Thin Film Electrolyte Research Articles

Na3Zr2Si2PO12-Polymer Composite Electrolyte for Solid State Sodium Batteries.

The integration of the flexibility of organic polymer electrolyte and high ionic conductivity of the ceramic electrolyte is attempted in search of efficient and safer battery. Composite solid polymer electrolyte (CSPE) provides high ionic conductivity with a sustainable thin film of electrolyte having the synergistic effect of ionic liquid and active inorganic filler. The CSPE is synthesized by the solution cast technique using Na3Zr2Si2PO12 (NZSP) as ceramic and poly(vinylidene fluoride-hexafluoropropylene) with Salt-Ionic liquid as polymer electrolyte. X-ray diffraction (XRD) of CSPE includes amorphous nature due to the polymer part as well as crystalline peaks of ceramic NZSP, simultaneously. The prepared CSPE sample shows homogeneous and interconnected surface morphology is observed by Scanning electron microscopy (SEM) image. Thermogravimetric analysis (TGA) shows electrolyte is thermally stable up to 200 °C and differential scanning calorimetry (DSC) reveals decrease in degree of crystallinity due to NZSP addition in the CSPE. By complex impedance spectroscopy (CIS), room temperature ionic conductivity of the prepared CSPE is found ~1.03 mS/cm. The dielectric behaviour of the prepared electrolyte is also studied to investigate the ion dynamics within the sample. The cationic transference number is 0.53 and the electrochemical stability window (ESW) of the CSPE is 4.9 V which is suitable for sodium solid-state batteries applications.

Slurry Casted Ultrathin Li3Zr2Si2PO12 Electrolyte Film for Solid-State Lithium Metal Batteries.

Thin and flexible solid-state electrolyte (SSE) films with high ionic conductivity and low interfacial resistance are urgently required for lithium metal batteries (LMBs). However, it's still challenging to reduce the film thickness to <20µm, especially for those with high ceramic contents. Herein, a facile slurry casting method is developed to prepare the ultra-thin (14µm) Li3Zr2Si2PO12 (LZSP) films with ceramic content up to 91% using a composite polymer binder, polyvinylidene fluoride (PVDF), and polyethylene oxide (PEO). It shows that PEO not only enhanced the film flexibility but also makes it be easily peeled off to form a freestanding membrane, PLN. To promote the interfacial ion transport, PEO/lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) is introduced to the film surface, and the resultant tri-layer film, PPLN, shows a satisfying room temperature ionic conductivity of 0.116mScm-1, high Li+ transference number of 0.79, and good compatibility with metal lithium. As a result, LMBs using LiFePO4 cathode and PPLN electrolyte exhibit excellent safety as well as electrochemical performances in the wide temperature range between room temperature (RT) and 100°C.

Interfacial Modification for High-Efficient Reversible Protonic Ceramic Cell with a Spin-Coated BaZr0.1Ce0.7Y0.2O3-δ Electrolyte Thin Film.

Slurry spin coating is an effective approach for the fabrication of protonic ceramic electrolyte thin films. However, weak adhesion between the electrode and spin-coated electrolyte layers in electrochemical cells due to the low sinterability of the proton-conducting perovskite materials usually lead to a high interfacial resistance and thus a low performance. Herein, we report a method to improve the interfacial connection and boost the performance of protonic ceramic cells based on a BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte. Ni-BZCY anode functional layer, BZCY electrolyte layer and La0.6Sr0.4Co0.2Fe0.8O3-δ-BZCY cathode functional layer are all fabricated by slurry spin coating. The electrode functional layers and the components of the electrolyte slurry influence the microstructure of the single cell and the kinetics of the electrochemical processes significantly. A peak power density of 2345 mW cm-2 is achieved at 700 °C in the fuel cell mode, and a current density of -3.0 A cm-2 is obtained at an applied voltage of 1.3 V in the electrolysis mode.

