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This review provides a focused discussion on the structures and ionic conduction mechanisms of inorganic solid-state proton and hydride anion conductors.
Abstract The oxygen ion conductivity of polycrystalline samples of Sm‐doped ceria and of Gd‐doped ceria is studied as a function of doping fraction and temperature using impedance spectroscopy allowing the separation of bulk and grain boundary conductivity. The introduction of a fine spacing for the Sm dopant fraction allows the clear identification of the dopant fraction leading to the largest bulk conductivity. At 267°C, the largest bulk conductivity is shown for Ce 0.93 Sm 0.07 O 1.965 . With increasing temperature, indications of an increase in the dopant fraction, which leads to the maximum in conductivity, are found. For the grain boundary conductivity, the maximum appears at larger dopant fractions compared to the bulk conductivity. The largest total conductivity for both dopants is again found for Sm‐doped ceria. In literature, different syntheses and sample preparation methods led to larger total conductivities for Gd‐doped ceria. In this work, we demonstrate that the variation of sintering conditions leads to scattering in the conductivity over one order of magnitude. Finally, we demonstrate that, in nominally pure cerium oxide, impurities dominate the ionic conductivity.
Predicting practical rates of transport in condensed phases enables the rational design of materials, devices and processes. This is especially critical to developing low-carbon energy technologies such as rechargeable batteries. For ionic conduction, the collective mechanisms, variation of conductivity with timescales and confinement, and ambiguity in the phononic origin of translation, call for a direct probe of the fundamental steps of ionic diffusion: ion hops. However, such hops are rare-event large-amplitude translations, and are challenging to excite and detect. Here we use single-cycle terahertz pumps to impulsively trigger ionic hopping in battery solid electrolytes. This is visualized by an induced transient birefringence, enabling direct probing of anisotropy in ionic hopping on the picosecond timescale. The relaxation of the transient signal measures the decay of orientational memory, and the production of entropy in diffusion. We extend experimental results using in silico transient birefringence to identify vibrational attempt frequencies for ion hopping. Using nonlinear optical methods, we probe ion transport at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale, and demonstrate the connection between activated transport and the thermodynamics of information.
Redox reactions that occur at the electrodes of batteries require transport of both ions and electrons to the active centers. Reported is the synthesis of a block copolymer that exhibits simultaneous electronic and ionic conduction. A combination of Grignard metathesis polymerization and click reaction was used successively to synthesize the block copolymer containing regioregular poly(3-hexylthiophene) (P3HT) and poly(ethylene oxide) (PEO) segments. The P3HT-PEO/LiTFSI mixture was then used to make a lithium battery cathode with LiFePO.sub.4 as the only other component. All-solid lithium batteries of the cathode described above, a solid electrolyte and a lithium foil as the anode showed capacities within experimental error of the theoretical capacity of the battery. The ability of P3HT-PEO to serve all of the transport and binding functions required in a lithium battery electrode is thus demonstrated.
The practical application of lithium (Li) metal battery is impeded by the Li dendrite growth and unstable solid electrolyte interphase (SEI) layer. Herein, an ultra-stretchable and ionic conducting chemically crosslinked pressure-sensitive adhesive (cPSA) synthesized via the copolymerization of 2-ethylhexyl acrylate and acrylic acid with poly(ethyleneglycol)dimethacrylate as crosslinker (short for 70cPSA), is developed as both artificial SEI layer and solid polymer electrolyte (SPE) for stable Li-metal electrode, enabling all-solid-state Li metal batteries with excellent cycling performance. As an artificial SEI layer, the 70cPSA-modified electrodes exhibit excellent electrochemical performance in Li|70cPSA@Cu half cells and 70cPSA@Li|70cPSA@Li symmetric cells. In full cells with LiFePO 4 (LFP) as cathode, the 70cPSA@Li|LFP cell exhibits stable cycling performance over 250 cycles. Utilized as SPE, the all-solid-state Li|SPE|LFP cell delivers excellent cycling stability with a capacity retention of 86% over 500 cycles. With high-voltage LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) as cathode, the Li|SPE|NMC811 cell exhibits a discharge capacity of 124.3 mAh g -1 with a capacity retention of 71% after 200 cycles. Furthermore, the rational design of PSAs and investigation of their dual role for stable and safe Li-metal batteries may shed a light on adhesive polymers for battery applications.
