Solid Electrolyte Thin Films Research Articles

Renewable symmetric supercapacitors assembled with lignin nanoparticles-based thin film electrolyte and carbon aerogel electrodes

Lignin as a natural biopolymer is becoming increasingly in demand due to its eco-friendly properties, while lignin-based electrolyte with high conductivity and reliable durability for applications in supercapacitors is still challenging. Herein, a facile method to prepare lignin nanoparticles (LNPs)-based solid electrolyte thin film (LF) was proposed through chemical cross-linking reaction. The fabricated LF exhibited a distinctive spongy porous structure with the ionic conductivity of 3.26 mS cm−1, demonstrating the exceptional flexibility and favorable mechanical properties. Moreover, the assembly of all-LNPs-based symmetric supercapacitor (SSC) devices was achieved using LF electrolyte and LCA electrodes for the first time, confirming the LF3 electrolyte superior to commercial cellulose separator in capacitive behaviour. This SSC device exhibited a specific capacitance of 122.7 F g−1 at 0.5 A g−1 and the maximum energy density of 17.04 W h kg−1. Furthermore, the incorporation of sodium alginate (SA) significantly enhanced the ionic conductivity of SA/LF3 electrolyte, and the resulting SSC device delivered a higher specific capacitance of 174.5 F g−1 at 0.5 A g−1 and the maximum energy and power densities of 24.24 W h kg−1 and 5023 W kg−1, respectively. This study proposes a promising approach for sustainable utilization of lignin in energy storage applications.

Ionic Conduction-Based Polycrystalline Oxide Gamma Ray Detection - Radiation-Ionic Effects.

Newly discovered opto-ionic effects in metal oxides provide unique opportunities for functional ceramic applications. The authors generalize the recently demonstrated grain boundary opto-ionic effect observed in solid electrolyte thin films under ultraviolet (UV) irradiation to a radiation-ionic effect that can be applied to bulk materials and used for gamma-rays (γ-rays) detection. Near room temperature, lightly doped Gd-doped CeO2, a polycrystalline ion conducting ceramic, exhibits a resistance ratio change ≈103 and reversible response in ionic current when exposed to 60Co γ-ray (1.1 and 1.3 MeV). This is attributed to the steady state passivation of space charge barriers at grain boundaries, that act as virtual electrodes, capturing radiation-induced electrons, in turn lowering space charge barrier heights, and thereby exclusively modulating the ionic carrier flow within the ceramic electrolytes. Such behavior allows significant electrical response under low fields, that is, < 2 V cm-1, paving the way to inexpensive, sensitive, low-power, and miniaturizable solid-state devices, uniquely suited for operating in harsh (high temperature, pressure, and corrosive) environments. This discovery presents opportunities for portable and/or scalable radiation detectors benefiting geothermal drilling, small modular reactors, nuclear security, and waste management.

(Digital Presentation) Fabrication and Characterization of 4Sc4YSZ/LSM-4Sc4YSZ Novel Electrode-Supported Half-Cell Composition for Solid Oxide Electrochemical Cells

Scandium and Yttrium co-doped ZrO2 (4Sc4YSZ) thin film solid electrolyte has exhibited improved conductivities and phase stability by considering advantages of both Y-doped zirconia (YSZ) and Sc-doped zirconia (ScSZ). To further investigate the promising properties of this co-doped composition, a solid electrolyte thin film of 4Sc4YSZ deposited on a new LSM-4Sc4YSZ composite electrode was conducted. In this study, the effect of pre-sintering temperature (1000°C, 1150°C, and 1300°C) of the LSM-4Sc4YSZ electrode substrate in the deposition of a dense solid electrolyte film was studied. X-ray diffraction (XRD) analysis of all the LSM-4Sc4YSZ composite electrodes revealed distinct phases of rhombohedral LSM and cubic 4Sc4YSZ. Also, the thin film electrolytes exhibited cubic 4Sc4YSZ with calculated lattice parameters of a equal to 5.10 Å, 5.10 Å, and 5.09 Å deposited on the electrode substrate pre-sintered at 1000°C, 1150°C, and 1300°C, respectively. The obtained lattice parameters were comparable with the reference LSM (PDF card no. 000-053-0058) and 4Sc4YSZ (PDF card no. 01-080-4524). Morphological characterization via scanning electron microscopy (SEM) showed that the thin film solid electrolyte with LSM-4Sc4YSZ electrode pre-sintered at 1300°C has a relatively dense microstructure than those with lower pre-sintering electrode temperatures. In addition, the thin film deposited on the 1300°C LSM-4Sc4YSZ obtained the lowest average thickness of 12.81 µm as compared to the 1000°C and 1150°C LSM-4Sc4YSZ with thickness values of 38.32 µm and 27.99 µm, respectively. The electrochemical performance of the fabricated half-cell was analyzed using electrochemical impedance spectroscopy (EIS). The total conductivity, as calculated from the EIS results, of 4Sc4YSZ/LSM-4Sc4YSZ half-cell pre-sintered at 1300°C is 0.0726 S/cm at 700°C under oxygen gas flow environment.

