Solid-state Conductors Research Articles

Synthesis and Characterization of Bis (mercaptoacetamido)-butanediol Dihydrazone Coordination Polymers

Coordination polymers of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd (II) with bis-bidentate ligand delivered from mercaptoacetic acid and 2,3 butanedione dihydrazone have been prepared. All polychelates are coloured, amorphous solid insoluble in water and common organic solvents and characterized with the aid of analytical, magnetic, spectral and thermal studies. The Mn(II),Co(II) and Ni(II) polychelates are of a six co-ordinated octahedral structure, where as Zn(II) and Cd(II) polychelates are found to be four co-ordinated while Cu(II) exhibit square planer structure respectively. Elemental analysis indicators a metal: ligand ratio 1:1 by using graphical Freeman–Carrol method various thermodynamics parameters have also been evaluated. Thermal stability of the complexes have been tested for their antibacterial activity against the bacteria E coli, Bacillus sp, stappylocous and Pseudomonus sp. The solid state conductivity of ligand and complexes were also measured in their compressed pettet from in the temperature range 310-450 K and all complexes were are found to be semiconducting in behaviour.

Solid-State Hydroxide Ion Conductivity in Silver(I) Oxide, Ag2O

Solid-State Hydroxide Ion Conductivity in Silver(I) Oxide, Ag₂O

A theoretical perspective on solid-state ionic interfaces.

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'.

Modular MPS3-Based Frameworks for Superionic Conduction of Monovalent and Multivalent Ions.

Next-generation batteries based on more sustainable working ions could offer improved performance, safety, and capacity over lithium-ion batteries while also decreasing the cost. Development of next-generation battery technology using "beyond-Li" mobile ions, especially multivalent ions, is limited due to a lack of understanding of solid state conduction of these ions. Here, we introduce ligand-coordinated ions in MPS3-based (M = Mn, Cd) solid host crystals to simultaneously increase the size of the interlayer spacing, through which the ions can migrate, and screen the charge-dense ions. The ligand-assisted conduction mechanism enables ambient temperature superionic conductivity of various next-generation mobile ions in the electronically insulating MPS3-based solid. Without the coordinating ligands, all of the compounds show little to no ionic conductivity. Pulsed-field gradient nuclear magnetic resonance spectroscopy suggests that the ionic conduction occurs through a hopping mechanism, where the cations are moving between H2O molecules, instead of a vehicular mechanism which has been observed in other hydrated layered solids. This modular system not only facilitates tailoring to different potential applications but also enables us to probe the effect of different host structures, mobile ions, and coordinating ligands on the ionic conductivity. This research highlights the influence of cation charge density, diffusion channel size, and effective charge screening on ligand-assisted solid state ionic conductivity. The insights gained can be applied in the design of other ligand-assisted solid state ionic conductors, which will be especially impactful in realizing solid state multivalent ionic conductors. Additionally, the ion-intercalated MPS3-based frameworks could potentially serve as a universal solid state electrolyte for various next-generation battery chemistries.

Electrically Conductive Peptide Fibers as Direct Electron Transfer Scaffolds for Enzymatic Electrocatalysis

Biology provides many sources of inspiration for synthetic and multi-functional nanomaterials. Naturally evolved proteins possess a range of unique functions and self-assembly behavior. Some of these have electron transport functions as part of metabolic processes. Their flexible design and potential for stimuli responsiveness make proteins ideal building blocks of bioelectronic interfaces. In biosensor and electrocatalysis applications, bioelectronic materials are designed to interconvert biological signals or processes into electronic signals and vice versa. In this work, we designed a peptide fiber structure that exhibits stimuli-responsive self-assembly and the capacity to transport electrical current over micrometer long distances. Hierarchically ordered nanofibers of α-helical coiled-coil peptides were assembled using a pH responsive structure ordering motif comprising of two neighboring lysine residues. Cryo-EM structures of these assemblies reveal a novel organization of α-helical peptides in a cross coiled coil arrangement that exhibits electrical conductivity. Both solid-state and solution-based electrochemical characterization show that these fibers are conductive. Single-fiber conductive AFM determined that the solid-state electrical conductivity is on a similar order of magnitude with conductive cytochrome filaments from bacteria. Solution deposited fiber films approximately doubled the electroactive surface area of the electrode, confirming their conductivity in aqueous environments. Furthermore, these fibers can be used as scaffolds for redox enzyme immobilization for electrochemical biosensing. Progress towards immobilized enzymatic devices will be discussed as well. This work further expands the field of stimuli-responsive and multifunctional nanomaterials by using peptide assemblies as structural supports for future implementation in bioelectronic and bioelectrochemical systems.

