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Neutron diffraction, thermogravimetry, and high temperature solution calorimetry measurements reveal insights into proton and oxygen-ion kinetics in BaCo 0.4 Fe 0.4 Zr 0.2− X Y X O 3− δ triple ionic–electronic conducting ceramics.
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Here, in order to design more effective solid polymer electrolytes, it is important to decouple ion conductivityfrom polymer segmental motion. To that end, novel polymers based on oxanorbornene dicarboximidemonomers with varying lengths of oligomeric ethylene oxide side chains have been synthesized usingring opening metathesis polymerization. These unique polymers have a fairly rigid and bulky backboneand were used to investigate the decoupling of ion motion from polymer segmental dynamics. Ionconductivity was measured using broadband dielectric spectroscopy for varying levels of added lithiumsalt. The conductivity data demonstrate six to seven orders of separation in timescale of ion conductivityfrom polymer segmental motion for polymers with shorter ethylene oxide side chains. However,commensurate changes in the glass transition temperatures T g reduce the effect of decoupling in ionconductivity and lead to lower conductivity at ambient conditions. These results suggest that both anincrease in decoupling and a reduction in T g might be required to develop solid polymer electrolytes withhigh ion conductivity at room temperature.
Highlights: • We synthesized Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}-x wt% 40.2Li{sub 2}O·5.7Y{sub 2}O{sub 3}·54.1SiO{sub 2} (x = 1–10) composites. • Density of the composite samples is higher than one of the sintered Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}. • The composition with x = 5 has high total conductivity, 2.5 × 10{sup −5} S cm{sup −1} at 25 °C. - Abstract: We have investigated the effect of lithium yttrium-silicate glass 40.2Li{sub 2}O·5.7Y{sub 2}O{sub 3}·54.1SiO{sub 2} on the density and total conductivity of tetragonal Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}. An optimal sintering temperature (1200 °C) was selected on the basis of a composite with 1 wt% of the glass having the highest density and total conductivity after annealing at this temperature. A series of composites Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}-x wt% 40.2Li{sub 2}O·5.7Y{sub 2}O{sub 3}·54.1SiO{sub 2} (x = 1–10) was prepared. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential scanning calorimetry. The data revealed that the sintering additive interacted with Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}, causing the glass to crystallize during annealing. The conductivity of the composites was studied using complex impedance spectroscopy over a temperature range of 20–250 °C. The composite with x = 5 exhibited the highest total conductivity at room temperature: 2.5 × 10{sup −5} S cm{sup −1}.
This paper develops a model to predict and interpret the performance of an elevated-temperature, electrochemical, membrane-assisted, water-gas-shift process. The process uses separated feed streams of H 2 O and CO to produce separated streams of H 2 and CO 2 , without an external electrical power source. The dense ceramic membrane is mixed ionic-electronic-conducting (MIEC) gadolinium-doped ceria (GDC) and the porous composite electrodes are Ni-YSZ. At elevated temperature, GDC conducts both oxygen ions and small polarons. The present process uses chemical potential to drive the process. Electrochemical oxidation of CO proceeds within the composite anode and H 2 O reduction proceeds within the composite cathode. At high temperature (e.g., T > 700 °C), GDC has significant electronic leakage in the form of a reduced-cerium small polaron, which supports the charge-transfer reactions. In a typical electrolyzer or fuel cell, this leakage is significantly problematic. However, the present process depends on the leakage current to complete the electrochemical circuit. Model development and validation is based on measured material properties and reactor performance. Potential applications include using CO-rich blast-furnace off gases in steel processing, producing separated streams of H 2 and CO 2 .
Hydrophobic alkyl side chains steer water toward the charge-ion pair, giving rise to large interconnected water clusters that promote ion conduction.
V 2 O 5 is deemed as one of the most promising cathode materials for next-generation high-capacity lithium-ion batteries (LIBs). It possesses a theoretical capacity of 294 mAh g -1 , which is much higher than conventional cathodes. But, there are many issues to be solved before its practical use, including poor cycle life and unsatisfactory rate performance, mainly owing to its low electronic conductivity and ionic diffusivity, as well as structural instability. Our work reports three types of V 2 O 5 asymmetric membranes synthesized by using an adapted reverse-osmosis membrane technology combined with sol-gel chemistry, aiming to stabilize the cyclability and improve the rate performance. V 2 O 5 asymmetric membrane cathodes prepared using graphene as the conductive additives have a specific capacity of approximately 160 mAh g -1 at a current density of 100 mA g -1 with no capacity degradation after 380 cycles. It is also found that the annealing temperature and the choice of conductive additives can affect the morphology of V 2 O 5 nanoparticles and the overall electrode cyclability. Furthermore, we find that a lower annealing temperature (300 vs. 400 °C) and the addition of graphene are beneficial to long-term cycling performance.
