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1.
Proc Natl Acad Sci U S A ; 121(18): e2316493121, 2024 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-38657039

RESUMO

Since the 1980s, the paddlewheel effect has been suggested as a mechanism to boost lithium-ion diffusion in inorganic materials via the rotation of rotor-like anion groups. However, it remains unclear whether the paddlewheel effect, defined as large-angle anion group rotations assisting Li hopping, indeed exists; furthermore, the physical mechanism by which the anion-group dynamics affect lithium-ion diffusion has not yet been established. In this work, we differentiate various types of rotational motions of anion groups and develop quaternion-based algorithms to detect, quantify, and relate them to lithium-ion motion in ab initio molecular dynamics simulations. Our analysis demonstrates that, in fact, the paddlewheel effect, where an anion group makes a large angle rotation to assist a lithium-ion hop, does not exist and thus is not responsible for the fast lithium-ion diffusion in superionic conductors, as historically claimed. Instead, we find that materials with topologically isolated anion groups can enhance lithium-ion diffusivity via a more classic nondynamic soft-cradle mechanism, where the anion groups tilt to provide optimal coordination to a lithium ion throughout the hopping process to lower the migration barrier. This anion-group disorder is static in nature, rather than dynamic and can explain most of the experimental observations. Our work substantiates the nonexistence of the long-debated paddlewheel effect and clarifies any correlation that may exist between anion-group rotations and fast ionic diffusion in inorganic materials.

2.
Proc Natl Acad Sci U S A ; 120(35): e2306272120, 2023 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-37603750

RESUMO

Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film.

3.
Rep Prog Phys ; 87(2)2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38052072

RESUMO

The charge density wave (CDW) instability, usually occurring in low-dimensional metals, has been a topic of interest for longtime. However, some very fundamental aspects of the mechanism remain unclear. Recently, a plethora of new CDW materials, a substantial fraction of which is two-dimensional or even three-dimensional, has been prepared and characterised as bulk and/or single-layers. As a result, the need for revisiting the primary mechanism of the instability, based on the electron-hole instability established more than 50 years ago for quasi-one-dimensional (quasi-1D) conductors, has clearly emerged. In this work, we consider a large number of CDW materials to revisit the main concepts used in understanding the CDW instability, and emphasise the key role of the momentum dependent electron-phonon coupling in linking electronic and structural degrees of freedom. We argue that for quasi-1D systems, earlier weak coupling theories work appropriately and the energy gain due to the CDW and the concomitant periodic lattice distortion (PLD) remains primarily due to a Fermi surface nesting mechanism. However, for materials with higher dimensionality, intermediate and strong coupling regimes are generally at work and the modification of the chemical bonding network by the PLD is at the heart of the instability. We emphasise the need for a microscopic approach blending condensed matter physics concepts and state-of-the-art first-principles calculations with quite fundamental chemical bonding ideas in understanding the CDW phenomenon in these materials.

4.
Small ; 20(33): e2311195, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38775620

RESUMO

Over the past decade, solid-state batteries have garnered significant attentions due to their potentials to deliver high energy density and excellent safety. Considering the abundant sodium (Na) resources in contrast to lithium (Li), the development of sodium-based batteries has become increasingly appealing. Sulfide-based superionic conductors are widely considered as promising solid eletcrolytes (SEs) in solid-state Na batteries due to the features of high ionic conductivity and cold-press densification. In recent years, tremendous efforts have been made to investigate sulfide-based Na-ion conductors on their synthesis, compositions, conductivity, and the feasibility in batteries. However, there are still several challenges to overcome for their practical applications in high performance solid-state Na batteries. This article provides a comprehensive update on the synthesis, structure, and properties of three dominant sulfide-based Na-ion conductors (Na3PS4, Na3SbS4, and Na11Sn2PS12), and their families that have a variety of anion and cation doping. Additionally, the interface stability of these sulfide electrolytes toward the anode is reviewed, as well as the electrochemical performance of solid-state Na batteries based on different types of cathode materials (metal sulfides, oxides, and organics). Finally, the perspective and outlook for the development and practical utilization of sulfide-based SE in solid-state batteries are discussed.