Triazolium bromoferrates – An alternative choice for ionic liquids

Four triazolium salts of iron were synthesized. One of them had melting point below 100 °C classifying it as an ionic liquid. Crystal structures of three salts were measured by X-Ray diffraction. DFT calculations of the synthesized anions were performed in order to help with the identification of measured Raman spectra signals, which were used to confirm the presence of tetrabromoferrate anions. Conductivities of the solutions of synthesized salts as well as their solid state conductivities were measured, confirming them as useful electrolytes and solid state conductors. This research expands the scope of cations of ionic liquids to rarely used in this regard triazoles. Additionally, atypical anions namely FeBr4− and FeBr42− were used giving interesting insights into crystal structures of triazolium ferrate salts.

A full solid-state conceptual magnetocaloric refrigerator based on hybrid regeneration

The environmental friendliness and high efficiency of magnetocaloric refrigeration make it a promising substitute for vapor compression refrigeration. However, the common use of heat transfer fluid in conventional passive magnetic regenerators (PMRs) and active magnetic regenerators (AMRs) makes only partial materials contribute to the regeneration process, which produces large regeneration loss and greatly limits the regeneration efficiency and refrigeration performance at high frequency. Herein, we propose a new conceptual hybrid magnetic regenerator (HMR) composed of multiple solid-state high thermal conductivity materials (HTCMs) and magnetocaloric materials (MCMs), in which both HTCM and MCM elements participate in the regeneration process. This novel working mode could greatly reduce regeneration losses caused by dead volume, pressure losses, and temperature nonuniformity in heat transfer substances to markedly improve regeneration efficiency at high working frequencies. Using the experimentally obtained adiabatic temperature change and magnetic work and with the help of finite element simulation, a maximum temperature of 26 K, a dramatically large cooling power of 8.3kW/kg, and a maximum ideal exergy efficiency of 54.2% are achieved at the working frequency of 10Hz for an ideal prototype device of a rotary HMR magnetocaloric refrigerator, which shows potential for achieving an integrative, advanced performance against current AMR/PMR systems.

A simplified mathematical modeling approach for thermal runaway of Li(Ni0.8Co0.1Mn0.1)O2 pouch cells based on thermal runaway experimental data

Currently, the numerical modeling methods used to characterize the thermal runaway and propagation mechanisms in NCM811 pouch batteries still face numerous challenges. This is primarily due to the uncertainties in thermal runaway reactions and the immense computational demands encountered when modeling begins at the granular level of the cell. To address this issue, this study designed a series of experiments for an NCM811 pouch battery. By employing experimental data, reasonable assumptions were made regarding the combined effects of solid-state thermal conduction, electrochemical heating, and fluid-solid heat transfer through gas jet streams. A simplified thermal runaway mathematical modeling method based on experimental data was proposed, effectively tackling the problem. This framework was then applied to thermal runaway experiments on a single NCM811 battery used in this study, providing essential input parameters for three-dimensional numerical modeling of modules composed of multiple batteries in multiphysics simulation software. The simulation results derived from the proposed method were in good agreement with experimental data. This study can characterize the thermal runaway and thermal propagation characteristics of battery modules using single-cell thermal runaway experiments. Moreover, the proposed modeling approach not only predicted the experimental outcomes of the NCM811 pouch battery with reasonable accuracy but also provided smoother data, elucidating the highly fluctuating trends observed in experimental data. This method also offers guidance for designing fire prevention and smoke exhaust systems for battery packs. This study presents a novel approach for the mathematical modeling of thermal runaway and thermal propagation in battery modules using NCM811 pouch batteries, contributing to the ongoing development of lithium-ion battery module design.

