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1.
Altern Ther Health Med ; 29(5): 262-267, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37052974

RESUMO

Context: Knee osteoarthritis (KOA) is a degenerative disorder that significantly affects patients' quality of life. Acupuncture and exercise are the most popular treatments currently. The outcomes for acupuncture for KOA, however, are controversial, with some researchers finding that the addition of acupuncture to exercise therapy provided no additional improvement in pain scores. Objective: The study intended to evaluate the therapeutic effects for KOA of exercise in combination with acupuncture on acupoints selected using the Traditional Chinse Medicine (TCM) theory of Equal Impact on Tendons, Bones, and Muscles (EITBM) in comparison with that of acupoints selected using classical consensus for the treatment. Design: The research team performed a randomized controlled trial. Setting: The study took place in the Department of Acupuncture and Moxibustion at the First Affiliated Hospital of Hebei University of Chinese Medicine in Shijiazhuang, Hebei, China. Participants: Participants were 70 patients with KOA who visited the hospital between December 2020 and February 2021. Intervention: Participants in both group received acupuncture plus exercise therapy. The research team randomly assigned participants to one of two groups: (1) 35 to the intervention group, which received acupuncture using acupoints selected using EITBM, and (2) 35 to the control group, which received acupuncture using the classical consensus acupoints. Both groups performed a 25-min session of acupuncture three times weekly for 4 weeks, with the exercise therapy following the acupuncture each time. Outcome Measures: The research team assessed clinical efficacy at baseline and postintervention. The primary outcome measures included assessments: (1) of knee joint pain using a visual analog scale (VAS), (2) of knee joint pain, flexibility, and function using the Western Ontario and McMaster University Osteoarthritis Index (WOMAC) pain subscale; and (3) joint range of motion (ROM). The secondary outcome measures included measurement of serum levels of interleukin-1 beta (IL-1ß), tumor necrosis factor alpha (TNF-α), and matrix metalloproteinase-13 (MMP-13) using enzyme-linked immunosorbent assays (ELISA). Results: The VAS and WOMAC scores significantly decreased for both groups between baseline and postintervention, and the intervention group's decrease was significantly greater than that of the control group. The ROM of knee flexion was significantly higher in both groups postintervention than at baseline, and the intervention group's increase was significantly higher than that of the control group. The serum IL-1ß, TNF-α, and MMP-13 also significantly decreased postintervention in both groups, and the intervention group's levels were significantly lower than those of the control group. The total effective rate was 94.1% in the intervention group, 32 out of 34 participants, and 75.8% in the control group, 25 out of 33 participants, which was significantly different. Conclusions: Acupuncture, in combination with exercise, can relieve symptoms, improve joint function, and reduce pro-inflammatory cytokines (IL-1ß and TNF-a) as well as MMP-13 for patients with KOA. The outcomes for acupuncture using EITBM acupoints were significantly better than those of the acupoints selected using classical consensus.


Assuntos
Terapia por Acupuntura , Osteoartrite do Joelho , Humanos , Osteoartrite do Joelho/terapia , Metaloproteinase 13 da Matriz , Pontos de Acupuntura , Fator de Necrose Tumoral alfa , Consenso , Qualidade de Vida , Resultado do Tratamento , Dor , Tendões , Músculos , Artralgia
2.
Nat Mater ; 20(6): 841-850, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33479526

RESUMO

Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF2 and CuF2. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-LixFeyF3, which is structurally related to α-/ß-LiMn2+Fe3+F6 and which topotactically transforms to B- and then C-LixFeyF3, before forming LiF and Fe. Lithiation of FeF2 and CuF2 results in a buffer phase between FeF2/CuF2 and LiF. The resulting principles will aid future developments of a wider range of isomorphic metal fluorides.