The ordered structure A 2 B 2 O 6 O’ in pyrochlores engenders twin rows of inequivalent anion sublattices each centred on alternating cations. While it is known that cation antisite disorder augments the ionic conductivity by several orders of magnitude, the local cation environment around the anions and the dynamic anion reordering during the cation disordering are not well-elucidated. Using atomistic simulations on Gd 2 Zr 2 O 7 , we first show that the anions engage in concerted hops to the neighbouring tetrahedral sites mostly along with the $\langle$1 0 0$\rangle$ direction while completely avoiding the octahedral sites. While the initially vacant 8 a sites start accommodating oxygen ions with increasing cation disorder, they show noticeable reluctance even at significant levels of disorder. We have also tracked both the distribution of available oxygen sites following random cation disorder, which is dependent only on cation disordering, and the probability of occupation of these sites. Interestingly, the available oxygen sites show a non-monotonic dependence on the number of B ions in the nearest neighbouring shell while the occupation probability of all the available oxygen sites increases monotonically. A tetrahedral oxygen site thus has a better probability of being occupied when it has a greater number of second neighbour B ions. This article is part of the Theo Murphy meeting issue 'Understanding fast-ion conduction in solid electrolytes'.
Heterostructured multilayers have been controversially reported to alter the oxygen ion conductivity of solid electrolytes by inducing interfacial mechanical strain. Here, we fabricated thin film multilayers composed of 9 mol% Y 2 O 3 doped ZrO 2 (YSZ) and Ce 1-x Zr x O 2 (CZO) to systematically quantify the effects of tensile strain on the oxygen-ion conduction behavior in YSZ. A significant advantage of using CZO is that its lattice parameter can be continuously varied by adjusting the Ce/Zr atomic ratio, simplifying the strain control over the neighboring YSZ layers. Three different sets of multilayers composed of YSZ with CeO 2 , or with Ce 0.70 Z r0.30 O 2 (CZO30), or with Ce 0.55 Zr 0.45 O 2 (CZO45) were prepared on Al 2 O 3 substrates with interfacial lattice mismatch of +5.2%, +3.7%, and +2.9%, respectively. When decreasing the individual layer thicknesses from 35 nm to 5 nm, all of the multilayers exhibited little change of the conductivity, with values consistently near that of bulk YSZ. X-ray diffraction results indicate that the interfacial strains were largely relaxed. In conclusion, suggestions that multilayers are unable to effect ionic conductivity changes must therefore consider the difficulties in obtaining lattice mismatch-based elastic strain, even at <3% mismatch.
The permeation of ions through narrow water-filled channels is essential to life and of rapidly-growing importance in technology. Reaching an understanding of the mechanisms underlying the permeation process requires an interdisciplinary approach, where ideas drawn from physics are of particular importance and have brought encouraging progress in recent years. This Introduction sets into context the several ground-breaking papers presented in the Entropy Special Issue on "The Physics of Ionic Conduction in Narrow Biological and Artificial Channels''.
Dense and uniform Li 6.25 Al 0.25 La 3 Zr 2 O 12 (Al-doped LLZO) solid-electrolyte film of ~24 µm thickness is successfully fabricated by room temperature aerosol deposition (AD) method. The process optimization study revealed that careful control of particle size and morphology is one of critical determinants in the development of a compact AD membrane. Notably, our method facilitated an impressive ionic conductivity of approximately 10 –5 S cm –1 , bypassing the necessity for post-annealing processes, a milestone in itself. However, it is hypothesized that the attained conductivity is somewhat restrained by factors such as smaller grain size and potential surface degradation due to moisture exposure during fabrication, indicating avenues for further research. Looking forward, detailed investigations into the film's microstructure and its impact on transport properties will be a focal point, alongside potential enhancements through post-annealing and particle coating strategies. Finally, this research hints at a promising trajectory for the development of high-efficiency solid-state battery technology.