5.
Small ; 20(8): e2305765, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37821399

RESUMO

Solid proton electrolytes play a crucial role in various electrochemical energy storage and conversion devices. However, the development of fast proton conducting solid proton electrolytes at ambient conditions remains a significant challenge. In this study, a novel acidified nitrogen self-doped porous carbon material is presented that demonstrates exceptional superprotonic conduction for applications in solid-state proton battery. The material, designated as MSA@ZIF-8-C, is synthesized through the acidification of nitrogen-doped porous carbon, specifically by integrating methanesulfonic acid (MSA) into zeolitic imidazolate framework-derived nitrogen self-doped porous carbons (ZIF-8-C). This study reveals that MSA@ZIF-8-C achieves a record-high proton conductivity beyond 10-2  S cm-1 at ambient condition, along with good long-term stability, positioning it as a cutting-edge alternative solid proton electrolyte to the default aqueous H2 SO4 electrolyte in proton batteries.

6.
Small ; : e2404702, 2024 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-39367553

RESUMO

Grain boundary (GB) mass transport, and chemistry exert a pronounced influence on both the performance and stability of electrodes for solid oxide electrochemical cells. Lanthanum strontium cobalt ferrite (LSCF6428) is applied as a model mixed ionic and electronic conducting (MIEC) perovskite oxide. The cation-vacancy distribution at the GBs is studied at both single and multi-grain scales using high-resolution characterization techniques and computational approaches. The accumulation of oxygen vacancies ( V O · · $V_O^{ \cdot \cdot }$ ) in the GB region, rather than necessarily at the GB core, results in an enhancement of the oxygen diffusivity by 3 - 4 orders of magnitude along the GBs (Dgb). At 350 °C, the oxygen tracer diffusion coefficient (D*) is measured as 2.5 × 10-14 cm2 s-1. The Dgb is determined to be 2.8 × 10-10 cm2 s-1 assuming a crystallographic GB width (δcrystal) of 1 nm, and 2.5 × 10-11 cm2 s-1 using a chemically measured δchem of 11.10 nm by atom probe tomography (APT). The origin of the concomitant changes in the cation composition is also investigate. In addition to the host cations, strong Na segregation is detected at all the GBs examined. Despite the low (ppm) level of this impurity, its presence can affect the space charge potential (Φ0). This, in turn, will influence the evolution of GB chemistry.

7.
Small ; 20(34): e2309735, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38618655

RESUMO

Solid oxide fuel cells (SOFCs) are paving the way to clean energy conversion, relying on efficient oxygen-ion conductors with high ionic conductivity coupled with a negligible electronic contribution. Doped rare earth aluminates are promising candidates for SOFC electrolytes due to their high ionic conductivity. However, they often suffer from p-type electronic conductivity at operating temperatures above 500 °C under oxidizing conditions caused by the incorporation of oxygen into the lattice. High entropy materials are a new class of materials conceptualized to be stable at higher temperatures due to their high configurational entropy. Introducing this concept to rare earth aluminates can be a promising approach to stabilize the lattice by shifting the stoichiometric point of the oxides to higher oxygen activities, and thereby, reducing the p-type electronic conductivity in the relevant oxygen partial pressure range. In this study, the high entropy oxide (Gd,La,Nd,Pr,Sm)AlO3 is synthesized and doped with Ca. The Ca-doped (Gd,La,Nd,Pr,Sm)AlO3 compounds exhibit a higher ionic conductivity than most of the corresponding Ca-doped rare earth aluminates accompanied by a reduction of the p-type electronic conductivity contribution typically observed under oxidizing conditions. In light of these findings, this study introduces high entropy aluminates as a promising candidate for SOFC electrolytes.