3.
Chem Rev ; 120(9): 4169-4221, 2020 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-32267697

RESUMO

Fast ion conduction in solid-state matrices constitutes the foundation for a wide spectrum of electrochemical systems that use solid electrolytes (SEs), examples of which include solid-state batteries (SSBs), solid oxide fuel cells (SOFCs), and diversified gas sensors. Mixing different solid conductors to form composite solid electrolytes (CSEs) introduces unique opportunities for SEs to possess exceptional overall performance far superior to their individual parental solids, thanks to the abundant chemistry and physics at the new interfaces thus created. In this review, we provide a comprehensive and in-depth examination of the development and understanding of CSEs for SSBs, with special focus on their physiochemical properties and mechanisms of ion transport therein. The origin of the enhanced ionic conductivity in CSEs relative to their single-phase parents is discussed in the context of defect chemistry and interfacial reactions. The models/theories for ion movement in diversified composites are critically reviewed to interrogate a general strategy to the design of novel CSEs, while properties such as mechanical strength and electrochemical stability are discussed in view of their perspective applications in lithium metal batteries and beyond. As an integral component of understanding how ions interact with their composite environments, characterization techniques to probe the ion transport kinetics across different temporal and spatial time scales are also summarized.

4.
Angew Chem Int Ed Engl ; 61(50): e202214796, 2022 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-36259391

RESUMO

The development of rechargeable Ca metal batteries (RCMBs) is hindered by the Ca2+ passivating solid electrolyte interphases (SEIs). The cation solvation structure dictated by electrolyte chemistry plays a critical role in the SEIs properties. While a relatively weak cation-solvent binding is preferred in Li metal anodes to promote anion-derived SEIs, we demonstrate an enhanced Ca deposition/stripping reversibility under a strong cation-solvent interaction, which is materialized in strongly-solvating solvent and highly-dissociated salt combinations. Such electrolyte formulations benefit the formation of solvent-occupied solvation structure and minimize the anion reduction, resulting in organic-rich/CaF2 -poor SEIs for reversible Ca metal anodes. Furthermore, RCMBs paired with an organic cathode using the optimized electrolytes are demonstrated as a proof-of-concept. Our work reveals the paradigm shift in SEIs design for Ca metal anodes, opening up new opportunities for emerging RCMBs.

5.
Angew Chem Int Ed Engl ; 61(14): e202116560, 2022 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-35088500

RESUMO

Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast-charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn2+ -ion diffusion. Moreover, steady-state Zn metal plating/stripping with Coulombic efficiency above 99 % is achieved at 10-100 mA cm-2 in a reasonably high concentration (3 M) ZnSO4 electrolyte. Significantly, a long-term cycling-stable Zn metal electrode is realized with a depth of discharge of 66.7 % under 50 mA cm-2 in both Zn||Zn symmetrical cells and MnO2 ||Zn full cells.

6.
J Chem Phys ; 154(17): 174111, 2021 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-34241052

RESUMO

Cathodes are critical components of rechargeable batteries. Conventionally, the search for cathode materials relies on experimental trial-and-error and a traversing of existing computational/experimental databases. While these methods have led to the discovery of several commercially viable cathode materials, the chemical space explored so far is limited and many phases will have been overlooked, in particular, those that are metastable. We describe a computational framework for battery cathode exploration based on ab initio random structure searching (AIRSS), an approach that samples local minima on the potential energy surface to identify new crystal structures. We show that by delimiting the search space using a number of constraints, including chemically aware minimum interatomic separations, cell volumes, and space group symmetries, AIRSS can efficiently predict both thermodynamically stable and metastable cathode materials. Specifically, we investigate LiCoO2, LiFePO4, and LixCuyFz to demonstrate the efficiency of the method by rediscovering the known crystal structures of these cathode materials. The effect of parameters, such as minimum separations and symmetries, on the efficiency of the sampling is discussed in detail. The adaptation of the minimum interatomic distances on a species-pair basis, from low-energy optimized structures to efficiently capture the local coordination environment of atoms, is explored. A family of novel cathode materials based on the transition-metal oxalates is proposed. They demonstrate superb energy density, oxygen-redox stability, and lithium diffusion properties. This article serves both as an introduction to the computational framework and as a guide to battery cathode material discovery using AIRSS.

