Solid-state Cells Research Articles

Comprehensive device simulation of perovskite solar cell with CuFeO2 as hole transport layer

Abstract Solid-state organic-inorganic halide perovskite solar cells have attracted increasing interest due to their potential as high-efficiency, low-cost photovoltaic devices. In this study, we comprehensively simulate CH₃NH₃PbI₃ perovskite-based solar cells with CuFeO₂ as the hole transport material (HTM) layer, and compare them to cells using Spiro-OMETAD and Cu₂O as HTM layers, utilizing SCAPS-1D software. The effects of absorber thickness, back contact work function, CuFeO₂ thickness, acceptor concentration, and defect density at the CH₃NH₃PbI₃/CuFeO₂ interface are analyzed. The results indicate that delafossite CuFeO₂ is a promising HTM that could significantly enhance the performance of perovskite-based solar cells. TiO₂/CH₃NH₃PbI₃/CuFeO₂ solar cells demonstrate comparable photovoltaic performance to those using traditional Spiro-OMETAD when the back contact electrode work function exceeds 4.9 eV, and superior performance compared to those with Cu₂O and Spiro-OMETAD at work functions below 4.8 eV. A high acceptor concentration exceeding 10¹⁶ cm⁻³ in CuFeO₂ is recommended to achieve optimal photovoltaic performance. These simulation results highlight the significant potential of employing CuFeO₂ as an HTM layer in CH₃NH₃PbI₃ perovskite-based solar cells as an alternative to the organic Spiro-OMETAD.

Numerical study of P3HT-based hybrid solid-state qantum dot solar cells with CdS quantum dots employing different metal oxides using SCAPS-1D

This study presents a comprehensive numerical investigation into solid-state quantum dot solar cells (SSQDSCs) utilizing P3HT poly(3-hexylthiophene) as both a hole transport and absorber layer employing SCAPS-1D simulation software, the research explores the performance of cells composed of FTO (Fluorine-doped Tin Oxide) as the front contact, integrated with different metal oxides (Titanium dioxide (TiO2), zinc oxide (ZnO), and tin dioxide (SnO2), CdS (Cadmium sulfide )quantum dots, P3HT, and Pt (platinum )as the back contact namely Hybrid solar cell. The thickness of each layer is systematically optimized, and the influence of various CdS quantum dots sizes is thoroughly examined. The study also dived into the characterization of interface defects at the P3HT/CdS junction, involving modifications to the electron affinity of P3HT. Additionally, the impact of metal work function variations was also investigated analyzing at each case critical parameters such as open-circuit voltage (VOC), short-circuit current density (JSC), fill factor (FF), power conversion efficiency (PCE) and quantum efficiency. The results demonstrate that optimization of these parameters has the potential to elevate solar cell efficiency to 18%. These simulation findings offer valuable insights for comparative analysis and a deeper understanding of the challenges encountered in experimental research.

Unveiling the Role of Filler Characteristics in Enhancing the High-Voltage Performance of Succinonitrile-Based Solid-State Lithium-Metal Batteries.

For exploiting high-energy lithium-metal batteries, it is of utmost importance to develop electrolytes that possess exceptional ionic conductivity and an extensive electrochemical stability range. In this study, 3D PAN nanofibers and polymer electrolytes incorporating various inorganic fillers with different Lewis acid-base properties were fabricated. PAN@Al-SSE exhibits exceptional ionic conductivity (0.48 mS·cm-2 at room temperature), a high Li+ transference number (0.41), and a wide electrochemical window (5.26 V). The device is able to operate stably in Li symmetric cells for more than 1000 h under a potential of 0.03 V under a current density of 0.2 mA·cm-2. Besides, the groundbreaking technology equips high-voltage Li-LiCoO2 solid-state batteries with exceptional cycling performance (91.3% and 82.1% retention after 100 cycles at 0.2 and 1 C, respectively) at room temperature. Mechanistic studies indicate that the Lewis acid-base properties of surface fillers are instrumental and crucial to form a stable solid-electrolyte interphase layer. γ-Al2O3, in particular, with more Lewis acid sites, ensures the dissociation of LiTFSI and induces the excessive decomposition and polymerization of succinonitrile. There exists an equilibrium effect between dissociation and polymerization in a succinonitrile-based solid electrolyte, which plays a critical role in improving the manifestation of succinonitrile-based solid-state lithium cells, especially under high-voltage conditions.

The Regulation of Solid Electrolyte Interphase on Composite Lithium Anodes in Solid-State Batteries.