Self-assembly of water-filled molecular saddles to generate diverse morphologies and high proton conductivity.

The design of single-component organic compounds acting as efficient solid-state proton conduction (SSPC) materials has been gaining significant traction in recent times. Molecular design and controlled self-assembly are critical components in achieving highly efficient SSPC. In this work, we report the design, synthesis, and self-assembly of an organic macrocyclic aza-crown-type compound, P2Mac, which complements synthetic ease with efficient SSPC. P2Mac is derived from the pyridine-2,6-dicarboxamide (PDC) framework and contains polar amide and amine residues in its inner region, while aromatic residues occupy the periphery of the macrocycle. The crystal structure analysis revealed that P2Mac adopts a saddle-shaped geometry. Each P2Mac molecule interacts with one water molecule that is present in its central polar cavity, stabilized by a network of five hydrogen bonds. We could self-assemble P2Mac in a variety of unique, aesthetically pleasing morphologies such as micron-sized octahedra, hexapods, as well as hollow nanoparticles, and microrods. The water-filled polar channels formed through the stacking of P2Mac allow attaining a high proton conductivity value of 21.1 mS cm-1 at 27 °C under a relative humidity (RH) of 95% in the single crystals of P2Mac, while the as-prepared P2Mac pellet sample exhibited about three-orders of magnitude lower conduction under these conditions. The low activation energy of 0.39 eV, calculated from the Arrhenius plot, indicates the presence of the Grotthus proton hopping mechanism in the transport process. This report highlights the pivotal role of molecular design and self-assembly in creating high-performance SSPC organic materials.

Tetradecahedral Cu@Ag core–shell powder with high solid-state dewetting and oxidation resistance for low-temperature conductive paste

We demonstrate a novel tetradecahedral Cu@Ag core–shell powder with large Ag shell grains, which has better solid-state dewetting resistance, oxidation resistance and conductivity compared to conventional spherical Cu@Ag core–shell powder.

Mg-doped cathodic properties and solid-state ionic conduction in P2-type layered material for Na-ion batteries and supercapacitors

Sodium-ion batteries and supercapacitors look promising candidates as an alternative solution for electrochemical energy storage due to their decent energy density, low cost, good reversibility, and high abundance on the Earth's surface.

(Invited) A Dive into the Complex Mechanisms That May or May Not Increase Li/Na Mobility in Solid State Conductors

The conductivity of Li and Na has achieved remarkably high values in some materials, higher than what has been achieved in liquid electrolytes. Because there is no mobile solvation shell in solid-state conductors, the maximum of conductivity is essentially unlimited. I will discuss our current understanding of the compositional and structural elements that contribute to very high alkali ion mobility. This will include a discussion, of activated complexes that create concerted motion, possible high-entropy effects, the effect of (poly)anions, and structural topology.

Electrochemical Behavior of Tris(2,2'-bipyridine)Iron Complex in 1-Butyl-1-Methylpyrrolidinium Bis(fluorosulfonyl)Amide Ionic Liquid in the Presence and Absence of Lithium Ion

