shows that Zn doping can improve the ionic conductivity of LAGP moderately and it can be used as a solid electrolyte for fabricating all-solid-state batteries.

Solvation Structures and Transport Mechanisms of Cations in Water-in-Bisalt Electrolytes for High-Concentration Lithium-Ion Batteries Revealed by Molecular Dynamics Simulations.

The development of safe and cost-effective electrolytes for rechargeable batteries is currently underway. While water-based electrolytes hold promise, their restricted electrochemical stability window poses a challenge. Combining multiple ionic species emerges as a promising strategy to broaden this stability window and optimize Li-ion battery performance. This study focuses on dual-cation electrolytes, which blend lithium and potassium acetates to enhance the electrochemical characteristics of the solution at high concentrations. We investigated the solvation structure of each ion and its interactions on a molecular level. Our analysis reveals that ion clusters and aggregates are formed through shared acetate and water molecules at high salt concentrations. Furthermore, the residence time analyses of atom pairs indicate that cations diffuse in vehicular mode at low concentrations. In contrast, they switch to a structural mode at high concentrations due to diminishing water content. This study offers a comprehensive model for exploring diverse solvation structures of cations and gaining insights into their diffusion mechanisms within water-in-bisalt electrolytes for aqueous Li-ion batteries.

Designing Nonflammable Liquid Electrolytes for Safe Li-Ion Batteries.

Li-ion batteries are essential technologies for electronic products in the daily life. However, serious fire safety concerns that are closely associated with the flammable liquid electrolyte remains a key challenge. Tremendous effort has been devoted to designing nonflammable liquid electrolytes. It is critical to gain comprehensive insights into nonflammability design and inspire more efficient approaches for building safer Li-ion batteries. This review presents current mechanistic understanding of safety issues and discusses state-of-the-art nonflammable liquid electrolytes design for Li-ion batteries based on molecule, solvation, and battery compatibility level. Various safety test methods are discussed for reliable safety risk evaluation. Finally, the challenges and perspectives of the nonflammability design for Li-ion electrolytes are summarized.

Understanding the Solid-Electrolyte-Interface (SEI) Formation in Glyme Electrolyte Using Time-Of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS).

Lithium-ion batteries are commonly used for energy storage due to their long lifespan and high energy density, but the use of unsafe electrolytes poses significant health and safety concerns. An alternative source is necessary to maintain electrochemical efficacy. This research demonstrates new safe glyme-based electrolytes for silica/carbon (SiOx/C) nanocomposite derived from Australian rice husk (RH). The quality of SiOx/C was preserved by using deep eutectic solvent-based pre-treatment and single-step carbonization, which was confirmed through the X-ray analysis of the crystalline phase of silica. The electrochemical assessment of SiOx/C anode using various glyme-based electrolytes for LIBs was carried out. Among them, the resultant half cells based on diglyme electrolyte is superior to others with the first discharge capacity at 1274 mAh/g and a reversible discharge capacity of 759.7 mAh/g. Ex-situ SEM and Time-of-Flight Secondary Ion Mass Spectrometry (ToF- SIMS) analysis of the electrode indicated that diglyme not only improves the capacity but also sustains the electrode architecture for longer cycle life with more LiF-based components and also showed the absence of HF components. Importantly, the addition of fluoroethylene carbonate (FEC) additive enhanced the cycling stability. These results provide a new perspective on developing advanced SiOx/C anode using glyme electrolytes for Li-ion batteries.

Electrochemical Removal of HF from Carbonate-based LiPF6-containing Li-ion Battery Electrolytes

Due to the hydrolytic instability of LiPF6 in carbonate-based solvents, HF is a typical impurity in Li-ion battery electrolytes. HF significantly influences the performance of Li-ion batteries, for example by impacting the formation of the solid electrolyte interphase at the anode and by affecting transition metal dissolution at the cathode. Additionally, HF complicates studying fundamental interfacial electrochemistry of Li-ion battery electrolytes, such as direct anion reduction, because it is electrocatalytically relatively unstable, resulting in a LiF passivation layer. Methods to selectively remove ppm levels of HF from LiPF6-containing carbonate-based electrolytes are limited. We introduce and benchmark a simple yet efficient electrochemical method to selectively remove ppm amounts of HF from LiPF6-containing carbonate-based electrolytes. The basic idea is the application of a suitable potential to a high surface-area metallic electrode upon which only HF reacts (electrocatalytically) while all other electrolyte components are unaffected under the respective conditions.