Abstract An efficient method to incorporate a cobaltocenium cation into polymers for anion exchange membranes is described. A cobaltocenium-containing norbornene derivative has been synthesized. It can be homopolymerized, or copolymerized with norbornene, by ring-opening metathesis polymerization (ROMP) with quantitative yields. The composition of the random copolymers can be precisely controlled by adjusting the feed ratio of the monomers. Additionally, the resulting polymers can be cast into thin robust membranes. The morphology of the membranes is characterized by humidity controlled SAXS and TEM, showing disordered interconnected cobaltocenium domains. The high ionic conductivity suggests that such membranes are good candidates for anion exchange membranes.
Nonaqueous redox flow batteries (NARFBs) are a promising class of energy storage devices, but the lack of a chemically stable, conductive membrane that exhibits size-selectivity over redox-active species prevents their broader implementation. Recently, metal–organic frameworks (MOFs) have been implemented into mixed-matrix membranes (MMMs) for NARFBs, but the effects of the MOF linker functionality on membrane properties are not well-understood. In this work, we develop a series of MOF-based MMMs by blending postsynthetically modified variants of UiO-66-NH2 with poly(ethylene-co-vinyl acetate). The modification of UiO-66-NH2 with sulfate groups initially resulted in poor dispersion throughout the MMMs, but when dual-modified with poly(N-isopropylacrylamide), MOF dispersion throughout the MMM was improved, and ionic conductivity was significantly higher than the UiO-66-NH2 MMMs. Furthermore, the dual-modified MMMs demonstrated excellent size-selectivity by blocking redox active species transport. This work demonstrates a synergy between the MOF functional groups to improve MMM properties critical for the development of practical NARFBs.
Single crystals of NaHoP{sub 2}O{sub 7} diphosphate have been prepared by the flux method and its structural and physical properties have been investigated. It crystallizes in the monoclinic system with the space group P2{sub 1}/n and its parameters are: a=8.6796(4) Å, b=5.3677(2) Å, c=13.6904(6) Å, β=106.120° (2), V=612.75 (5) Å{sup 3}, Z=4. The structure of NaHoP{sub 2}O{sub 7} consists of a three-dimensional framework of HoO{sub 6} octahedra, linked by P{sub 2}O{sub 7} diphosphate units, forming tunnels running parallel to [0 1 0], which are occupied by Na atoms. The infrared and Raman vibrational spectra have been investigated. Activation energy was obtained from Arrhenius plots (Ln σT versus 1000/T) and found to be 1.27 eV. The coupling of the structural analysis with the BVS model for NaHoP{sub 2}O{sub 7} has better interpret the measurements of the ionic conductivity and the most probably transport pathway model was determined. - Graphical abstract: Schematic representation of the structural arrangement of NaHoP{sub 2}O{sub 7} shows the sodium conduction pathway along the [0 1 0] direction. Highlights: • Single crystals of NaHoP{sub 2}O{sub 7} were prepared by flux method and characterized by single-crystal X-ray data. • The conductivity and loss spectra were analysed in order explain the mechanism of conduction. • The most probably conduction pathway are determined.
While amorphous materials are often approximated to have a statistically homogeneous atomic structure, they frequently exhibit localized structural heterogeneity that challenges simplified models. This study uses 4D scanning transmission electron microscopy to investigate the strain and structural modifications around gas bubbles in amorphous Bi 2 O 3 induced by argon irradiation. We present a method for determining strain fields surrounding bubbles that can be used to measure the internal pressure of the gas. Compressive strain is observed around the cavities, with higher-order crystalline symmetries emerging near the cavity interfaces, suggesting paracrystalline ordering as a result of bubble coarsening. This ordering, along with a compressive strain gradient, indicates that gas bubbles induce significant localized changes in atomic packing. By analyzing strain fields with maximum compressive strains of 3%, we estimate a lower bound on the internal pressure of the bubbles at 2.5 GPa. These findings provide insight into the complex structural behavior of amorphous materials under stress, particularly in systems with gas inclusions, and offer new methods for probing the local atomic structure in disordered materials. Although considering structural heterogeneity in amorphous systems is non-trivial, these features have crucial impacts on material functionalities, such as mechanical strength, ionic conductivity, and electronic mobility.