Solid-state lithium metal batteries (SSLMBs) with solid polymer electrolyte (SPE) are highly promising for next-generation energy storage due to their enhanced safety and energy density. However, the stability of the solid electrolyte interphase (SEI) on the lithium metal/SPE interface is a major challenge, as continuous SEI degradation and regeneration during cycling lead to capacity fading. This article investigates the SEI formation on lithium anodes (l-SEI) and composite lithium anodes (c-SEI) in solid-state lithium metal batteries. The composite anodes form a uniform Li2S-rich inorganic SEI layer and a thinner organic SEI layer, effectively passivating the interface for enhanced cycling stability. Specifically, the full cells with c-SEI anodes sustain over 400 cycles at 0.5 C under a high areal capacity of 2.0 mAh cm-2. Moreover, the reversible high-loading solid-state pouch cells exhibit exceptional safety even after curling and cutting. These findings offer valuable insights into developing composite electrodes with robust SEI for solid-state polymer-based lithium metal batteries.

Li2.9Fe0.9Zr0.1Cl6 as Redox-Active Catholyte for Solid-State Li-Ion Batteries.

Solid electrolytes are one of the key challenges that hinder the commercialization of all-solid-state batteries. Most efforts have been made to advance the development of solid electrolytes as separators, while the development of catholytes, particularly redox-active catholytes, has been less extensively studied. The high loading of catholytes in composite cathodes, while facilitating ionic conduction, drastically decreases the energy density of the battery. Here, we report an alternative strategy to improve the energy density by using Li2.9Fe0.9Zr0.1Cl6 as a redox-active catholyte. With a composite cathode containing uncoated LiCoO2 and Li2.9Fe0.9Zr0.1Cl6, the solid-state cell not only shows excellent rate capability and stable long-term cycling, benefiting from the high ionic conductivity of Li2.9Fe0.9Zr0.1Cl6, but also shows a high cathode specific capacity of ∼153 mAh·g-1. This study broadens the chemical space of the materials design for lithium-ion conductors with redox-active elements (e.g., Fe, Ti, V, and Cr), offering new opportunities to reduce the cost and improve the energy density for all-solid-state batteries.

Direct Precursor Route for the Fabrication of LLZO Composite Cathodes for Solid-State Batteries.

Solid-state batteries based on Li7La3Zr2O12 (LLZO) garnet electrolyte are a robust and safe alternative to conventional lithium-ion batteries. However, the large-scale implementation of ceramic composite cathodes is still challenging due to a complex multistep manufacturing process. A new one-step route for the direct synthesis of LLZO during the manufacturing of LLZO/LiCoO2 (LCO) composite cathodes based on cheap precursors and utilizing the industrially established tape casting process is presented. It is shown that Al, Ta:LLZO can be formed directly in the presence of LCO from metal oxide precursors (LiOH, La2O3, ZrO2, Al2O3, and Ta2O5) by heating to 1050°C, eliminating the time- and energy-consuming synthesis of preformed LLZO powders. In addition, performance-optimized gradient microstructures can be produced by sequential casting of slurries with different compositions, resulting in dense and flat phase-pure cathodes without unwanted ion interdiffusion or secondary phase formation. Freestanding cathodes with a thickness of 85µm, a relative density of 95%, and an industrial relevant LCO loading of 15mg show an initial capacity of 82 mAh g-1 (63% of the theoretical capacity of LCO) in a solid-state cell with Li metal anodes, which is comparable to conventional LCO/LLZO cathodes and can be further improved in the future.

Investigation of Solid Polymer Electrolytes for NASICON-Type Solid-State Symmetric Sodium-Ion Battery.

The inevitable shift toward renewable energy and electrification necessitates earth-abundant sodium reserves for next-generation Na-based energy storage technologies. By coupling the benefits of solid electrolytes over traditional nonaqueous electrolytes due to their safety hazards, solid-state sodium-ion batteries hold huge prospects in the future. This work presents a comprehensively developed solid-state sodium-ion symmetric full cell operating at room temperature enabled through a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based polymer electrolyte and modified NASICON-structured positive and negative electrodes. Among the investigated polymer electrolytes, PVDF-HFP-NaTFSI was found to outperform other counterparts by achieving a higher ionic conductivity and delivered an appreciable electrochemical stability window. By further delving into the properties of PVDF-HFP-NaTFSI, it was found to possess the least crystallinity, minimal porous structure, lowest melting point, and fusion enthalpy, indicating better ion transport than other investigated polymer electrolytes. The as-assembled solid-state battery revealed a storage capacity of 74 mAh g-1 at 0.1 C with a specific energy density of 130 Wh kgcathode_active_material-1 and demonstrated an impressive capacity retention of 84% of the initial capacity after 200 cycles. The structure and morphology retention of the cycled electrode and electrolyte through postmortem analysis bolster the electrochemo-mechanical stability of the developed solid cell. The findings reported here on polymer electrolytes persuade expedient solutions for developing ambient temperature solid-state sodium-ion batteries with promising electrochemical performance for commercialization in the near future.