7.
Phys Chem Chem Phys ; 17(48): 32547-55, 2015 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-26597695

RESUMO

Lithium-rich anti-perovskites (LiRAPs) are a promising family of solid electrolytes, which exhibit ionic conductivities above 10(-3) S cm(-1) at room temperature, among the highest reported values to date. In this work, we investigate the defect chemistry and the associated lithium transport in Li3OCl, a prototypical LiRAP, using ab initio density functional theory (DFT) calculations and classical molecular dynamics (MD) simulations. We studied three types of charge neutral defect pairs, namely the LiCl Schottky pair, the Li2O Schottky pair, and the Li interstitial with a substitutional defect of O on the Cl site. Among them the LiCl Schottky pair has the lowest binding energy and is the most energetically favorable for diffusion as computed by DFT. This is confirmed by classical MD simulations, where the computed Li ion diffusion coefficients for LiCl Schottky systems are significantly higher than those for the other two defects considered and the activation energy in LiCl deficient Li3OCl is comparable to experimental values. The high conductivities and low activation energies of LiCl Schottky systems are explained by the low energy pathways of Li between the Cl vacancies. We propose that Li vacancy hopping is the main diffusion mechanism in highly conductive Li3OCl.

8.
Nat Comput Sci ; 4(3): 210-223, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38467870

RESUMO

Orbital-free density functional theory (OFDFT) is a quantum chemistry formulation that has a lower cost scaling than the prevailing Kohn-Sham DFT, which is increasingly desired for contemporary molecular research. However, its accuracy is limited by the kinetic energy density functional, which is notoriously hard to approximate for non-periodic molecular systems. Here we propose M-OFDFT, an OFDFT approach capable of solving molecular systems using a deep learning functional model. We build the essential non-locality into the model, which is made affordable by the concise density representation as expansion coefficients under an atomic basis. With techniques to address unconventional learning challenges therein, M-OFDFT achieves a comparable accuracy to Kohn-Sham DFT on a wide range of molecules untouched by OFDFT before. More attractively, M-OFDFT extrapolates well to molecules much larger than those seen in training, which unleashes the appealing scaling of OFDFT for studying large molecules including proteins, representing an advancement of the accuracy-efficiency trade-off frontier in quantum chemistry.

9.
ACS Appl Mater Interfaces ; 15(13): 16584-16592, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36947678

RESUMO

Zinc metal is emerging as the promising anode for aqueous Zn-ion batteries. However, corrosion and undesirable Zn dendrite growth limit their practical application in the large-scale energy storage area. Herein, a mountain-valley micro/nanostructure is successfully fabricated on the surface of the Zn anode via a femtosecond-laser filament texturing (FsLFT) technique. Beneficial from the large surface area and spontaneously generated ZnO coating layer, the FsLFT-Zn electrode demonstrates a slow corrosion rate with a current density of 0.62 mA cm-2 and a stable cycle life over 3000 h under 1 mA cm-2, superior to the original Zn anode. Simulation of the electric fields reveals that the enlarged surface area is responsible for the outstanding performance of the FsLFT-Zn electrode. This study not only proposes a novel strategy to suppress dendrite growth toward highly stable AZIBs but also opens a new avenue to solve similar issues in other metal batteries.

10.
Nat Commun ; 14(1): 1674, 2023 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-36966129

RESUMO

The discovery of 250-kelvin superconducting lanthanum polyhydride under high pressure marked a significant advance toward the realization of a room-temperature superconductor. X-ray diffraction (XRD) studies reveal a nonstoichiometric LaH9.6 or LaH10±Î´ polyhydride responsible for the superconductivity, which in the literature is commonly treated as LaH10 without accounting for stoichiometric defects. Here, we discover significant nuclear quantum effects (NQE) in this polyhydride, and demonstrate that a minor amount of stoichiometric defects will cause quantum proton diffusion in the otherwise rigid lanthanum lattice in the ground state. The diffusion coefficient reaches ~10-7 cm2/s in LaH9.63 at 150 gigapascals and 240 kelvin, approaching the upper bound value of interstitial hydrides at comparable temperatures. A puzzling phenomenon observed in previous experiments, the positive pressure dependence of the superconducting critical temperature Tc below 150 gigapascals, is explained by a modulation of the electronic structure due to a premature distortion of the hydrogen lattice in this quantum fluxional structure upon decompression, and resulting changes of the electron-phonon coupling. This finding suggests the coexistence of the quantum proton fluxion and hydrogen-induced superconductivity in this lanthanum polyhydride, and leads to an understanding of the structural nature and superconductivity of nonstoichiomectric hydrogen-rich materials.