Fabrication and Characterization of LiNi1/3Mn1/3Co1/3O2/Li0.6La0.4TiO3/Li4Ti5O12 Full Cell All-Solid-State Thin Film Li-Ion Batteries for Energy Applications

Recent days, natural calamities caused by the global warming and climate changes are major concern for the entire globe and there is a pressing need to address such issues to save the mankind from further havoc and devastation. To reduce the carbon emission, countries are shifting dramatically towards renewable sources for their energy needs for their day-to-day life. Li ion batteries are in the forefront of the battle towards the sustainable growth and development due to their high energy density and renewable in nature. In the present case, we report on development of thin film based all-solid-state batteries (ASSB) for energy applications. LiNi1/3Mn1/3Co1/3O2 (NMC), Li0.6La0.4TiO3 (LLTO) and Li4Ti5O12 (LTO) materials are employed as a cathode, solid electrolyte and anode layers for fabricating a full cell all-solid-state thin film batteries. All the layers are fabricated employing RF sputtering technique. Before fabricating the full cell, individual layers are fabricated and their electrochemical and/or ionic conductivity properties are explored. Li0.6La0.4TiO3 solid electrolyte thin films are seen to exhibit room temperature in-plane ionic conductivity in the order of 10-3 S/cm. NMC thin film with the thickness of 100 nm exhibits specific capacity of 91 µAh/cm2 and the redox peaks at 3.8 V and 3.5 V. LTO anode thin films shows the specific capacity close to 100 mAh/cm2and the redox peaks around 1.5 V. XRD pattern of NMC/LLTO/LTO full cell shows the diffraction peaks corresponding to all the three layers. Cross-sectional scanning electron microscope (SEM) image indicates the uniform coating and presence of all the layers. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) along with the energy dispersive X-ray is employed to image the cross-sectional details and the elements present in each layer of the full cell all-solid-state thin film battery. Impedance spectroscopy was employed to calculate the total conductivity of the fabricated full cell. Obtained results indicates that the full cell NMC/LLTO/LTO thin film batteries can be fabricated employing a sputtering technique for the energy applications. Figure 1

Highly Conducting Sc and Y co-doped Zirconia Solid Electrolyte Thin Films Prepared via Pulsed Laser Deposition for Solid Oxide Electrochemical Cells Applications

Scandium (Sc) and yttrium (Y) co-doped ZrO2 thin films were fabricated via pulsed laser deposition (PLD). The target material, 4 mol% Sc2O3 and 4 mol% Y2O3 co-doped ZrO2 (ScYSZ), was first synthesized via a solid-state reaction. The ScYSZ thin film was deposited on SiO2-Si substrate by laser ablation, using a Q-switched Nd3+:YAG laser (λ = 266 nm) and substrate temperatures of 600 and 800 oC. Micro-structural and conductivity properties of the resulting as-deposited thin films were investigated. X-ray diffraction (XRD) sample patterns revealed that the as-deposited polycrystalline films can be indexed to a cubic structure. In addition, varying the oxygen partial pressures during the deposition was studied. FE-SEM images revealed dense and crack-free surface morphologies achieved at lower oxygen partial pressures (0.01 Pa and 0.1 Pa) and rough surface with porous morphology at high oxygen partial pressures (1.0 Pa and 10 Pa). The thickness of the film is about 120 nm for the thin film deposited at 800 oC substrate temperature (TS). The total conductivity of the thin film was measured using electrochemical impedance spectroscopy (EIS). Interestingly, the calculated total conductivity of the deposited ScYSZ thin film, 0.1 Pa and TS at 800 oC, revealed about 2.8x10-1 S/cmat 700 oC and with activation energy (Ea) of 0.78 eV from 500 oC to 700 oC. The fabricated as-deposited ScYSZ thin film is one of the highest reported highly conducting solid electrolytes that is a promising material for fuel cell or electrolysis cell applications.