Effect of Ca doping on Li ion conductivity of Ge and Ta doped garnet LLZO

The series Li6.55+xGe0.05La3-xCaxZr1.75Ta0.25O12 (x = 0, 0.05, 0.10, 0.15, 0.20) was prepared by conventional solid state reaction method with the sintering temperature of 1050 °C for 7.30 h by substituting Ca at the La site to increase the Li ion conductivity. The synergistic effects of Ca incorporation on Li6.55Ge0.05La3Zr1.75Ta0.25O12 were studied using various structural and electrochemical analyses. X-ray diffraction, scanning electron microscopy, and Impedance analysis were used to determine the crystal structure, morphology, and AC conductivity of the prepared ceramic samples, respectively. The highest conductivity of 9.95 x 10−4 S/cm was obtained for a 0.05 Ca ceramic sample with minimum activation energy of 0.23 eV. The DC polarization measurements confirmed the dominance of ionic conduction in 0.05 Ca ceramic. The results obtained make the 0.05 Ca ceramic sample a promising candidate as solid electrolytes for all solid state Li-ion batteries (ASSLIBs).

Effect of Li6.4La3Zr1.4Ta0.6O12 Fillers on the Interfacial Properties between Composite PEO-LiTFSI Electrolytes with Li Metal during Cycling.

PEO-LiX solid polymer electrolyte (SPE) with the addition of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) fillers is considered as a promising solid-state electrolyte for solid-state Li-ion batteries. However, the developments of the SPE have caused additional challenges, such as poor contact interface and SPE/Li interface stability during cycling, which always lead to potentially catastrophic battery failure. The main problem is that the real impact of LLZTO fillers on the interfacial properties between SPE and Li metal is still unclear. Herein, we combined the electrochemical measurement and in situ synchrotron-based X-ray absorption near-edge structure (XANES) imaging technology to study the role of LLZTO fillers in directing SPE/Li interface electrochemical performance. In situ XRF-XANES mapping during cycling showed that addition of an appropriate amount of LLZTO fillers (50 wt %) can improve the interfacial contact and stability between SPE and Li metal without reacting with the PEO and Li salts. Additionally, it also demonstrated the beneficial effect of LLZTO particles for suppressing the interface reactions between the Li metal and PEO-LiTFSI SPE and further inhibiting Li-metal dendrite growth. The Li|LiFePO4 batteries deliver long cycling for over 700 cycles with a low-capacity fade rate of 0.08% per cycle at a rate of 0.3C, revealing tremendous potential in promoting the large-scale application of future solid-state Li-ion batteries.

Co-Intercalation-Free Graphite Anode Enabled by an Additive Regulated Interphase in an Ether-Based Electrolyte for Low-Temperature Lithium-Ion Batteries.

Graphite (Gr) anode, which is endowed with high electronic conductivity and low volume expansion after Li-ion intercalation, establishes the basis for the success of rocking-chair Li-ion batteries (LIBs). However, due to the high barrier of the Li-ion desolvation process, sluggish transport of Li ions through the solid electrolyte interphase (SEI) and the high freezing points of electrolytes, the Gr anode still suffers from great loss of capacity and severe polarization at low temperature. Here, 1,2-diethoxyethane (DEE) with an intrinsically wide liquid region and weak solvation ability is applied as an electrolyte solvent for LIBs. By rationally designing the additives of electrolytes, an intact SEI with fast Li-ion conductivity is constructed, enabling the co-intercalation-free Gr anode with long-term stability (91.8% after 500 cycles) and impressive low-temperature characteristics (82.6% capacity retention at -20 °C). Coupled with LiFePO4 and LiNi0.8Mn0.1Co0.1O2 cathodes, the optimized electrolyte also demonstrates low polarization under -20 °C. Our work offers a feasible approach to enable ether-based electrolytes for low-temperature LIBs.