8.
Small ; : e2404297, 2024 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-39282822

RESUMO

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 1·10-1 S cm-1 at 90 °C, decreasing only moderately to 4·10-2 S cm-1 at room temperature, and to >1·10-3 S cm-1 at -20 °C, corresponding to activation energies as low as 0.19 eV. 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.

9.
Small ; 20(6): e2304164, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37775941

RESUMO

Flexible composite polymer electrolytes (CPEs) with inorganic electrolyte fillers dispersed in polymer electrolytes integrate the merits of the polymer and inorganic electrolytes and have attracted much attention in recent years. In order to increase the electrochemical performance, especially the low lithium (Li)-ion transference number in traditional dual-ion Li salt-containing CPEs, single-ion conductive CPEs are synthesized with a single-ion polymer conductor (SIPC) as the matrix and Li6.4 La3 Zr1.4 Ta0.6 O12 (LLZTO) particles as the active fillers. The single-ion conductive CPEs show a high Li-ion transference number (up to 0.96), high room-temperature (RT) ionic conductivity (>1.0 × 10-4 S cm-1 ), wide electrochemical stability window (>5.0 V, vs Li/Li+ ), and excellent long-term cycling stability with Li metal at RT (3200 h). Based on the SIPC-LLZTO CPE, the solid-state lithium metal batteries with LiFePO4 - and LiCoO2 -based cathodes deliver average discharge capacities of 159 mAh g-1 for 600 cycles and 119 mAh g-1 for 200 cycles at RT, respectively. This study sheds light on the design of high-performance CPEs for next-generation solid-state lithium metal batteries.

10.
Small ; 20(22): e2307536, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38126666

RESUMO

Poly (3,4-ethylenedioxythiophene) (PEDOT) doped with polystyrene sulfonate (PSS) is the most used conducting polymer from energy to biomedical applications. Despite its exceptional properties, there is a need for developing new materials that can improve some of its inherent limitations, e.g., biocompatibility. In this context, doping PEDOT is propose with a robust recombinant protein with tunable properties, the consensus tetratricopeptide repeated protein (CTPR). The doping consists of an oxidative polymerization, where the PEDOT chains are stabilized by the negative charges of the CTPR protein. CTPR proteins are evaluated with three different lengths (3, 10, and 20 identical CTPR units) and optimized varied synthetic conditions. These findings revealed higher doping rate and oxidized state of the PEDOT chains when doped with the smallest scaffold (CTPR3). These PEDOT:CTPR hybrids possess ionic and electronic conductivity. Notably, PEDOT:CTPR3 displayed an electronic conductivity of 0.016 S cm-1, higher than any other reported protein-doped PEDOT. This result places PEDOT:CTPR3 at the level of PEDOT-biopolymer hybrids, and brings it closer in performance to PEDOT:PSS gold standard. Furthermore, PEDOT:CTPR3 dispersion is successfully optimized for inkjet printing, preserving its electroactivity properties after printing. This approach opens the door to the use of these novel hybrids for bioelectronics.


Assuntos
Materiais Biocompatíveis , Compostos Bicíclicos Heterocíclicos com Pontes , Condutividade Elétrica , Polímeros , Compostos Bicíclicos Heterocíclicos com Pontes/química , Polímeros/química , Materiais Biocompatíveis/química , Poliestirenos/química , Engenharia de Proteínas/métodos , Íons , Eletrônica
11.
Chemistry ; 30(30): e202400782, 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38517200

RESUMO

The synthesis and properties of a series of 11,11,12,12-tetracyano-9,10-anthraquinodimethane (TCAQ) inspired electron acceptors based on thiophene-fused quinone and triptycene motifs is presented. This has yielded insights into structure-property relationships for establishing and modulating simultaneous two-electron reduction processes in TCAQ analogues. These new compounds were synthesised using a Friedel-Crafts acylation between triptycene and thiophene-3,4-dicarbonyl chloride. Isomeric para-quinones featuring a [c]-fused thiophene on one side and a ß,ß- or α,ß-fused triptycene on the other were isolated alongside a thiophene-3,4-diketone which bears two triptycene fragments. Knoevenagel condensation of these products with malononitrile produced a quinoidal bis(dicyanomethylene), an oxo-dicyanomethylene and an acyclic bis(dicyanomethylene). This series of new electron accepting molecules has been studied using X-ray crystallography and the implications of their 3D structures on NMR and UV/vis absorbance spectroscopy and cyclic voltammetry results have been ascertained with conclusions underpinned by computational methods.