(Invited) Nanostructured Solid State Battery Architectures Enabled by Atomic Layer Deposition

Solid state batteries (SSBs) are considered the most promising next-generation energy storage technology both due to their increased safety over conventional wet Li-ion cells and their ability to fabricate novel architectures with simultaneous high energy and power density. However, the ionic conductivities of many solid electrolyte materials are orders of magnitude lower than liquid carbonate-based electrolytes. In order to offer SSBs with competitive charge/discharge rates, SSB active layers need to be thin (for fast ion diffusion) but have a large surface area (to enable large ion flux from anode to cathode). These geometric constraints establish the need for 3D electrode (and solid electrolyte) structures for a high performance battery architecture. Atomic layer deposition (ALD) is ideally suited to fabricate such devices due to its highly conformal nature and Angstrom-scale thickness control, however many challenges remain with materials fabrication and process integration.I will discuss development of both plasma-enhanced ALD (PEALD) and thermal ALD processes for the Li, Na, and K alkali polyphosphazene (A*PON) electrolytes1,2,3,4. The PEALD A*PON processes, by virtue of their 4-precursor synthesis route, allow some degree of chemical composition tuning. The thermal A*PON processes, unlike their PEALD counterparts, have a predetermined P-N ratio fixed by use of the precursors, however there is a tradeoff between the low temperature deposition enabled using plasma-based A*PON processes, and the conformality offered using the thermal A*PON processes. I will discuss and compare the reaction mechanisms and growth behavior among the entire family of A*PON solid electrolyte thin films, as well as discuss the integration challenges on the path to developing all-ALD planar and 3D SSBs. Pearse, A.; Schmitt, T.; Sahadeo, E.; Stewart, D. M.; Kozen, A.; Gerasopoulos, K.; Talin, A. A.; Lee, S. B.; Rubloff, G. W.; Gregorczyk, K. E., Three-Dimensional Solid-State Lithium-Ion Batteries Fabricated by Conformal Vapor-Phase Chemistry. ACS Nano 2018, 12 (5), 4286-4294. Pearse, A. J.; Schmitt, T. E.; Fuller, E. J.; El-Gabaly, F.; Lin, C.-F.; Gerasopoulos, K.; Kozen, A. C.; Talin, A. A.; Rubloff, G.; Gregorczyk, K. E., Nanoscale Solid State Batteries Enabled by Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte. Chemistry of Materials 2017, 29 (8), 3740-3753. Nuwayhid, R. B.; Jarry, A.; Rubloff, G. W.; Gregorczyk, K. E., Atomic Layer Deposition of Sodium Phosphorus Oxynitride: A Conformal Solid-State Sodium-Ion Conductor. ACS Applied Materials & Interfaces 2020, 12 (19), 21641-21650. Kozen, A. C.; Pearse, A. J.; Lin, C-F.; Noked, M.; Rubloff, G. W.; Atomic Layer Deposition of the Solid Electrolyte LiPON. Chemistry of Materials 2015, 27 (15), 5324-5331.

Influence of Au, Pt, and C Seed Layers on Lithium Nucleation Dynamics for Anode-Free Solid-State Batteries.