11.
Nat Commun ; 14(1): 6501, 2023 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-37845205

RESUMO

Exploiting solid electrolyte (SE) materials with high ionic conductivity, good interfacial compatibility, and conformal contact with electrodes is essential for solid-state sodium metal batteries (SSBs). Here we report a crystalline Na5SmSi4O12 SE which features high room-temperature ionic conductivity of 2.9 × 10-3 S cm-1 and a low activation energy of 0.15 eV. All-solid-state symmetric cell with Na5SmSi4O12 delivers excellent cycling life over 800 h at 0.15 mA h cm-2 and a high critical current density of 1.4 mA cm-2. Such excellent electrochemical performance is attributed to an electrochemically induced in-situ crystalline-to-amorphous (CTA) transformation propagating from the interface to the bulk during repeated deposition and stripping of sodium, which leads to faster ionic transport and superior interfacial properties. Impressively, the Na|Na5SmSi4O12|Na3V2(PO4)3 sodium metal batteries achieve a remarkable cycling performance over 4000 cycles (6 months) with no capacity loss. These results not only identify Na5SmSi4O12 as a promising SE but also emphasize the potential of the CTA transition as a promising mechanism towards long-lasting SSBs.

12.
ACS Nano ; 17(19): 19459-19469, 2023 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-37768556

RESUMO

Low-temperature lithium metal batteries are of vital importance for cold-climate condition applications. Their realization, however, is plagued by the extremely sluggish Li+ transport kinetics in the vicinity of Li metal anode at low temperatures. Different from the widely adopted electrolyte engineering, a functional interphase design concept is proposed in this work to efficiently improve the low-temperature electrochemical reaction kinetics of Li metal anodes. As a proof of concept, we design a hybrid polymer-alloy-fluoride (PAF) interphase featuring numerous gradient fluorinated solid-solution alloy composite nanoparticles embedded in a polymerized dioxolane matrix. Systematic experimental and theoretical investigations demonstrate that the hybrid PAF interphase not only exhibits superior lithiophilicity but also provides abundant ionic conductive pathways for homogeneous and fast Li+ transport at the Li-electrolyte interface. With enhanced interfacial dynamics of Li-ion migration, the as-designed PAF-Li anode works stably for 720 h with low voltage hysteresis and dendrite-free electrode morphology in symmetric cell configurations at -40 °C. The full cells with PAF-Li anode display a commercial-grade capacity of 4.26 mAh cm-2 and high capacity retention of 74.7% after 150 cycles at -20 °C. The rational functional interphase design for accelerating ion-transfer kinetics sheds innovative insights for developing high-areal-capacity and long-lifespan lithium metal batteries at low temperatures.

13.
Adv Mater ; 35(30): e2301684, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37120149

RESUMO

It is challenging to achieve long-term stability of perovskite solar cells due to the corrosion and diffusion of metal electrodes. Integration of compact barriers into devices has been recognized as an effective strategy to protect the perovskite absorber and electrode. However, the difficulty is to construct a thin layer of a few nanometers that can delay ion migration and impede chemical reactions simultaneously, in which the delicate microstructure design of a stable material plays an important role. Herein, ZrNx barrier films with high amorphization are introduced in p-i-n perovskite solar cells. To quantify the amorphous-crystalline (a-c) density, pattern recognition techniques are employed. It is found the decreasing a-c interface in an amorphous film leads to dense atom arrangement and uniform distribution of chemical potential, which retards the interdiffusion at the interface between ions and metal atoms and protect the electrodes from corrosion. The resultant solar cells exhibit improved operational stability, which retains 88% of initial efficiency after continuous maximum power point tracking under 1-Sun illumination at room temperature (25 °C) for 1500 h.

14.
ACS Appl Mater Interfaces ; 14(16): 18373-18382, 2022 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-35420418

RESUMO

Lithium-rich ternary phosphides are recently found to possess high ionic conductivity and are proposed as promising solid electrolytes (SEs) for solid-state batteries. While lithium ions can facilely transport within these materials, their electrochemical and interfacial stability in complex battery setups remain largely uncharacterized. We study the phase stability and electrochemical stability of phosphide-type SEs via first-principles calculations and thermodynamic analysis. Our results indicate that these SEs have intrinsic electrochemical stability windows narrower than 0.5 V. The SEs exhibit low anodic limits of about 1 V vs Li/Li+ due to the oxidation of the electrolytes to form various P binary compounds, indicating the poor electrochemical stability in contact with the cathode. In particular, we find that the thermodynamic driving force of such electrochemical decomposition is critically dependent on the new phases formed at the interfaces. Therefore, these phosphides might not be suitable as electrolytes. Despite the electrochemical instability, further calculations of Li diffusion kinetics show that the Li conduction is highly efficient through face-sharing octahedral and tetrahedral sites with low energy barriers, in spite of the possible variation of the local environments. In addition, an analysis of the terminal decomposition products shows impressive Li storage capacity as high as 2547 mAh·g-1 based on the conversion mechanism, indicating they are capable as high-rate and energy-dense anode materials for battery applications.