12.
Macromol Rapid Commun ; 45(4): e2300557, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-37880914

RESUMO

Eutectogels are gaining attention in flexible device applications for their superior ionic conductivity, stability, biocompatibility, and cost-effectiveness. However, most existing eutectogels suffer from low strength and toughness. Herein, ultra-tough and highly stretchable polyacrylamide (PAM) eutectogels featuring a dual-crosslinked network comprising chemical cross-linking and physical cross-linking facilitated by metal coordination bonds and hydrogen bonds are developed. This is achieved through a controlled strategy involving polymerization of acrylamide in a coordinated metal salt-type deep eutectic solvent (DES) combined with a non-coordinated choline chloride (ChCl)-type DES mixture. By varying the molar ratio of these two types of DES, exceptional and adjustable mechanical properties of the resulting eutectogel are achieved, including a high tensile strength ranging from 2.9 to 8.2 MPa and elongation at break ranging from 1725 to 747%, at a 70 wt% DES content. Furthermore, the reversible non-covalent crosslinking in these eutectogels enables self-recovery and self-healing capabilities of eutectogels. The prepared eutectogels also exhibit outstanding ionic conductivity (3.56 mS cm-1 ), making them well-suited for use as strain sensors in human motion detection. The toughening strategy is universally effective for creating tough eutectogels using coordinated metal salt-type DES with various metal ions, as well as a diverse range of coordinatable polymers.


Assuntos
Acrilamida , Solventes Eutéticos Profundos , Humanos , Colina , Condutividade Elétrica , Ligação de Hidrogênio , Cloreto de Sódio
13.
Philos Trans A Math Phys Eng Sci ; 382(2281): 20230313, 2024 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-39246077

RESUMO

Solid-state ionic conductors find application across various domains in materials science, particularly showcasing their significance in energy storage and conversion technologies. To effectively utilize these materials in high-performance electrochemical devices, a comprehensive understanding and precise control of charge carriers' distribution and ionic mobility at interfaces are paramount. A major challenge lies in unravelling the atomic-level processes governing ion dynamics within intricate solid and interfacial structures, such as grain boundaries and heterophases. From a theoretical viewpoint, in this Perspective article, my focus is to offer an overview of the current comprehension of key aspects related to solid-state ionic interfaces, with a particular emphasis on solid electrolytes for batteries, while providing a personal critical assessment of recent research advancements. I begin by introducing fundamental concepts for understanding solid-state conductors, such as the classical diffusion model and chemical potential. Subsequently, I delve into the modelling of space-charge regions, which are pivotal for understanding the physicochemical origins of charge redistribution at electrified interfaces. Finally, I discuss modern computational methods, such as density functional theory and machine-learned potentials, which offer invaluable tools for gaining insights into the atomic-scale behaviour of solid-state ionic interfaces, including both ionic mobility and interfacial reactivity aspects. This article is part of the theme issue 'Celebrating the 15th anniversary of the Royal Society Newton International Fellowship'.

14.
Sensors (Basel) ; 24(3)2024 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-38339503

RESUMO

In this study, the coupled ordinary differential equations for the galloping of the first two modes in iced bundled conductors, including in-plane, out-of-plane, and torsional directions, are derived. Furthermore, through numerical analysis, the critical conditions of this modal galloping are determined in the range of wind speed-sag parameters, and the galloping patterns and variation laws in different parameter spaces are analyzed. The parameter space is then divided into five regions according to the different galloping modes. Under the multimodal coupling mechanism of galloping, the impact of single and two kinds of coupled mode galloping on the spatial nonlinear behavior is explored. The results reveal that the system exhibits an elliptical orbit motion during single mode galloping, while an "8" motion pattern emerges during coupled mode galloping. Moreover, two patterns of "8" motion are displayed under different parameter spaces. This research provides a theoretical foundation for the design of transmission lines.