In the concept of anode-free lithium-ion batteries, cells are manufactured with a bare anode current collector where the lithium metal anode is electrochemically formed from the lithium-containing cathode during the first charge cycle. While this concept has many attractive aspects from a manufacturing and energy density standpoint, stable plating and stripping remain challenging. We have investigated gold, platinum, and amorphous carbon as seed layers placed between the copper current collector and the lithium phosphorus oxynitride thin-film solid electrolyte. These layers guide lithium nucleation and improve the plating and stripping dynamics. All seed layers facilitate reversible lithium plating and stripping even at high current densities up to 8 mA cm-2. Of particular note is the amorphous carbon seed layer, which allowed a significant reduction in plating potential from 300 mV to as low as 50 mV. These results underscore the critical role of seed layers in improving the efficiency of anode-free solid-state batteries and open the door to simplified manufacturing of anode-free battery designs.

Features of forming a low-temperature cubic Li7La3Zr2O12 film by tape casting

Currently, interest to lithium and lithium-ion all-solid-state power sources is rapidly growing all over the world. However, several issues should be addressed before all-solid-state batteries production: high resistance values of the solid electrolyte membrane and poor contact between electrolyte and electrode materials. The transition to thin-film technologies is one of the promising ways to solve these problems. Tape casting can be proposed to obtain thin-film solid electrolytes. In this research, the features of the structure formation, morphology and lithium-ion conductivity of Li7La3Zr2O12 films were investigated. Li7La3Zr2O12 films with the thickness of 35 µm were obtained by tape casting on Ni substrate. The influence of organic components’ content on homogeneous coatings formation was established. Heat treatment conditions for dried films were chosen based on differential scanning calorimetry and optical dilatometry. Phase change from tetragonal to low-temperature cubic modification occurs after annealing the Li7La3Zr2O12 films at 700 °C and higher. The annealed Li7La3Zr2O12 films have developed surface, which can lead to improved contact between the solid electrolyte and an electrode in an electrochemical cell. Li7La3Zr2O12 films annealed at 800 °C have the highest lithium-ion conductivity values (2.5·10–7 and 1.5·10–5 S·cm–1 at 90 and 215 °С, respectively). The technology of Li7La3Zr2O12 films formation with the thickness of ~23 µm by tape casting was developed.

(Digital Presentation) Fabrication and Characterization of 4Sc4YSZ/LSM-4Sc4YSZ Novel Electrode-Supported Half-Cell Composition for Solid Oxide Electrochemical Cells

Scandium and Yttrium co-doped ZrO2 (4Sc4YSZ) thin film solid electrolyte has exhibited improved conductivities and phase stability by considering advantages of both Y-doped zirconia (YSZ) and Sc-doped zirconia (ScSZ). In this study, a solid electrolyte thin film of 4Sc4YSZ deposited on a new LSM-4Sc4YSZ composite electrode was conducted. To obtain a dense electrolyte, the effect of pre-sintering temperature of the LSM-4Sc4YSZ electrode substrate in the deposition of the 4Sc4YSZ thin film was investigated. X-ray diffraction (XRD) analysis revealed distinct phases of rhombohedral peaks for LSM and cubic peaks for the composite 4Sc4YSZ component and deposited thin film electrolytes. It was observed from the morphological results via scanning electron microscopy (SEM) that pre-sintering of the electrode substrate affects the densification of the deposited solid electrolyte. A dense 4Sc4YSZ thin film electrolyte was obtained by pre-sintering the LSM-4Sc4YSZ electrode at 1300°C than those deposited on the substrates with lower pre-sintering temperatures.

Highly Conducting Sc and Y co-doped Zirconia Solid Electrolyte Thin Films Prepared via Pulsed Laser Deposition for Solid Oxide Electrochemical Cells Applications

Scandia and yttria-stabilized zirconia (ScYSZ) have been widely used as electrolyte materials for solid oxide electrochemical cells (SOEC) applications due to its high ionic conductivity and stable mechanical and thermal properties. In this study, ScYSZ thin films were fabricated via pulsed laser deposition (PLD) method at substrate deposition temperature (Ts ) of 800 °C with varying oxygen oxygen partial pressures (). The as-deposited ScYSZ thin films were characterized using X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and electrochemical impedance spectroscopy (EIS). XRD analysis revealed that all fabricated films, even with varying , have a polycrystalline cubic-fluorite structure. Morphological FESEM images revealed a good-quality dense ScYSZ electrolyte thin film with no visible cracks. Notably, a high total conductivity thin film of about 2.8x10-1 S/cm at 700 °C and low activation energy (Ea ) of 0.78 eV, from 500°Cto 700 °C, were achieved. Interestingly, the PLD-prepared ScYSZ dense solid electrolyte showed a higher total conductivity than the reported conductivities of zirconia-based solid oxide electrolytes.