Structure and molecular interactions in 1‑ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ion pair conformers: abinitio DFT based study

Density functional theory (DFT) calculations with Grimme’s B97D functional including dispersion are employed to provide both structural and electronic insight into the multifold interactions occurring in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid [EMI][TFSI], which is currently being targeted for applications in next-generation Li-ion battery electrolytes. The geometric structure, interaction energy and natural bond orbital analysis of the ion-pair conformers of [EMI][TFSI] show differences from the conventional H-bonds. A total of six stable [EMI][TFSI] ion pair conformers were observed. Our results show that a doubly ionic H-bond exists between [EMI]+ and [TFSI]− ion pair conformers. The greater the number of multiple H-bond type interactions, the greater the absolute value of the interaction energy. Moreover, results from the NBO analysis show that, for [EMI][TFSI] ion pair conformers, charge transfer occurs mainly from the lone pairs of oxygen and nitrogen atom to the σ-type anti-bonding orbital of the C–H and π-type anti-bonding orbitals of N–C bonds. This was evident from the values of the stabilization energy E(2) associated with each electron delocalization from the donor to acceptor orbitals. There exist large numbers of multiple concomitant hydrogen bonds, but the values of the stabilization energy E(2) are generally small (E(2)n→\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ o$$\\end{document}σ* < 3 kcal/mol) for the individual H-bond interactions. The shorter the C–H···O and/or C–H···N bond is, the larger charge transfer, and the larger the stabilization energy E(2) associated with electron delocalization from donor to acceptor. Generally, the [EMI][TFSI] ion pair conformers tend to form multiple but bent H bonds, reducing the strength of the individual H bonds from a potential (linear) maximum.

Phonon DOS-Based Machine Learning Model for Designing High-Performance Solid Electrolytes in Li-Ion Batteries

In the present work, a machine learning (ML) model was built to design solid electrolytes with improved ionic conductivity for Li-ion batteries (LIBs), and the model was based on the phonon density of states (PhDOS). Compounds with PhDOS calculations were collected from the Materials Project (MP) and processed to obtain frequencies and PhDOS to calculate the total phonon band center, a proxy for ionic conductivity. Total phonon band centers were involved in a learning process using four ML algorithms (extra random trees (XT), gradient boosting (GB), extreme gradient boosting (XGB), and decision trees (DT)). The cross-validation results from the algorithms showed that the performance of the XT-model was superior and confirmed through density functional theory- (DFT-) based phonon calculations conducted on LiYO3, Li4CO4, LiNiO3, LiGeO3, and LiSiO3. The XT-model was then used to predict the total phonon band centers of new compounds where these had no phonon calculations beforehand. Experimental validation of the XT-model involved electrochemical impedance spectroscopy (EIS) measurements on two compounds: Li2CO3 from the high range and Li6PS5Cl from the low range. Additionally, LiBiO2 that is predicted to have low total phonon band center, according to the XT-model, was considered further to estimate its potential as solid electrolyte in LIBs.

Non-flammable electrolyte for large-scale Ni-rich Li-ion batteries: Reducing thermal runaway risks

We present a novel, non-flammable electrolyte for Ni-rich 18650 cylindrical lithium-ion batteries (LIBs) based on a blend of triethyl phosphate (TEP) and fluorinated ethylene carbonate (FEC). We conducted a comprehensive analysis of the electrolyte, including electrochemical tests, safety evaluations, electrode surface characterizations, and quantum calculations, to elucidate its property-function relationship. We found that combining TEP with a concentrated FEC as a co-solvent (1.2 M LiPF6 in TEP/FEC, 30/70 %v) resulted in a robust solid electrolyte interface (SEI) predominantly composed of lithium fluoride (LiF). This innovation improved the SEI's stability and suppressed electrolyte decomposition during extended cycling, leading to consistent battery performance. Our findings introduce a promising non-flammable electrolyte solution for LIBs that offers both thermal runaway prevention and seamless integration into existing battery manufacturing processes. This positions it as a potential alternative to solid-state electrolytes in advanced battery technology, with the potential to revolutionize the field.