15.
Angew Chem Int Ed Engl ; 63(5): e202315537, 2024 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-38081781

RESUMO

The ion/chemical-based modulation feature of organic mixed ionic-electronic conductors (OMIECs) are critical to advancing next generation bio-integrated neuromorphic hardware. Despite achievements with polymeric OMIECs in organic electrochemical neuronal synapse (OENS). However, small molecule OMIECs based OENS has not yet been realized. Here, for the first time, we demonstrate an effective materials design concept of combining n-type fused all-acceptor small molecule OMIECs with subtle side chain optimization that enables robustly and flexibly modulating versatile synaptic behavior and sensing neurotransmitter in solid or aqueous electrolyte, operating in accumulation modes. By judicious tuning the ending side chains, the linear oligoether and butyl chain derivative gNR-Bu exhibits higher recognition accuracy for a model artificial neural network (ANN) simulation, higher steady conductance states and more outstanding ambient stability, which is superior to the state-of-art n-type OMIECs based OENS. These superior artificial synapse characteristics of gNR-Bu can be attributed to its higher crystallinity with stronger ion bonding capacities. More impressively, we unprecedentedly realized n-type small-molecule OMIECs based OENS as a neuromorphic biosensor enabling to respond synaptic communication signals of dopamine even at sub-µM level in aqueous electrolyte. This work may open a new path of small-molecule ion-electron conductors for next-generation ANN and bioelectronics.

16.
Angew Chem Int Ed Engl ; : e202412173, 2024 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-39205422

RESUMO

Aqueous Zn-ion batteries (AZIBs) are promising for the next-generation large-scale energy storage. However, the Zn anode remains facing challenges. Here, we report a cyclodextrin polymer (P-CD) to construct quasi-single ion conductor for coating and protecting Zn anodes. The P-CD coating layer inhibited the corrosion of Zn anode and prevented the side reaction of metal anodes. More important is that the cyclodextrin units enabled the trapping of anions through host-guest interactions and hydrogen bonds, forming a quasi-single ion conductor that elevated the Zn ion transference number (from 0.31 to 0.68), suppressed the formation of space charge regions and hence stabilized the plating/striping of Zn ions. As a result, the Zn//Zn symmetric cells coated with P-CD achieved a 70.6 times improvement in cycle life at high current densities of 10 mA cm-2 with 10 mAh cm-2. Importantly, the Zn//K1.1V3O8 (KVO) full-cells with high mass loading of cathode materials and low N/P ratio of 1.46 reached the capacity retention of 94.5% after 1000 cycles at 10 A g-1; while the cell without coating failed only after 230 cycles. These results provide novel perspective into the control of solid-electrolyte interfaces for stabilizing Zn anode and offer a practical strategy to improve AZIBs.

17.
Angew Chem Int Ed Engl ; : e202412401, 2024 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-39243107

RESUMO

All-solid-state potassium metal batteries have caught increasing interest owing to their abundance, cost-effectiveness, and high energy/power density. However, their development is generally constrained by the lack of suitable solid-state electrolytes. Herein, we report a new complex KCB9H10·2C3H4N2, synthesized by grinding and heating the mixture of potassium decahydrido-monocarba-closo-decaborate (KCB9H10) and imidazole (C3H4N2) under mild conditions, to achieve the K-ion superionic solid-state electrolyte. The crystal structure was revealed as an orthorhombic lattice with the space group of Pna21 by FOX software. The diffusion properties for K+ in the crystal structure were calculated using the climbing image nudged elastic band (CI-NEB) method. KCB9H10·2C3H4N2 exhibited a high ionic conductivity of 1.3 × 10-4 S cm-1 at 30 °C, four orders of magnitude higher than that of KCB9H10. This ionic conductivity is also the highest value of hydridoborate-based K+ conductors reported. Moreover, KCB9H10·2C3H4N2 demonstrated a K+ transference number of 0.96, an electrochemical stability window of 1.2 to 3.2 V vs. K/K+, and good stability against the K metal coated by a layer of potassium imidazolate (KIm). These great performances make KCB9H10·2C3H4N2 a promising K-ion solid-state electrolyte.