In-Situ Thermo-Mechanical Characterization and Strain Engineering of Lipon Thin Films

High temperature multi-optical-stress sensor (HTMOSS) has been used to characterize the coefficient of thermal expansion (CTE) and yield stress of 1-micron thick LiPON films. Six fully dense, amorphous films were deposited on glass and sapphire substrates. The films were then annealed at temperatures ranging from 80 to 200 C for 3 hours. The CTE of LiPON is found to be approximately 4.1e-6, and argued to be independent of the substrate type. Because of this intermediate CTE value, by varying the substrate, we could impose either tension and compression due to thermal mismatch to the film. We observed further that the yield stress of the film is approximately 60 MPa under compression and 100 MPa under tension. Using constant-load hold at and beyond yield point, the films were found to relieve the stress developed during heating with visco-plastic deformation, which led to permanent residual stress during cooling as high as 120 MPa in either tension or compression depending on substrate type. We also found that at annealing temperature higher than 140 C LiPON lost ductility which could be due to composition changes as indicated by XPS measurement. The stress-relief mechanism at constant-load indicates that LiPON may be beneficial as a protective layer against dendrites penetration. Moreover our experimental platform proves that it's an effective method to engineer strain into thin-film solid electrolytes that could be extended to other materials like LLZO or sulfide electrolyte.

Low temperature preparation of YSZ-based thin-film limiting current type oxygen sensor

Oxygen sensors based on YSZ solid electrolyte thin films have great application prospects due to their advantages in miniaturization and integration. Here, we report the gas sensing performance of Pt/YSZ/Pt oxygen gas sensors with low preparing temperatures. YSZ thin films with (200) preferred orientation have been prepared by room temperature RF magnetron sputtering combined with annealing at a temperature of 650 °C. The 700 nm-thick YSZ films exhibit an obvious limiting current platform, and the limiting current IL shows a linear dependence on oxygen concentration X(O2) (in the range of 6%–21%). Moreover, the devices with 700 nm-thick YSZ films worked well at the temperature range from 500 to 650 °C, and a linear relationship between logIL and 1000/T has been observed. These results demonstrate that YSZ thin films prepared by low temperature magnetron sputtering combined with the annealing process can reduce the working temperature.

A micro room temperature oxygen sensor based on LaF3 solid electrolyte thin film

PurposeDetecting O2 gas in a confined space at room temperature is particularly important to monitor the work process of precision equipment. This study aims to propose a miniaturized, low-cost, mass-scale produced O2 sensor operating around 30°C.Design/methodology/approachThe O2 sensor based on lanthanum fluoride (LaF3) solid electrolyte thin film was developed using MEMS technology. The principle of the sensor was a galvanic cell H2O, O2, Pt | LaF3 | Sn, SnF2 |, in which the Sn film was prepared by magnetron sputtering, and the LaF3 film was prepared by thermal resistance evaporation.FindingsThrough pretreatments, the sensor’s response signal to 40% oxygen concentration was enhanced from 1.9 mV to 46.0 mV at 30°C and 97.0% RH. Tests at temperatures from 30°C to 50°C and humidity from 32.4% RH to 97.0% RH indicated that the output electromotive force (EMF) has a linear relationship with the logarithm of the oxygen concentration. The sensitivity of the sensor increases with an increase in both humidity and temperature in the couple mode, and the EMF of the sensor follows well with the Nernst equation at different temperatures and humidity.Practical implicationsThis research could be applied to monitor the oxygen concentration below 25% in confined spaces at room temperature safely without a power supply.Originality/valueThe relationship between temperature and humidity coupling and the response of the sensor was obtained. The nano-film material was integrated with the MEMS process. It is expected to be practically applied in the future.