Decoupling of ion-transport from polymer segmental relaxation and higher ionic-conductivity in poly(ethylene oxide)/succinonitrile composite-based electrolytes having low lithium salt doping.

Only limited enhancement in room-temperature ionic-conductivity for poly(ethylene oxide), PEO, based electrolytes is possible due to coupling between ionic-conductivity and segmental relaxation. In the present study, we have achieved ionic-conductivity of 1.07 × 10-3 and 6.20 × 10-4 S cm-1 at 313 and 298 K, respectively, by adding 45 wt% of succinonitrile (SN) in PEO having low LiTFSI loading (Li : EO = 1 : 20). This enhancement in the ionic-conductivity is attributed to faster ion transport (diffusion coefficient, D = 3.63 × 10-5 cm2 s-1) occurring through the ion-transport channels as confirmed by positron annihilation lifetime spectroscopy. The ionic-transport through these channels is observed to be highly decoupled from the segmental relaxations as confirmed using broadband dielectric spectroscopy through Ratner's approach. The observed decoupling of ionic-conductivity from PEO segmental relaxation in PEO-SN composite-based electrolytes would be useful to design rather inexpensive all solid-state polymer electrolytes for Li ion batteries.

Boron-containing fullerene-based salts with cyclic carbonate solvents as electrolytes for Li-ion batteries and beyond.

Replacement of carbon atoms by a heteroatom in fullerene is a promising route that enhances the electronic properties of fullerenes and results in hetero fullerene-based effective agents ensuring applications in vivid fields of the solar cell, cathode materials for batteries, etc. Towards the development of new electrolyte salts, attention has been paid to facilitating ion mobility in particular and moderate stability of the anions in addition. From the atomistic molecular dynamics simulation studies, for the first time, we uncover that the boron-containing hetero fullerene, C59B- anion-based LiC59B, and NaC59B salts in cyclic carbonate solvents can act as efficient electrolytes by improving the transport phenomenon of the metal ions in solution, importantly for Li+ and satisfactorily for Na+ as compared to their commonly used BF4- anion based salts. Additionally, our study revealed that apart from LiC59B, and NaC59B salts, C58B22- based MgC58B2 salt can facilitate the ionic conductivity of the electrolyte. The properties of the proposed electrolyte under an electric field and different temperatures were investigated. Some of the bulk properties of the used electrolytes to some extent were found to be improved in the presence of these salts. The first principle-based electrochemical calculations further justify the stability of the proposed anions. The initial investigation from the Reactive force-field (ReaxFF) based atomistic simulations study elucidates that LiC59B reduces the decomposition of the EC solvent compared to LiBF4 and facilitates solvent stability.

A structural study on a specific Li-ion ordered complex in dimethyl carbonate-based dual-cation electrolytes.

Dimethyl carbonate (DMC) is a linear carbonate solvent commonly used as an electrolyte for electric double-layer capacitors (EDLCs) and Li-ion batteries. However, there are serious problems with the use of DMC as an electrolyte solvent: (1) low ionic conductivity when using Li salts (e.g. LiBF4) and (2) liquid-liquid phase separation when using spiro-type quaternary ammonium salts (e.g. SBPBF4). Dual-cation electrolytes, i.e., bi-salt (SBPBF4 and LiBF4) in DMC, are promising candidates to avoid the phase separation issue and to enhance the total and Li+ conductivities. Herein, we reported a specific Li-ion structure in DMC-based dual-cation electrolytes by combining high-energy X-ray total scattering (HEXTS) and all-atom molecular dynamics (MD) simulations. Quantitative radial distribution function analysis based on experimental and simulation results revealed that the phase-separated SBPBF4/DMC (i.e., the bottom phase of 1 M SBPBF4/DMC) forms long-range ion ordering based on the structured SBP+-BF4- ion pairs. When adding LiBF4 salt into SBPBF4/DMC (i.e., dual-cation electrolyte), the ordered SBP+-BF4- structure disappeared owing to the formation of Li-ion solvation complexes. We found that in the dual-cation electrolyte Li ions form multiple Li+-Li+ ordered complexes in spite of relatively low Li-salt concentration (1 M), being a promising Li+-conducting medium with reduced Li salt usage and low viscosity.