15.
Adv Mater ; 34(39): e2202892, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35641316

RESUMO

Efforts to enable fast charging and high energy density lithium-ion batteries (LIBs) are hampered by the trade-off nature of the traditional electrode design: increasing the areal capacity usually comes with sacrificing the fast charge transfer. Here a single-layer chunky particle electrode design is reported, where red-phosphorus active material is embedded in nanochannels of vertically aligned graphene (red-P/VAG) assemblies. Such an electrode design addresses the sluggish charge transfer stemming from the high tortuosity and inner particle/electrode resistance of traditional electrode architectures consisting of randomly stacked active particles. The vertical ion-transport nanochannels and electron-transfer conductive nanowalls of graphene confine the direction of charge transfer to minimize the transfer distance, and the incomplete filling of nanochannels in the red-P/VAG composite buffers volume change locally, thus avoiding the variation of electrodes thickness during cycling. The single-layer chunky particle electrode displays a high areal capacity (5.6 mAh cm-2 ), which is the highest among the reported fast-charging battery chemistries. Paired with a high-loading LiNi0.6 Co0.2 Mn0.2 O2 (NCM622) cathode, a pouch cell shows stable cycling with high energy and power densities. Such a single-layer chunky particle electrode design can be extended to other advanced battery systems and boost the development of LIBs with fast-charging capability and high energy density.

16.
Nat Commun ; 13(1): 7763, 2022 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-36522319

RESUMO

Carbon dioxide capture is essential to achieve net-zero emissions. A hurdle to the design of improved capture materials is the lack of adequate tools to characterise how CO2 adsorbs. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a promising probe of CO2 capture, but it remains challenging to distinguish different adsorption products. Here we perform a comprehensive computational investigation of 22 amine-functionalised metal-organic frameworks and discover that 17O NMR is a powerful probe of CO2 capture chemistry that provides excellent differentiation of ammonium carbamate and carbamic acid species. The computational findings are supported by 17O NMR experiments on a series of CO2-loaded frameworks that clearly identify ammonium carbamate chain formation and provide evidence for a mixed carbamic acid - ammonium carbamate adsorption mode. We further find that carbamic acid formation is more prevalent in this materials class than previously believed. Finally, we show that our methods are readily applicable to other adsorbents, and find support for ammonium carbamate formation in amine-grafted silicas. Our work paves the way for investigations of carbon capture chemistry that can enable materials design.

17.
ACS Appl Mater Interfaces ; 13(33): 39271-39281, 2021 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-34375074

RESUMO

Solid-state batteries based on ceramic electrolytes are promising alternatives to lithium-ion batteries with better safety and energy density. While solid electrolytes such as the garnet-type Li7La3Zr2O12 (LLZO) are chemically stable with lithium metal, their rigidity leads to poor interfacial contact with the cathodes. Nonflammable organic phosphates, however, are characterized by a liquid nature and can immerse the conventional porous cathodes to form a good contact. However, the phosphates are unstable with lithium metal anodes. We design a quasi-solid Janus electrolyte based on the ceramic LLZO and a trimethyl phosphate (TMP) gel which combines the best of both worlds. The electrochemical window of the Janus electrolyte is significantly extended compared with the TMP to accommodate the lithium metal anode. The contact between the cathode and the electrolyte is maintained by the semifluid nature of the TMP gel. A lithium-metal battery with such a Janus electrolyte can stably cycle at room temperature at 1C while still retaining a capacity of 115 mAh g-1 over 100 times. In contrast, the batteries based on LLZO and TMP individually cannot function properly. More importantly, despite the quasi-solid nature, the battery does not contain flammable functional parts and can alleviate the safety concerns of current batteries containing organic-type electrolytes. This work provides a simple but effective strategy for safe, inexpensive, and energy-dense solid-state batteries.