Electrical, transport, and optical properties of a novel PVB-NaNO3 complexed solid polymer electrolyte thin-films for solid-state battery

The thin films of solid polymer electrolyte were made using Polyvinyl Butyral (PVB), and Sodium Nitrate (NaNO3) of different compositions, using Methanol as a solvent, by ‘solution casting technique. Then, this Polymer electrolyte thin films were checked using different characterization techniques like UV–visible spectroscopy, FTIR, XRD, and DC conductivity studies. The electrolyte sample with 30 wt% of NaNO3 showed maximum conductivity of 1.52x10-11 S cm−1 at 338 K and 4.01x10-8 Scm−1 at 393 K. The Cole-Cole graphs of AC conductivity were plotted using the impedance spectroscopy data, for PVB70%: NaNO330% concentration which showed the conductivity of 7.07x10-10 Scm−1 at 333 K and 6.54x10-7Scm−1 at 393 K. Using Wagner’s polarization technology, the carriers which led to the conduction of charge transport in the electrolyte films were found. It was identified that the ions were predominantly the charge transport carriers. The absorption spectra for the samples were calculated using a UV Spectrometer in the wavelength range of 250–900 nm. In Pure PVB polymer, the optical absorption is very less and this increases gradually when the salt NaNO3 concentration is increased. For the combination of PVB 70%: NaNO3 30% concentration, maximum absorption is seen at the wavelength 530 nm. For the same combination, there was a minimum absorption edge and it shifts towards the maximum energy above this concentration. The photon energy range lies between 2.4 eV and 1.6 eV, which shows that the band gap of the doped samples decreases.

Sulfide solid electrolyte thin film with high ionic conductive from slurry-casting strategy for all-solid-state lithium batteries

Sulfide solid electrolyte thin film with high ionic conductive from slurry-casting strategy for all-solid-state lithium batteries

Lithium-preserved sintering method for perovskite-based solid electrolyte thin films via flash light sintering for all-solid-state lithium-ion batteries

A novel rapid sintering method, namely flash-light sintering, was applied as a post-treatment for spin-coated lithium lanthanum titanate thin films to prevent lithium evaporation and obtain fully dense thin films with perovskite structures.

Amorphous Solid Electrolyte Thin Film and Its Battery Application

Amorphous Solid Electrolyte Thin Film and Its Battery Application

A Three-Dimensionally Interconnected Composite Polymer Electrolyte for Solid-State Batteries

High energy density of solid-state batteries requires a thin solid electrolyte separator layer (<30 μm), that can sustain high currents and is easily processable. Polymer-ceramic composite electrolytes can potentially fulfill these requirements by combining the advantages of each type. Ceramic electrolytes have high room-temperature ionic conductivity, transference number of one, and mechanical strength to suppress lithium dendrites, whereas polymer electrolytes are easily processable and can form conformable interfaces with the electrodes. High interfacial-impedance between polymer and ceramic electrolytes make the composites with dispersed ceramic particles less attractive.1 A composite electrolyte architecture where a three-dimensionally interconnected porous ceramic is filled with polymer electrolyte, previously reported by our group, can avoid the interfacial impedance issue, although for thin composite membranes, the interfacial impedance between ceramic framework and excess polymer layer on top/bottom surface will still dominate the overall impedance.2 Here we will present fabrication and electrochemical evaluation of ~150 μm thick composite electrolytes with the above-described 3D-interconnected ceramic architecture. The 3-D framework is obtained by partially sintering Ohara ceramic particle tapes obtained via tape casting, which are filled with curable polymer electrolyte precursors. To obtain a thin (5 μm), uniform polymer electrolyte layer on both surfaces, spray coating was employed. The resulting composite membrane exhibited good dendritic resistance in symmetric cell cycling, improved transference number compared to the polymer electrolytes. We also found significantly improved flexibility of the composite electrolytes with plasticization, however, at the cost of reduction in ionic conductivity due to damage to the ceramic network caused by plasticizer-induced swelling of the cross-linked polymer electrolyte. This research was sponsored by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy for the Vehicle Technologies Office’s Advanced Battery Materials Research Program (Tien Duong, Program Manager). This abstract has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). References Chen, X. C.; Liu, X.; Samuthira Pandian, A.; Lou, K.; Delnick, F. M.; Dudney, N. J., Determining and Minimizing Resistance for Ion Transport at the Polymer/Ceramic Electrolyte Interface. ACS Energy Letters 2019, 4 (5), 1080-1085.Palmer, M. J.; Kalnaus, S.; Dixit, M. B.; Westover, A. S.; Hatzell, K. B.; Dudney, N. J.; Chen, X. C., A three-dimensional interconnected polymer/ceramic composite as a thin film solid electrolyte. Energy Storage Materials 2020, 26, 242-249.