(Invited) Streamlined Production of Protonic Ceramic Electrochemical Cells Via Ultrasonic Spray Coating

Thin solid oxide films are crucial for developing high-performance solid oxide-based electrochemical devices aimed at decarbonizing the global energy system. This presentation introduces ultrasonic spray coating technique (USC) for producing <10 µm thin electrolyte films, as well as uniform 4×4 cm2 oxygen electrode films, with a systematic process optimization considering solid loading rates, spray passes, and annealing temperature etc. Notably, the integrated approach highlights the versatility of USC in addressing both oxygen electrode and electrolyte fabrication challenges. The resulting protonic ceramic electrochemical cells, fabricated with these optimized parameters, exhibit remarkable electrochemical performance, structural integrity, and stability in both fuel cell and electrolysis modes. This presentation provides a holistic perspective on scalable production techniques, showcasing the potential of ultrasonic spray coating for advancing large-sized solid oxide electrochemical cells.

Thin Film Based Membrane Electrode Assemblies for Solid-State Ammonia Synthesis

Ammonia is the of the most crucial chemicals and currently primarily produced through the Haber-Bosch process causing the industrial ammonia production to emit more CO2 than any other chemical-making reaction. While the current primary function of ammonia lies within the fertilizer production, it can also be directly used as a fuel for power generation or in the maritime industry. Compared to hydrogen, ammonia has superior storage and transportation capabilities due to its greater volumetric energy density and mild conditions for liquefication. Given the need of reducing global carbon emissions, ammonia could be synthesized electrochemically using air, water and electricity by the Solid-State Ammonia Synthesis (SSAS). Protonic ceramic cells operate within an intermediate temperature regime of around 450 - 550 °C which is well suited for this process. Within our work, we present a tubular membrane electrode unit entirely made of ceramic components based on a barium zirconate thin film electrolyte. An ammonia production rate of 9.06 × 10-10 mol s-1 cm-2 and a Faradaicefficiency of 6.58% were achieved using a NiO-BaZr0.7Ce0.2Y0.1O3- δ | BaZr0.8Y0.2O3- δ | Ru@Ba0.5Sr0.5TiO3-δ cell.A key innovation lies in the production of dense BaZr0.8Y0.2O3-δ electrolyte layers, ranging from 1 to 5 µm in thickness, utilizing a Closed-Field Unbalanced Magnetron Sputtering (CFUMS) process. This technique allows precise adjustments of stoichiometric ratios within the perovskite structure, offering improved sputtering yields compared to conventional methods. Furthermore, the crystallinity, phase purity, and microstructure of sputter-deposited thin films are enhanced through selective laser annealing (SLA), resulting in high-density films composed of single-phase BaZr0.8Y0.2O3-δ with average crystallite sizes of 200 nm while avoiding substrate damage from thermal stress. Electrochemical performance was evaluated through impedance spectroscopy, half-cell tests and full cell tests providing insights into the efficacy of the developed tubular membrane reactor for the electrochemical synthesis of ammonia. The results demonstrate the feasibility of utilizing ceramic proton conductors in SSAS, particularly highlighting the potential of high-pressure operation up to 80 bars in tubular cells at relatively low temperatures around 450 °C, thereby achieving attractive NH3 production rates.This research contributes to the evolving landscape of sustainable ammonia synthesis by presenting a novel approach that integrates advanced materials and manufacturing techniques. Electrification and decentralization of the ammonia supply chain will expand the market by supporting its current use as fertilizer source and enable a new route as green energy carrier paving the way for an ammonia-based economy. Figure 1

Study on the Performance and Mechanism of Morpholine Salt Volatile Corrosion Inhibitors on Carbon Steel