Ionic liquids composed of bis(fluorosulfonyl)amide (FSA–) have been investigated as the promising electrolytes for rechargeable batteries because of the formation of favorable solid electrolyte interphase (SEI) for some alkali metal ions in addition to relatively low viscosity. The FSA–-based ionic liquids are also considered to be applied to redox flow batteries, which utilize the electrode reactions of soluble species on inert electrodes. However, few electrode reactions of dissolved species have been explored in the FSA–-based ionic liquids. On the other hand, ion-conductive membranes are necessary for development of redox flow batteries. An inorganic solid-state conductor, lithium ion conductive glass ceramics (LICGC, Li1+x+y Al x (Ti,Ge)2-x Si y P3-y O12), is one of the possible membranes usable in ionic liquids containing Li+. In the present study, the electrochemical behavior of tris(2,2'-bipyridine)iron complexes, [Fe(bpy)3]2+, was investigated in BMPFSA (BMP = 1-butyl-1-methylpyrrolidinium) in the presence and absence of Li+.The redox reactions of [Fe(bpy)3]3+/2+, [Fe(bpy)3]2+/+, [Fe(bpy)3]+/0, and [Fe(bpy)3]0/– were observed by cyclic voltammetry in the absence of Li+. However, these reactions were affected by the SEI formation at a negative potential region in the presence of Li+. The donor number of BMPFSA was estimated from the formal potential of [Fe(bpy)3]3+/2+. The diffusion coefficients of [Fe(bpy)3]3+ and [Fe(bpy)3]2+ were determined by chronoamperometry. The standard rate constant for [Fe(bpy)3]3+/2+ was evaluated by electrochemical impedance spectroscopy. The relationship between these kinetic parameters and physical properties was discussed.

Recent advances in open-shell mixed conductors—From molecular radicals to polymers

Mixed conductors have recently garnered attention in the chemical physicist community due to their distinctive conducting nature and numerous potential applications. These species transport charges via both ionic and electronic pathways, where the coupling between these pathways facilitates an alternative mode of charge transport. Among the various mixed conductors examined, stable open-shell organic compounds are emerging as a promising class of materials. They have the potential to supplant existing organic mixed conductors thanks to their superior conductivity, ease of processing, environmental stability, and functional adaptability. Notably, recent advancements in open-shell macromolecules have been remarkable, ranging from their unprecedented solid-state electrical conductivity to their versatile roles in electrochemistry. Similarly, recent strides in small molecular open-shell species deserve attention. The solid-state electronic properties of these small molecular radicals can be compared to those of macromolecular (non-)conjugated organics materials, and they also play a significant role in wet (electrolyte-based) chemistry. In this review article, we offer a comprehensive overview of open-shell organic compounds, encompassing both small and macromolecular radicals. We particularly emphasize their role as a mixed conductor in various applications, the unique context of each species, and the interconnections between them.

P and Fe doping, a strategy to develop light and magnetic responsive multifunctional materials: The case of LiMn2O4

The current work reports an unprecedented multifunctional material with optical activity and a modified magnetic response by a unique combination of doping with P and Fe into the spinel LiMn2O4. Through inductively coupled plasma – optical emission spectroscopy, X-ray absorption near-edge spectroscopy, X-ray diffraction and scanning transmission electron microscopy, the chemical composition, oxidation state and the crystalline structure are determined. Solid-state UV-Vis spectroscopy, magnetic susceptibility and electronic conductivity reveal the critical importance of the interaction between iron and phosphorus when simultaneously doping the crystalline structure of LiMn2O4. The presence of Fe and P considerably increases charge carrier concentration as a mechanism for enhancing electronic conductivity. Fe and P doping also creates Fe-Fe spin interactions that allow double electron optical excitations. This opens a pathway to create multifunctional materials for light-assisted charging lithium-ion batteries. P doping also induces the formation of magnetic clusters arising from the Fe-O-Fe, Fe-O-Mn and Mn-O-Mn spin exchange interactions. The magnetic response of the materials is strongly influenced by the relative amount of Fe in octahedral or tetrahedral sites of the spinel structure. Such ferrimagnetic behaviour has not been reported before LiMn2O4 doped with Fe or P separately. The potential applicability of this newly identified magnetic feature was demonstrated by a significant capacity gain when a lithium-ion cell is exposed to a static external magnetic field.