Highlights: • Li{sub 2}SiO{sub 3}-modified LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} with well-defined octahedral morphology have been controllably obtained. • The combination of the modification of fast ions conductor and solid state method will be an optional method. • The cyclic performance and rate capability of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4}-based materials have been significantly improved. - Abstract: A simple solid state method was utilized to synthesize excellent spinel Li{sub 2}SiO{sub 3}-modified LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} cathodes. Dual-modification of coating and doping of fast-ion conductor Li{sub 2}SiO{sub 3} leads to stable crystal structure and additional three-dimensional (3-D) channels for Li{sup +}-ion diffusion, and protects the electrode surface from electrolyte attack. The Li{sub 2}SiO{sub 3}-modified material possesses coexistence of ordered P4{sub 3}32 and disordered Fd-3m phases. As a result of improved structure, morphology and conductivity, the Li{sub 2}SiO{sub 3}-modified LiNi{sub 0.5}Mn{sub 1.5}O{sub 4} shows more superior cyclic performance, rate capability and high temperature stability than the pristine: capacity retention of 95.17% at 0.1 C after 100 cycles vs. that of 79.23%; rate capability of 130–89.1 mAh g{sup −1} at 0.1–10 C vs. that of 120–57.6 mAh g{sup −1}; and high temperature capacity retention of 99.42% at 0.1 C vs. that of 79.59%. Our study provides a facile approach to stabilize crystal structure, optimize morphology and conductivity, and thus enhance electrochemical performance of LiNi{sub 0.5}Mn{sub 1.5}O{sub 4}-based materials.
The Na-ion conducting solid electrolyte NASICON is a promising solid state electrolyte (SSE) for use in Na based electrochemical systems. The effects of particle morphology and synthesis of von Alpen type NASICON via hot-pressing were investigated. Spray dried particles were shown to improve mechanical and electrochemical properties. X-ray diffraction, scanning electron microscopy, impulse excitation measurements, Vickers hardness, and impedance spectroscopy were used to correlate relationships between phase purity, microstructure, mechanical properties, and electrochemical properties. Scanning electron microscopy showed the presence of a glass phase as between 19.08% and 28.23% area percentage and a ZrO 2 phase between 0.46% and 3.51% area percentage in the hot-pressed samples. Impulse excitation showed elastic modulus varying from 83.65 to 97.65 GPa. The first values of Poisson's ratio and shear modulus of NASICON are reported as between 0.23 and 0.26 and 33.87 to 38.79 GPa, respectively. Vickers hardness and fracture toughness measurements showed Vickers hardness ranging from 4.30 to 4.68 GPa and fracture toughness ranging from 1.05 to 1.09 MPa m ½ . Impedance spectroscopy showed grain conductivities ranging from 1.023 to 1.287 mS/cm, with grain boundary resistance percentages between 73.22 and 47.5%. Total conductivities ranged from 0.292 to 0.596 mS/cm, with 0.596 mS/cm being achieved at room temperature for the spray dried powders with lower grain boundary resistance percentages.
Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2-8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3-6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60 degrees C. Finally, conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90 degrees C.
The gas-phase conformations of dimers of the channel-forming membrane peptide gramicidin A (GA), produced from isobutanol or aqueous solutions of GA-containing nanodiscs (NDs), are investigated using electrospray ionization-ion mobility separation-mass spectrometry (ESI-IMS-MS) and molecular dynamics (MD) simulations. The IMS arrival times measured for (2GA + 2Na){sup 2+} ions from isobutanol reveal three different conformations, with collision cross-sections (Ω) of 683 Å{sup 2} (conformation 1, C1), 708 Å{sup 2} (C2), and 737 Å{sup 2} (C3). The addition of NH{sub 4}CH{sub 3}CO{sub 2} produced (2GA + 2Na){sup 2+} and (2GA + H + Na){sup 2+} ions, with Ω similar to those of C1, C2, and C3, as well as (2GA + 2H){sup 2+}, (2GA + 2NH{sub 4}){sup 2+}, and (2GA + H + NH{sub 4}){sup 2+} ions, which adopt a single conformation with a Ω similar to that of C2. These results suggest that the nature of the charging agents, imparted by the ESI process, can influence dimer conformation in the gas phase. Notably, the POPC NDs produced exclusively (2GA + 2NH{sub 4}){sup 2+} dimer ions; the DMPC NDs produced both (2GA + 2H){sup 2+} and (2GA + 2NH{sub 4}){sup 2+} dimer ions. While the Ω of (2GA + 2H){sup 2+} is similar to that of C2, the (2GA + 2NH{sub 4}){sup 2+} ions from NDs adopt a more compact structure, with a Ω of 656 Å{sup 2}. It is proposed that this compact structure corresponds to the ion conducting single stranded head-to-head helical GA dimer. These findings highlight the potential of NDs, combined with ESI, for transferring transmembrane peptide complexes directly from lipid bilayers to the gas phase. .