A series of morpholine salt volatile corrosion inhibitors (VCIs) were synthesized via solid-phase chemical reactions. The corrosion inhibition performance was assessed using evaporation weight loss, VCI capability, and corrosion weight loss tests. The corrosion inhibition mechanisms of the morpholine salt VCIs for carbon steel in atmospheric conditions were explored through electrochemical testing under thin film electrolytes, X-ray photoelectron spectroscopy (XPS), and computational simulations. Morpholine carbonate exhibited higher volatility. Corrosion weight loss tests showed an &gt;85% reduction for steel treated with morpholine benzoate or morpholine carbonate. The inhibitors’ inhibition mechanism, elucidated through X-ray photoelectron spectroscopy (XPS) and computational simulations, revealed that morpholine carbonate and benzoate form protective layers via physical and chemical adsorption on the steel surface, coordinating with iron atoms through nitrogen and oxygen atoms. Quantum chemical calculations demonstrated that morpholine carbonate had stronger adsorption energy and electron transfer capabilities, indicating superior corrosion inhibition performance over morpholine benzoate.

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.

Improved Reversibility of Thin-Film Solid Oxide Cells at 500 °C by Tailoring Sputtering Processes for Depositing Yttria-Stabilized Zirconia Electrolyte.

The present study investigates the impact of sputtering configurations on the microstructure and crystallinity of thin-film yttria-stabilized zirconia electrolytes for anodized aluminum oxide-supported all-sputtered thin-film reversible solid oxide cells. Employing various sputtering parameters, such as target-substrate distance and substrate rotation speed, the present study reveals distinct surface characteristics and crystalline structures of thin-film yttria-stabilized zirconia. The microstructure analysis includes scanning electron microscopy and atomic force microscopy examinations, uncovering the influence of the process parameters on the surface morphology, roughness, and grain size. X-ray diffraction data illustrate the texture preferences and crystallite characteristics. The electrochemical characterization of the reversible solid oxide cells demonstrates that the optimized sputtering configuration significantly outperforms the others in both SOFC and SOEC modes, showing exceptional current densities of 964 mA/cm2 at 1.3 V in electrolysis mode at 500 °C. Electrochemical impedance spectroscopy further reveals improved charge transfer reactions at the interface of the electrolyte. The enhanced electrochemical performance is attributed to the unique microstructure and crystallinity of the thin film of yttria-stabilized zirconia. The record-breaking electrolysis performance of this work at 500 °C underscores the potential of tailored sputtering parameters in optimizing the reversible solid oxide cell performance.

A computational framework for probabilistic modeling of galvanic corrosion for automotive applications

Abstract To address the need for reduced vehicle weight and improved environmental sustainability, the automotive industry has increasingly turned to mixing lightweight materials and alloys with metal alloys. However, this integration of dissimilar materials has heightened the risk of galvanic corrosion. This study addresses the gap in modeling of galvanic corrosion under dynamic thin film electrolyte by incorporating data derived from real-world weather conditions and finite element simulations. The presented model successfully captures the trend of galvanic corrosion rate for a given atmospheric environmental condition. The model predictions are compared with experimental data in the literature. Good agreements are observed. The model is further used for prediction of galvanic corrosion of two identical vehicles located in two different geographic locations (i.e., Miami Beach in Florida and Wendover in Nevada) in the year 2021 leveraging weather station data. Additionally, a Bayesian estimation method is used to account for uncertainties in the model parameters and estimation of the probability of failure.

Effect of hBN on Response Times of PEO-Based Electrochromic Devices

In this study, all solid state electrochromic devices (ECDs) without plasticizer such as propylene carbonate were fabricated by sol-gel spin coating method. WO3 nanoparticles and PEO based polymer electrolyte solutions with hBN and without hBN nanoparticles were prepared. These solutions were sol-gel spin- and dip-coated on ITO-glass, respectively. For determining the effect of hBN nanoparticles, four configuration of ECDs were fabricated. The fast bleaching and coloring times of fabricated ECDs were obtained with hBN nanoparticles in WO3 and PEO based polymer electrolyte thin films as 1.15 seconds. Glass/ITO/hBN-WO3/hBN-PEO-based-polymer electrolyte/ITO/Glass electrochromic device is turned on and off 60 times. After 60 cycle, the device coloring time changed to 2-3 seconds, bleaching times changed to 30 seconds.

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.