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Nanofluidic ionic transistors typically require gate voltages above 1 V and operate only at submillimolar ionic strengths, limiting their biocompatible applications. We demonstrate ionic transistors consisting of single sub-10 nm nanopores drilled in van der Waals (vdW) heterostructures with internal gate electrodes made of few-layer graphene. These devices deliver up to 10-fold current modulation at gate voltages as low as 0.3 V in 10 mM KCl, and ∼2-fold modulation at near-physiological 100 mM KCl. Baseline conductance with no gate shows surface-charge-dominated transport below 100 mM KCl, consistent with negatively charged hBN walls and ∼5 nm opening of the pores. The surface charge and the electrochemical asymmetry introduced by the three-electrode configuration govern the device’s behavior: negative gate voltage (V G ) enriches ionic concentrations and enhances current, whereas positive V G induces a local depletion zone that suppresses transport. The current modulation by V G is dependent on the polarity of the transmembrane potential and leads to ion current rectification. Molecular dynamics simulations of a nanopore in a hBN–graphene–hBN stack reveal confinement and surface charge-dependent suppression of the relative permittivity of interfacial water. Continuum modeling with radially varying interfacial water permittivity reproduces the asymmetric I–V characteristics and explains how the embedded gate sculpts local potential and ion concentrations. By enabling sub-0.5 V control of ionic transport at up to 100 mM salt concentrations, these devices address a key need in nanofluidics to create low-power ionic circuits and biosensing.
Microphase separated block copolymer electrolyte (BCE) systems are attractive candidates for electrochemical systems because the concentrated ionic groups in one block provide pathways for facile ion transport while the non-ionic block bestows mechanical integrity and suppresses excess water uptake. Numerous researchers have prepared and studied bulk BCEs as ion conductors, but these materials inherent complex nature and imprecise architecture makes it difficult to extract definitive conclusions how the macromolecular structure influences ion transport. In this work, the process of block copolymer lithography was demonstrated to create model nano-confined polymer electrolyte brushes that mimic lamellae structures found in bulk BCE membranes. Both nano-confined anion and cation conducting polymer brushes were prepared and excellent ionic conductivities (10 -2 S cm -1 to 10 -1 S cm -1 ) were obtained.
The results of the synthesis and characterization of the optimally doped La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4-δ} solid solution with x = 0, 0.1, 0.2 and 0.3 are reported. The versatility of these La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} materials is explained on the basis of structural features and the ability to accommodate oxygen nonstoichiometry. According to powder X-ray and neutron diffraction data, La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} adopts the tetragonal structure with oxygen vacancies occurring preferentially at the O{sub ap} sites within the {(La/Ca)O} layers of the perovskite blocks and the oxygen deviation from stoichiometry δ was found to be δ=0.0905(6). The bulk conductivity indicated an Arrhenius-type thermally activated process and oxygen vacancies are the possible ionic charge carriers at T=270 °C. An increase of the conductivity was detected when Ni was introduced. With nickel ratio variation, a strong correlation was observed between the Cu(Ni)-O{sub ap} apical bond length variation and the conductivity variation through controlling the O{sup 2−} ion migration. - Highlights: • We report the synthesis and structure of the La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (0≤x≤0.3; δ=0.0905) compounds. • La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (x=0.0, 0.2, 0.3) doped with Ni{sup 2+} have a higher conductivity than undoped La{sub 1.85}Ca{sub 0.15}CuO{sub 4−δ}. • At T=270 °C, sample x=0.3 has the highest conductivity (0.2915 sm{sup −1}).
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