Design and Performance Analysis Of Complete Solid-State Dye Sensitised Solar Cell Using Eosin-Y Xanthene Dye: a SCAPS -1D Simulation Study

This paper reports the theoretical simulation study of the performance of a complete solid-state dye-sensitised solar cell with Eosin-Y as the photosensitizer and PEDOT: PSS as the hole transport layer. SCAPS-1D software is used for the simulation under quasi-ideal conditions and got an optimised efficiency of 4.19%, which matches much with the reported experimental values in the literature. These finding indicates the potential of Eosin-Y as a cost-effective photosensitiser capable of performing even under dim light conditions.

Solid-State Oxide Fuel Cells

Solid-State Oxide Fuel Cell (SOFC) is an efficient energy conversion device that directly covers fuel's chemical energy into electricity. With a high energy conversion efficiency, it is not limited by the Carnot cycle. Fuel adaptability is wide, clean and pollution-free, all solid structure, do not use precious metal catalyst and other advantages. It is of great significance to achieve the goal of carbon peak and carbon neutrality target in China. However, there are some problems, mainly including: conductivity, relatively low conductivity of medium-temperature solid oxide fuel cells, which limits the performance of batteries, sintering, cost, and stability. To improve the conductivity, researchers are exploring different material combinations and doping strategies to optimize the crystal structure and chemical composition of the electrolyte. Finally, the importance of the electrolyte, the role of the oxygen vacancy, the influence of the doping elements, and the balance of the performance and the cost are drawn.

Simulating solid-state battery cathode manufacturing via wet-processing with resolved active material geometries

Prior to the development of a solid-state battery cell, researchers have limited knowledge about the microstructure of the electrodes and how they are affected by manufacturing. Therefore, numerical simulations can be considered as a powerful tool to link the fabrication process to the final microstructure of the electrode. In this paper, a numerical simulation of a wet-processed solid-state battery cathode with a formulation of 75 % LiNi9Mn0.5Co0.5O2 (NMC), 17.5 %LPSCl, 5 % Timcal C65 and 2.5 % Polyisobutene (PIB) is presented. From nano-computed tomography images, realistic shapes of active material particles are extracted and used in the simulation, which is well-calibrated to experimental data. In particular, we study the effects of calendering on the microstructure of the simulated cathode and deduce structure-property relations.

Engineering Mn Vacancies to Enhance Ion Kinetics in Layered Manganese Silicate for High-Energy and Durable Intercalation Pseudocapacitance.

Transition metal silicates (TMSs) are potential electrodes for aqueous metal-ion intercalation pseudocapacitors owing to their superior theoretical capacity and high structural stability. However, the narrow interlayer spacing and intrinsic inert basal plane of TMSs lead to sluggish ions and charge transfer, causing an undesirable energy storage performance. Herein, rich Mn vacancies are introduced in layered manganous silicates (M2-xS@FA) to expedite K+ diffusion, while enhancing charge storage capacity and prolonging lifespan. In situ characterizations validate the K+ intercalation pseudocapacitance mechanism with evident crystal structure and valence state variations in M2-xS@FA. Both theoretical calculations and electrochemical experimental evaluations elucidate the imperative role of Mn vacancies in enhancing K+ diffusion kinetics and electron transfer through increased interlayer spacing and activated basal plane. Mn vacancies further boost the charge storage capacity by providing additional K+ storage sites, while simultaneously reinforcing local atomic bonding within M2-xS@FA, thereby augmenting structural stability. The assembled aqueous asymmetric solid-state cell, featuring a M2-xS@FA cathode, demonstrates exceptional power and energy densities (144.08 W h kg-1 at 375.80 W kg-1) and ultralong lifespan (100% capacity retention after 10,000 cycles). This work heralds a paradigm whereby modulating cation vacancies in layered TMSs significantly enhances K+ storage and stability for high-energy intercalation pseudocapacitance.