Monolithic All-Solid-State High-Voltage Li-Metal Thin-Film Rechargeable Battery.

The substitution of an organic liquid electrolyte with lithium-conducting solid materials is a promising approach to overcome the limitations associated with conventional lithium-ion batteries. These constraints include a reduced electrochemical stability window, high toxicity, flammability, and the formation of lithium dendrites. In this way, all-solid-state batteries present themselves as ideal candidates for improving energy density, environmental friendliness, and safety. In particular, all-solid-state configurations allow the introduction of compact, lightweight, high-energy-density batteries, suitable for low-power applications, known as thin-film batteries. Moreover, solid electrolytes typically offer wide electrochemical stability windows, enabling the integration of high-voltage cathodes and permitting the fabrication of higher-energy-density batteries. A high-voltage, all-solid-state lithium-ion thin-film battery composed of LiNi0.5Mn1.5O4 cathode, a LiPON solid electrolyte, and a lithium metal anode has been deposited layer by layer on low-cost stainless-steel current collector substrates. The structural and electrochemical properties of each electroactive component of the battery had been analyzed separately prior to the full cell implementation. In addition to a study of the internal solid–solid interface, comparing them was done with two similar cells assembled using conventional lithium foil, one with thin-film solid electrolyte and another one with thin-film solid electrolyte plus a droplet of LP30 liquid electrolyte. The thin-film all-solid state cell developed in this work delivered 80.5 mAh g–1 in the first cycle at C/20 and after a C-rate test of 25 cycles at C/10, C/5, C/2, and 1C and stabilized its capacity at around 70 mAh g–1 for another 12 cycles prior to the start of its degradation. This cell reached gravimetric and volumetric energy densities of 333 Wh kg–1 and 1,212 Wh l–1, respectively. Overall, this cell showed a better performance than its counterparts assembled with Li foil, highlighting the importance of the battery interface control.

Effects of Oxygen Partial Pressure and Substrate Temperature on the Structure and Morphology of Sc and Y Co-Doped ZrO2 Solid Electrolyte Thin Films Prepared via Pulsed Laser Deposition.

Scandium (Sc) and yttrium (Y) co-doped ZrO2 (ScYSZ) thin films were prepared on a SiO2-Si substrate via pulsed laser deposition (PLD) method. In order to obtain good quality thin films with the desired microstructure, various oxygen partial pressures ( from 0.01 Pa to 10 Pa and substrate temperatures (Ts) from 25 °C to 800 °C were investigated. X-ray diffraction (XRD) patterns results showed that amorphous ScYSZ thin films were formed at room substrate temperature while cubic polycrystalline thin films were obtained at higher substrate temperatures (Ts = 200 °C, 400 °C, 600 °C, 800 °C). Raman spectra revealed a distinct Raman shift at around 600 cm−1 supporting a cubic phase. However, a transition from cubic to tetragonal phase can be observed with increasing oxygen partial pressure. Photoemission spectroscopy (PES) spectra suggested supporting analysis that more oxygen vacancies in the lattice can be observed for samples deposited at lower oxygen partial pressures resulting in a cubic structure with higher dopant cation binding energies as compared to the tetragonal structure observed at higher oxygen partial pressure. On the other hand, dense morphologies can be obtained at lower (0.01 Pa and 0.1 Pa) while more porous morphologies can be obtained at higher (1.0 Pa and 10 Pa).