The alkaline-earth zirconates (CaZrO 3 , SrZrO 3 , and BaZrO 3 ) are under active investigation as solid-state electrolytes in hydrogen fuel cells. Their performance as proton conductors depends critically on the properties of acceptor dopants. Here, we use first-principles calculations to study the role of acceptors and point defects in incorporating protons through an oxygen-vacancy-mediated process. For CaZrO 3 , we find that Zr Ca antisites suppress formation of oxygen vacancies. Other intrinsic point defects are shown not to hinder performance. Common unintentional impurities, such as C and N, are not good acceptors but can incorporate in other configurations. Our results show that the effectiveness of common dopants such as Sc and Y is limited by self-compensation due to their incorporation on the "wrong" cation site, where they act as donors. We demonstrate that using alkali metal dopants overcomes this problem, as the formation energy of compensating donors is very high. Alkali metal dopants also have low binding energies for protons, reducing their tendency to act as traps and hence enhancing proton conductivity. As a result, our guidelines for choosing acceptor dopants and optimizing synthesis conditions can greatly improve the efficacy of these proton-conducting oxides as solid-state electrolytes.
Highlights: • Compact anodic titanium oxide (CATO) and anodic TiO{sub 2} nanotubes (ATNTs) were compared. • A distinct transform from CATO films into the porous ATNTs was observed firstly. • FESEM evidences for oxygen bubble mould effect were provided firstly. • Formation mechanisms for different titanium oxide films are confirmed consistent. - Abstract: The formation mechanism of anodic TiO{sub 2} nanotubes (ATNTs) remains mysterious and complicated. Usually, ATNTs are fabricated in pure NH{sub 4}F electrolytes rather than mixed electrolytes and Ti anodizations are carried out under potentiostatic rather than galvanostatic conditions. In this work, anodizations under the potentiostatic and galvanostatic conditions are conducted. The formation processes of titanium oxide film in different mixed electrolytes are explored in detail. By changing the mass ratios of oxalic acid and ammonium fluoride, different kinds of anodic titanium oxide films are fabricated: the compact anodic titanium oxide (CATO) films, transient-state anodic titanium oxide films and porous films (ATNTs). A distinct transform from CATO films into ATNTs was observed. Cavities within oxide and hemispheric bottoms are found, confirming the presence of oxygen bubble mould. Based on the electronic current and ionic current model, a consistent formation mechanism for three kinds of anodic titanium oxide films in mixed electrolytes is proposed.
Abstract Li 10 Ge(PS 6 ) 2 (LGPS) is a highly concentrated solid electrolyte, in which Coulombic repulsion between neighboring cations is hypothesized as the underlying reason for concerted ion hopping, a mechanism common among superionic conductors such as Li 7 La 3 Zr 2 O 12 (LLZO) and Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP). While first principles simulations using molecular dynamics (MD) provide insight into the Li + transport mechanism, historically, there has been a gap in the temperature ranges studied in simulations and experiments. Here, we used a neural network potential trained on density functional theory (DFT) simulations, to run up to 40-nanosecond long MD simulations at DFT-like accuracy to characterize the ion conduction mechanisms across a range of temperatures that includes previous simulations and experimental studies. We have confirmed a Li + sublattice phase transition in LGPS around 400 K, below which the ab -plane diffusivity D a b ∗ is drastically reduced. Concomitant with the sublattice phase transition near 400 K, there is less cation-cation (cross) correlation, as characterized by Haven ratios closer to 1, and the vibrations in the system are more harmonic at lower temperature. Intuitively, at high temperature, the collection of vibrational modes may be sufficient to drive concerted ion hops. However, near room temperature, the vibrational modes available may be insufficient to overcome electrostatic repulsion, thus resulting in less correlated ion motion and comparatively slower ion conduction. Such phenomena of a sublattice phase transition, below which concerted hopping plays a less significant role, may be extended to other highly concentrated solid electrolytes such as LLZO and LATP.