Asymmetric transition of electrical resistance in an all-solid-state redox device with Fe3O4 and Li-ion electrolyte thin films for physical reservoir computing

In recent years, ion-gating devices have been used in artificial neuromorphic computing and achieved high performance for time-series data processing. However, the origin of this performance still needs to be clarified. In this study, we fabricated an all-solid-state redox device with functional material Fe3O4 and Li-ion conducting solid electrolytes, and the transient response of the electrical resistance of the Fe3O4 thin film to time-series data input was investigated. The transition between high and low electrical resistance states was asymmetric, and residual Li-ion in the thin film led to a hysteresis effect. These unique features, which are induced by ion-electron dynamics coupling, contributes to the high performance of physical reservoir computing utilizing an ion-gating device.

Converting a Commercial Separator into a Thin‐film Multi‐Layer Hybrid Solid Electrolyte for Li Metal Batteries

AbstractTo address the manifold challenges solid electrolytes (SE) do face in NMC‖Lithium metal batteries, we demonstrate that these can be overcome by converting a commercial Celgard 2500 separator into a jack of all trades hybrid solid electrolyte (HSE). This approach follows a multi‐layer electrolyte strategy, to better cope with the very different chemistries of the cathode, the bulk electrolyte material, and the Li metal anode. A cathode‐facing electrolyte layer based on lithium aluminum titanium phosphate (LATP) provides a high voltage stability of ≥4.5 V. High mechanical strength of the overall thin film electrolyte (≤50 μm) is achieved with a middle layer based on Celgard 2500. The layer on the anode side, based on polyethylene oxide (PEO), allows stable cycling of the lithium metal. High Coulombic efficiencies in NMC622‖Li metal cells (99.9 %) and LFP‖Li metal cells (99.9 %) enable long term cycling with high‐capacity retention of 46 % and 52 % after 1,000 cycles, respectively.

Electrochemical Synthesis of Ammonia via Nitrogen Reduction and Oxygen Evolution Reactions—A Comprehensive Review on Electrolyte-Supported Cells

The application of protonic ceramic electrolysis cells (PCECs) for ammonia (NH3) synthesis has been evaluated over the past 14 years. While nitrogen (N2) is the conventional fuel on the cathode side, various fuels such as methane (CH4), hydrogen (H2), and steam (H2O) have been investigated for the oxygen evolution reaction (OER) on the anode side. Because H2 is predominantly produced through CO2-emitting methane reforming, H2O has been the conventional carbon-free option thus far. Although the potential of utilizing H2O and N2 as fuels is considerable, studies exploring this specific combination remain limited. PCEC fabrication technologies are being developed extensively, thus necessitating a comprehensive review. Several strategies for electrode fabrication, deposition, and electrolyte design are discussed herein. The progress in electrode development for PCECs has also been delineated. Finally, the existing challenges and prospective outlook of PCEC for NH3 synthesis are analyzed and discussed. The most significant finding is the lack of past research involving PCEC with H2O and N2 as fuel configurations and the diversity of nitrogen reduction reaction catalysts. This review indicates that the maximum NH3 synthesis rate is 14 × 10−9 mol cm−2 s−1, and the maximum current density for the OER catalyst is 1.241 A cm−2. Moreover, the pellet electrolyte thickness must be maintained at approximately 0.8–1.5 mm, and the stability of thin-film electrolytes must be improved.

Mechanism of Ionomer Film Formation via Solution Drying.

Film formation via the drying of ionomer solutions is a crucial process that has a strong influence on the morphology and transport properties of polymer electrolyte membranes and thin films. However, the microscopic mechanism of this process remains unclear. Here, we elucidate this mechanism using a coarse-grained model based on all-atom molecular dynamics that accurately reproduces small-angle X-ray scattering spectra. In dilute ionomer solutions, ionomers form rod-like bundles with diameters of 1.5-2 nm. As the water solvent evaporates, these bundles gradually aggregate and connect to each other, while maintaining their diameter. Finally, the remaining water forms nanosized clusters surrounded by the surfaces of the bundles with hydrophilic sulfonate groups.