Bimetallic Anionic Organic Frameworks with Solid-State Cation Conduction for Charge Storage Applications.

A new phosphonate-based anionic bimetallic organic framework, with the general formula of A4 -Zn-DOBDP (wherein A is Li+ or Na+ , and DOBDP6- is the 2,5-dioxido-1,4-benzenediphosphate ligand) is prepared and characterized for energy storage applications. With four alkali cations per formula unit, the A4 -Zn-DOBDP MOF is found to be the first example of non-solvated cation conducting MOF with measured conductivities of 5.4×10-8 S cm-1 and 3.4×10-8 S cm-1 for Li4 - and Na4 - phases, indicating phase and composition effects of Li+ and Na+ shuttling through the channels. Three orders of magnitude increase in ionic conductivity is further attained upon solvation with propylene carbonate, placing this system among the best MOF ionic conductors at room temperature. As positive electrode material, Li4 -Zn-DOBDP delivers a specific capacity of 140 mAh g-1 at a high average discharge potential of 3.2 V (vs. Li+ /Li) with 90 % of capacity retention over 100 cycles. The significance of this research extends from the development of a new family of electroactive phosphonate-based MOFs with inherent ionic conductivity and reversible cation storage, to providing elementary insights into the development of highly sought yet still evasive MOFs with mixed-ion and electron conduction for energy storage applications.

Design principles for NASICON super-ionic conductors

Na Super Ionic Conductor (NASICON) materials are an important class of solid-state electrolytes owing to their high ionic conductivity and superior chemical and electrochemical stability. In this paper, we combine first-principles calculations, experimental synthesis and testing, and natural language-driven text-mined historical data on NASICON ionic conductivity to achieve clear insights into how chemical composition influences the Na-ion conductivity. These insights, together with a high-throughput first-principles analysis of the compositional space over which NASICONs are expected to be stable, lead to the successful synthesis and electrochemical investigation of several new NASICONs solid-state conductors. Among these, a high ionic conductivity of 1.2 mS cm−1 could be achieved at 25 °C. We find that the ionic conductivity increases with average metal size up to a certain value and that the substitution of PO4 polyanions by SiO4 also enhances the ionic conductivity. While optimal ionic conductivity is found near a Na content of 3 per formula unit, the exact optimum depends on other compositional variables. Surprisingly, the Na content enhances the ionic conductivity mostly through its effect on the activation barrier, rather than through the carrier concentration. These deconvoluted design criteria may provide guidelines for the design of optimized NASICON conductors.

SINGLE CRYSTALS GROWTH IN THE HOMOGENEITY REGION OF LOW-TEMPERATURE MODIFICATION OF Ag8GeS6

Cationic ion-conductors have found wide practical application as electric batteries. Among them the lithium-ion batteries are the most common commercially used. However, research is being actively carried out to improve the safety of these batteries. Among the possible compounds, silver-containing phases are attractive, since silver-ions, along with high values of ionic conductivity in solid-state, haven’t high chemical activity like the same alkali metal-ions. Realization of the crystal structure necessary for effective ion transport is observed in compounds of the argyrodite structure - a group of ternary chalcogenides and quaternary chalcohalogenides of multi-charged cations (Ge4+, Si4+, P5+). In this work, a study of heterovalent cationic P5+→Ge4+ substitution in the Ag8GeS6 enriched region was carried out. Single crystals of Ag8-x(Ge1-xPx)S6 (x = 0.25; 0.5) solid solutions were grown by the method of directional crystallization using a solution-melt technique. The grown single crystals are characterized by the absence of macrodefects, a dark gray color with a metallic luster, and dimensions of l = ~3 cm and d = 1.2 cm. Using the Rietveld refinement method, the crystal structure was established and the lattice parameters of Ag8-x(Ge1-xPx)S6 (x = 0.25; 0.5) solid solutions were determined. Established, that single crystals of Ag8-x(Ge1-xPx)S6 (x = 0.25; 0.5) solid solutions crystallize in the orthorhombic crystal system in a primitive cell with space group Pna21.
 Keywords: argyrodites; single crystals; directional crystallization; phase analysis.