Highlights: • Addition of the LBO glass enhance total ion conductivity up to four orders of magnitude. • Transport of Li{sup +} could be attributed to two media: grains and grain boundaries. • Sintering temperature is the most influential factor affecting the σ{sub tot}. • Melting of the LBO above 700 °C supports the sintering process. - Abstract: The LiTi{sub 2}(PO{sub 4}){sub 3} based composites containing amorphous Li{sub 3}BO{sub 3} were formed and investigated by means of X–ray diffractometry, thermogravimetry, scanning electron microscopy, impedance spectroscopy and density methods. The study shows that when a polycrystalline LiTi{sub 2}(PO{sub 4}){sub 3} material is sintered with Li{sub 3}BO{sub 3} glass, the resultant ceramics exhibit very high total ion conductivity. The maximum conductivity of 1.43 × 10{sup −4} S cm{sup −1} at 30 °C was achieved for the LTP–0.3LBO material sintered at 900 °C compared to 5.15 × 10{sup −8} S cm{sup −1} of the ceramic LiTi{sub 2}(PO{sub 4}){sub 3}.
To develop a new braze to replace the current state-of-the-art Ag-CuO reactive air braze (RAB), two approaches were proposed: 1) development of a new, self-passivating, silver-free braze and 2) development of a CuO-free, silver-based braze. For the first approach, an integrated computational-experimental method was used. Thermo-Calc® was utilized to quickly screen through hundreds of alloy systems to identify candidate braze compositions with the appropriate melting ranges. Material compositions, melting ranges, mechanical properties, oxidation resistance, and wetting characteristics of the candidate alloys were then analyzed experimentally. Substrate surface pre-treatments, active element additions, and novel brazing schemes were also investigated. Unfortunately, the current study failed to identify new silver-free braze compositions suitable for SOFC applications. To help measure the passivation characteristics of surface passivating braze oxide coatings, work was conducted to demonstrate, for the first time, that a variety of disparate and technologically-relevant thermal, mechanical, and electrochemical oxygen-exchange thin film material properties could all be obtained from in situ , current-collector-free wafer curvature measurements. Specifically, temperature or oxygen partial pressure induced changes in the curvature of 230 nm thick (100)-oriented Pr 0.1 Ce 0.9 O 1.95_x (10PCO) films atop 200 mm thick single crystal yttria stabilized zirconia or magnesium oxide substrates were used to measure the biaxial modulus, Young’s modulus, thermal expansion coefficient, thermochemical expansion coefficient, oxygen nonstoichiometry, chemical oxygen surface exchange coefficient, oxygen surface exchange resistance, thermal stress, chemical stress, thermal strain, and chemical strain of the model mixed ionic electronic conducting material 10PCO. The (100)-oriented thin film 10PCO thermal expansion coefficient, thermo-chemical expansion coefficient, oxygen nonstoichiometry, and Young’s modulus (which is essentially constant, at ~200 MPa, over the entire 280–700 °C temperature range in air) measured here were similar to those from other bulk and thin film 10PCO studies. In addition, the measured PCO10 oxygen surface coefficients were in agreement with those reported by other in situ , current collector- free techniques. However, the measured PCO10 oxygen surface exchange coefficients were significantly lower than those obtained from literature studies with large amounts of intentional or inadvertent precious metal surface coverage/contamination (suggesting that uncontaminated (100)-oriented 10PCO may not be a desirable SOFC cathode material). Taken together, this highlighted the advantages of using a sample’s mechanical response, instead of the more traditional electrical response, to probe the electrochemical properties of the ion-exchange materials used in solid oxide fuel cell, solid oxide electrolysis cell, gas-sensing, battery, emission control, water splitting, water purification, and other electrochemically-active devices. For the second approach, a novel silver-nickel brazing method was developed. It was demonstrated that transient porous nickel interlayers, instead of reactive element additions, could be used to promote Ag wetting on yttria stabilized zirconia (YSZ) and produce high-quality YSZ stainless steel (SS) braze joints. Mechanical tests on these reactive-element-free, silver-based SOFC braze joints, both before and after 500 hours of 750°C oxidation in air, showed that the braze and braze interface strength were higher than the underlying YSZ|NiO-YSZ substrate. The microstructural and compositional evolution of SS|Ag-Ni|YSZ braze joints exposed to dual atmosphere (air on one side and 4%H 2 -96%N 2 on the other side) for 300 hours