18.
ACS Appl Mater Interfaces ; 13(7): 8417-8425, 2021 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-33587588

RESUMO

Lithium-metal batteries (LMBs) are promising electrochemical energy storage devices with high energy densities. However, the extreme reactivity of metallic lithium, the large volumetric change of the electrode during cycling, and the notorious dendrite formation issues lead to low cyclic stability and safety concerns, hindering the practical application of LMBs. In particular, the intrinsic tendency of uneven lithium deposition and the large internal electrode stress lead to the piecing of solid electrolyte interphases (SEIs), thereby resulting in fast decay of the anode. We develop a facile laser processing technique to fabricate laser-structured copper foils (LSCFs) that are able to regulate the lithium deposition kinetics and increase the cycle life of LMBs. By simply scribing commercial foils using a 355 nm laser, microstructural features with fish-scale patterns are obtained. The lithium deposition follows a drastically different mode on the LSCF compared with commercial planar copper foils which relieves the internal stress of lithium and prohibits the piecing of SEI. A high Coulombic efficiency of >96% of the lithium metal anode is maintained for over 100 cycles on the LSCF at a current density of 1 mA cm-2 and an areal capacity of 1 mAh cm-2 while the benchmark decayed to below 80% after 50 cycles. Full cells based on LiFePO4 cathodes display a reasonable specific capacity of 125 mAh g-1 over 300 cycles at a rate of 1 C. This work provides a fast yet effective laser-based approach to construct highly stable lithium metal anodes.

19.
ACS Appl Mater Interfaces ; 12(49): 55011-55022, 2020 Dec 09.
Artigo em Inglês | MEDLINE | ID: mdl-33242955

RESUMO

Lithium-rich antiperovskites (APs) have attracted significant research attention due to their ionic conductivity above 1 mS cm-1 at room temperature. However, recent experimental reports suggest that proton-free lithium-rich APs, such as Li3OCl, may not be synthesized using conventional methods. While Li2OHCl has a lower conductivity of about 0.1 mS cm-1 at 100 °C, its partially fluorinated counterpart, Li2(OH)0.9F0.1Cl, is a significantly better ionic conductor. In this article, using density functional theory simulations, we show that it is easier to synthesize Li2OHCl and two of its fluorinated variants, i.e., Li2(OH)0.9F0.1Cl and Li2OHF0.1Cl0.9, than Li3OCl. The transport properties and electrochemical windows of Li2OHCl and the fluorinated variants are also studied. The ab initio molecular dynamics simulations suggest that the greater conductivity of Li2(OH)0.9F0.1Cl is due to structural distortion of the lattice and correspondingly faster OH reorientation dynamics. Partially fluorinating the Cl site to obtain Li2OHF0.1Cl0.9 leads to an even greater ionic conductivity without impacting the electrochemical window and synthesizability of the materials. This study motivates further research on the correlation between local structure distortion, OH dynamics, and increased Li mobility. Furthermore, it introduces Li2OHF0.1Cl0.9 as a novel Li conductor.

20.
Nanoscale Horiz ; 5(12): 1618-1627, 2020 Nov 23.
Artigo em Inglês | MEDLINE | ID: mdl-33165492

RESUMO

The recent revival of research on Na and K ion batteries has two benefits. It not only provides alternate energy storage technologies to Li ion batteries with potential cost advantages but also enhances our understanding of charge storage through systematic studies on alkali-metal ion batteries with increasing insertion ion sizes. Using MoS2 as a model material, the structure evolution upon the uptake of Li, Na, and K ions are compared through in situ TEM. Despite their larger size, insertion of K ions shows both the better electrochemical and structural stability. To understand this paradoxical and counter-intuitive phenomenon, in situ XRD is carried out to examine the phase transitions of MoS2 upon ion insertion, while ex situ TEM is further applied to closely examine the structures at the nanoscale. Complementary DFT calculations are performed to understand the kinetic/thermodynamic origins of the unusual stability. The result reveal that the less electrovalent K-S bond favors the intercalation process, resulting in preservation of the layered structure for stable cycling. This study provides a structural insight to design stable electrodes for the K-ion batteries.

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