SINGLE CRYSTALS GROWTH OF Ag7+x(P1-xGex)S6 (x = 0.1; 0.25; 0.33) SOLID SOLUTIONS

Ternary silver argyrodites exhibit a wide range of properties and are classified as promising solid-state conductors, thermoelectrics, photovoltaic and nonlinear optical materials. This is ensured by the peculiarity of the crystal structure of argyrodites, which combines a rigid anionic and a disordered cationic sublattice. This work is devoted to the development of a technological regime for growing high-quality single-crystalline samples of Ag7+x(P1-xGex)S6 (x = 0.1; 0.25; 0.33) solid solutions by the method of directed crystallization from the melt. Polycrystalline alloys of Ag7+x(P1-xGex)S6 (x = 0.1; 0.25; 0.33) solid solution were obtained from previously synthesized ternary Ag7PS6 and Ag8GeS6. The synthesis was carried out by a single-stage and single-temperature method at a maximum temperature of 1010°C. The phase composition of the synthesized alloys was determined by the XRD method. Phase analysis of the obtained polycrystalline alloys did not reveal reflections of impurity phases. The results of thermal studies of Ag7+x(P1-xGex)S6 alloys were used to develop a technological regime for single crystals growth. Ag7+x(P1-xGex)S6 single crystal was grown from the melt by the directional crystallization method. As a result of the research, high-quality single crystals of Ag7+x(P1-xGex)S6 solid solutions (x = 0.1; 0.25; 0.33) were obtained. According to the results of X-ray diffraction, it was established that the solid solution of the composition Ag7.1(P0.9Ge0.1)S6 crystallizes in the primitive cubic cell of SG P213, and the solid solutions Ag7.25(P0.75Ge0.25)S6 and Ag7.33(P0.67Ge0.33)S6 crystallizes in a metastable at room temperature high-temperature modification with SG F-43m.
 Keywords: argyrodites; single crystals; directional crystallization; phase analysis.

Experimental and numerical investigation of melting and solidification enhancement using Fibonacci-inspired fins in a latent thermal energy storage unit

The major challenge with phase change materials (PCMs) is their low thermal conductivity, eventuating long melting (charging) and solidification (discharging) times in latent thermal energy storage (LTES) units. Using extended surfaces (fins) is a popular method to resulve this issue, with recent developments in novel designs such as tree-like and fractal fins. The complex fin configurations improve the conduction while decreasing the natural convection effects by introducing additional shear stress to the melted PCM. The current work proposes a new fin design based on the Fibonacci sequence in a vertical LTES unit to improve the charging/discharging characteristic. The finned geometry is manufactured out of a solid block of aluminum using the wire-cutting technique. Based on the volume expansion method, an experimental setup is designed to observe the charging/discharging behavior. The PCM under study is RT42 and its density, volumetric thermal expansion coefficient and solid-state thermal conductivity are measured in house. Water is the chosen heat transfer fluid (HTF) set to a constant mass flow rate of about 99 kg/h and 96 kg/h for the melting and solidification processes, respectively. The water charging temperature is 61.5 °C while the water discharge temperature is 21.5 °C. A numerical model based on the enthalpy-porosity method is implemented to investigate the physics behind melting/solidification. A careful investigation of the mushy zone constant is performed based on comparing the experimental and numerical results for melting and solidification. The average liquid PCM velocity on the melt front is studied to evaluate the natural convection behavior. The effects of secondary flows and mixing on the melting process in the new geometry are studied by investigating the liquid PCM flow behavior during the charging. The proposed fin performed 20% better in total melting time than longitudinal fins by introducing more dispersed natural convection dominated regions. The reduction of 45% in solidification time is also established for the novel fin.