of isothermal 750 °C aging and 300 25°C/min 35-830 °C rapid thermal cycles were compared to a Ag-3CuO braze joint. In contrast to conventional Ag-CuO RAB brazes, the Ag-Ni brazes remained pore free and well bonded, suggesting that Ag-Ni brazes may be more suitable for long term SOFC operation than Ag-CuO brazes. Other applications inspired by the silver-nickel wetting process on various ceramic substrates were also explored. In support of efforts to identify new CuO-free Ag-based brazes, density functional theory and ab initio molecular dynamics calculations were performed to 1) understand silver wetting on YSZ, and 2) identify new oxides to promote silver wetting on YSZ. These simulations found that while the formation of dissolved oxygen clusters within molten silver at the YSZ interface promoted wetting, much greater wetting angle reductions came from the formation of metal oxide interlayers at the Ag-YSZ interface. Through the development of a simple descriptor, many simple metal oxides (single cation) were examined. Unfortunately, their ability to promote Ag wetting were less than that of CuO. However, expanding the search to multi-cation oxides led to several promising candidates, such as CuAlO 2 , CuGaO 2 , and Cu 3 TiO 4 ; all of which are also stable in the reducing SOFC conditions. Depending upon their solubility in molten Ag, these newly-identified oxides could either be pre-applied as wetting promoting interlayers or directly incorporated into Ag to form new reactive air brazes.
We demonstrate an instrument for spatially resolved measurements (mapping) of electrochemical impedance under various temperatures and gas environments. Automated measurements are controlled by a custom LabVIEW program, which manages probe motion, sample motion, temperature ramps, and potentiostat functions. Sample and probe positioning is provided by stepper motors. Dry or hydrated atmospheres (air or nitrogen) are available. The configurable heater reaches temperatures up to 500 °C, although the temperature at the sample surface is moderated by the gas flow rate. The local gas environment is controlled by directing flow toward the sample via a glass enclosure that surrounds the gold wire probe. Software and hardware selection and design are discussed. Reproducibility and accuracy are quantified on a Ba(Zr,Y)O 3-δ proton-conducting electrolyte thin film synthesized by pulsed laser deposition. The mapping feature of the instrument is demonstrated on a compositionally graded array of electrocatalytically active Ba(Co,Fe,Zr,Y)O 3-δ thin film microelectrodes. The resulting data indicate that this method proficiently maps property trends in these materials, thus demonstrating the reliability and usefulness of this method for investigating electrochemically active thin films.
Knowledge of intrinsic properties is of central importance for materials design and assessing suitability for specific applications. Self-assembling block copolymer electrolytes (BCEs) are of great interest for applications in solid-state energy storage devices. A fundamental understanding of ion transport properties, however, is hindered by the difficulty in deconvoluting extrinsic factors, such as defects, from intrinsic factors, such as the presence of interfaces between the domains. Here, we quantify the intrinsic ion transport properties of a model BCE system consisting of poly(styrene-block-ethylene oxide) (SEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt using a generalizable strategy of depositing thin films on interdigitated electrodes and self-assembling fully connected parallel lamellar structures throughout the films. Comparison between conductivity in homopolymer poly(ethylene oxide) (PEO)-LiTFSI electrolytes and the analogous conducting material in SEO over a range of salt concentrations (r, molar ratio of lithium ion to ethylene oxide repeat units) and temperatures reveals that between 20% and 50% of the PEO in SEO is inactive. Using mean-field theory calculations of the domain structure and monomer concentration profiles at domain interfaces-both of which vary substantially with salt concentration-the fraction of inactive PEO in the SEO, as derived from conductivity measurements, can be quantitatively reconciled with the fraction of PEO that is mixed with greater than a few volume percent of polystyrene. Despite the detrimental interfacial effects for ion transport in BCEs, the intrinsic conductivity of the SEO studied here (ca. 10 -3 S/cm at 90 degrees C, r = 0.085) is an order of magnitude higher than reported values from bulk samples of similar molecular weight SEO (ca. 10 -4 S/cm at 90 degrees C, r = 0.085). Finally, this work provides motivation and methods for pursuing improved BCE chemical design, interfacial engineering, and processing.