Polarization Reduction of a Novel Cell Configuration Based on Thin-Film Electrolyte on Porous Oxide Framework for Solid State Batteries Application

In early 1990s, rechargeable Li batteries using inorganic ionic conductors as solid electrolytes have been proposed. Because of their improved safety features, solid state batteries have received great attention recently. Although using Li metal as an ideal high-capacity anode has been a long-term goal, the critical issues remaining to be solved are the polarization contributed from the solid electrolyte and the electrode/electrolyte interface. Thus, to form a Li-conducting thin film with good adhesion with an adequate conducting and porous oxide framework in between Li anode and thin electrolyte may be a solution for the reduction of above-mentioned polarization observed in the solid state batteries. Thus, the main objective of this study is to (i) calculate/estimate the polarization reduction in a solid state cell using thin-film inorganic electrolyte and metallic Li as anode, (ii) to complete the experimental design for in-situ formation of thin electrolyte based on sol-gel deposition of an oxides precursor on a porous and conducting oxide framework followed by heat-treatment at temperatures > 700°C. The verification of polarization reduction contributed from the proposed thin-film electrolyte as well as the porous/conducting framework will be carried out in the near future.

Operando Ambient Pressure X Ray Photoelectron Spectroscopy for Li-Ion Battery Electrode/Electrolyte Interface Probing

Electrochemical reactions occur at the electrode/electrolyte interface. In lithium-ion batteries, the reversible Li ion insertion/desertion from the interfaces of electrodes gives the capacity of the battery. The surface phase transition and component chemical states change during the lithiation/delithiation in turn hugely effect the further battery capacity and reversibility. In the past decades, many ex-situ characterizations gave some insights of electrode surface behavior after cycling. However, the surface chemistry of electrode relies decisively on the real battery operation condition, e.g. the passive layer formed on the electrode surface changes dramatically with the absence of electrolyte. Therefore it is emerging and necessary to develop operando study for electrode/electrolyte interface probing during battery cycling.X-ray photoelectron spectroscopy (XPS) as a surface sensitive technique detects the photoelectrons ejected from core level with certain pass energy. The binding energy of the electrons give the information of chemical composition and chemical states of the materials. Ambient pressure XPS, developed rapidly in recent years after since it gives possibility of the participation of gas and/ liquid phase, enabling the observation of structure dynamics during chemical reactions, thereby unprecedentedly extended the application of the technique. A method called dip-and-pull is used for operando liquid/solid interface probing. With a typical three-electrode system, the electrode is pulled up from the electrolyte with still contact to liquid to maintain the circuit. A thin film of electrolyte formed with a shape of meniscus at the interface of electrode, electrolyte and atmosphere is probed through. The probing of the electrochemical active surface through the liquid can be achieved with an optimized liquid layer and surface condition.In this study Lithium cobalt oxide (LCO), as the most widely used positive electrode for Li-ion battery with rock salt layered structure optimized for reversible Li intercalation/deintercalation, is used for interface dynamics investigation. As Li is deintercalated from LCO structure, the charge transfer from Li+ to Co-O environment causes a phase change. It was commonly assumed that the charge due to the deintercalation of Li from structure is fully transferred to Co3+, i.e. the loss of one electron contributes to one Co4+ from Co3+ oxidation. However, it is recently reported that the real condition maybe more complicated. The charge transfer from Li+ to Oa- (a<2) might take place especially during high voltage due to the hybrid fermi level of O and Co which might increase the mobility of Oa- and further results in cobalt reduction and oxygen evolution reaction. But the mechanism of structure evolution under corresponding potentials are very unclear. In this study, with the operando probing with APXPS, it is discovered that a native phase of Co2+ may play an unignorable role in the charge transfer, giving some new understandings of phase transition during lithiation/delithiation (see figure 1). With the development of APXPS for battery probing, combining with software data treatment, a clearer picture of phase evolution is possible to be given by time-resolved probing with APXPS. Potentially hidden intermediate states during electrochemical reactions which cannot be given from ex-situ probing are resolved. Figure 1

(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.