18.
Angew Chem Int Ed Engl ; 63(18): e202401716, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38372050

RESUMO

High-capacity Ni-rich layered oxides are promising cathode materials for fabrication of lithium-ion batteries (LIBs) with high energy density. However, thermal runaway of LIBs with these cathodes leads to great safety concerns. In this study, single crystalline LiNi0.9Co0.05Mn0.05O2 (NCM-SC) has been prepared and a flexible optical fiber was buried inside the pouch-type LIBs with NCM-SC cathode to in situ study its real-time temperature evolution during charge/discharge process. NCM-SC exhibits an enhanced Li+ ions transportation efficiency and electrode reaction kinetics, which can effectively reduce the generation of polarization heat and mitigate the internal temperature rise of the pouch-type battery. Meanwhile, solid-electrolyte interface (SEI) film decomposition and gas accumulation are effectively alleviated, due to the enhanced thermal stability of SEI film formed on NCM-SC. Moreover, the single crystal architecture can effectively retard layered to spinal and rock-salt phase transition, mitigate the crack formation and structural collapse. Consequently, NCM-SC exhibits an excellent electrochemical performance and enhanced thermal stability.

19.
Angew Chem Int Ed Engl ; 63(17): e202400424, 2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38433094

RESUMO

Halide superionic conductors (SICs) are drawing significant research attention for their potential applications in all-solid-state batteries. A key challenge in developing such SICs is to explore and design halide structural frameworks that enable rapid ion movement. In this work, we show that the close-packed anion frameworks shared by traditional halide ionic conductors face intrinsic limitations in fast ion conduction, regardless of structural regulation. Beyond the close-packed anion frameworks, we identify that the non-close-packed anion frameworks have great potential to achieve superionic conductivity. Notably, we unravel that the non-close-packed UCl3-type framework exhibit superionic conductivity for a diverse range of carrier ions, including Li+, Na+, K+, and Ag+, which are validated through both ab initio molecular dynamics simulations and experimental measurements. We elucidate that the remarkable ionic conductivity observed in the UCl3-type framework structure stems from its significantly more distorted site and larger diffusion channel than its close-packed counterparts. By employing the non-close-packed anion framework as the key feature for high-throughput computational screening, we also identify LiGaCl3 as a promising candidate for halide SICs. These discoveries provide crucial insights for the exploration and design of novel halide SICs.

20.
Angew Chem Int Ed Engl ; : e202416288, 2024 Sep 18.
Artigo em Inglês | MEDLINE | ID: mdl-39291657

RESUMO

We present a series of newly developed donor-acceptor (D-A) polymers designed specifically for organic electrochemical transistors (OECTs) synthesized by a straightforward route. All polymers exhibited accumulation mode behavior in OECT devices, and tuning of the donor comonomer resulted in a three-order-of-magnitude increase in transconductance. The best polymer gFBT-g2T, exhibited normalized peak transconductance (gm,norm) of 298±10.4 S cm-1 with a corresponding product of charge-carrier mobility and volumetric capacitance, µC*, of 847 F V-1 cm-1 s-1 and a µ of 5.76 cm2 V-1 s-1, amongst the highest reported to date. Furthermore, gFBT-g2T exhibited exceptional temperature stability, maintaining the outstanding electrochemical performance even after undergoing a standard (autoclave) high pressure steam sterilization procedure. Steam treatment was also found to promote film porosity, with the formation of circular 200 - 400 nm voids. These results demonstrate the potential of gFBT-g2T in p-type accumulation mode OECTs, and pave the way for the use in implantable bioelectronics for medical applications.

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