Construction of flexible asymmetric composite polymer electrolytes for high-voltage lithium metal batteries with superior performance

The primary obstacle hindering the application of composite solid electrolytes lies in the varying demands posed by the Li metal anode and the cathode, which needs to be capable of suppressing dendrite growth and resisting high voltage simultaneously. In this work, a new asymmetric composite solid-state electrolyte prepared via electrospinning and in-situ polymerization is proposed to address these shortcomings. In this bilayer architecture, polyacrylonitrile (PAN) layer of high-voltage tolerance, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) layer of robust mechanical strength and good compatibility towards Li-anode are constructed, and metal-organic-frameworks (MOFs) are pre-embedded within both layers. The unique design provides a wide electrochemical stability window meanwhile ensures uniform lithium deposition. Remarkably, it exhibits a superior lithium utilization of 41 mAh cm−2 using a lean polymer electrolyte precursor and a high critical current density of 2.2 mA cm−2 with a thickness of 40 μm. Beneficial from the formation of a self-adjustable gradient solid electrolyte interphase in the Li/PVDF-HFP interface, the asymmetric electrolyte endows Li||Li and Li||NCM811 cells with excellent cycling stability. Moreover, the solid-state pouch cell exhibits reliable operation under extreme conditions. This work provides inspiration for the design and fabrication of composite solid electrolytes for next-generation high-voltage Li metal batteries.

Correlating Homogeneity and Microstructure of in Situ plated Li in “Anode-Free” Solid-State Batteries

Solid-state batteries utilizing Li metal anodes have the potential to offer increased safety and higher energy density compared to state-of-the-art Li-ion batteries. To achieve these energy density gains, the Li metal anode must be thin (<25 µm). Manufacturing of thin Li metal anodes is complicated by the reactivity of Li metal, which forms a thin passivation layer even in controlled environments. The “anode-free” cell manufacturing approach provides an alternative to these challenges. These cells are manufactured with a bare anode current collector (CC) and the Li metal anode is plated in situ at the CC/solid-state electrolyte interface during the first charging step using the Li stored in the cathode active material. While manufacturing cells with in situ formed Li anodes may offer benefits, removing all excess Li in the cell also poses many challenges. The Coulombic efficiency of these cells must be >99.99% to retain 90% capacity over 1,000 cycles [1]. Therefore, when the Li anode is formed in situ during the first charge, the temperature, pressure, and current density must be carefully tuned to optimize the reversibility of the plated Li. To achieve high reversibility of Li metal anodes, the plated Li should be dense, conformal to the current collector and solid-state electrolyte, homogeneous in thickness, and ideally have a small grain size. These objectives can be achieved by tuning the plating parameters during in situ Li deposition, including pressure, temperature, and current density. It has been previously shown that applying 5 MPa of pressure could improve the homogeneity of in situ formed Li anodes in solid-state cells [2].However, applying pressures >1 MPa is undesirable for practical applications [3]. Therefore, it is necessary to alter the in situ plated Li using other parameters, including the temperature and current density used during plating. Here, we show the effect of plating current density and temperature on the homogeneity and microstructure of in situ formed Li anodes in solid-state cells. It is demonstrated that optimized plating current protocols can improve the homogeneity of plated Li without the need for elevated temperatures. Finally, the relationship between the homogeneity of the in situ plated Li and the reversibility upon stripping is studied using unidirectional stripping experiments. These results illustrate the importance of carefully controlling the parameters for Li plating to enable high Coulombic efficiency in situ formed Li anodes in solid-state cells.

Ontology Creation and Database Implementation for Lab-Scale Solid-State Battery Cells

New developments and publications on alkali metal solid-state batteries are being published at a high rate, with the total number of publications now in the thousands, but the search and analysis of the data in these publications is still largely done using key words and through careful reading of the article and the supporting information. The challenges of efficiently searching and extracting data from thousands of publications in a field are also present in other fields, such as perovskite solar cells, for which a large (>15,000) set of cell data has been entered into a database that continues to be updated.1 A database for alkali metal (e.g., based on Na+ and Li+ conduction) solid-state cells that could be easily searched and that facilitated advanced forms of data analysis could accelerate research progress, and is consistent with efforts such as definition of the “Principles of the Battery Data Genome” and the BIG-MAP project.2 In this talk, we describe our approach to creating an ontology and database for lab-scale solid-state cells, along with results to date. Key areas for the ontology include component material identities, material properties, component properties (e.g., active material loading, mass fractions, thicknesses), processing conditions for materials and the cell itself (e.g., ball milling time, sintering time), and both performance (e.g., rate capability) and degradation (e.g., cycle life). Results based on several hundred solid state cells in our database are presented in terms of histogram plots, violin plots, correlation plots, and other representations. We also describe our efforts to integrate our ontology and tool with broader efforts in the field, and to make it broadly useful to battery researchers.1. Nature Energy, volume 7, pages 107–115 (2022) and https://www.perovskitedatabase.com/2. Joule 6, 2253–2271, October 19, 2022 and https://www.big-map.eu/dissemination/battinfo

(Invited) Exploitation of Advanced Materials and Process for Sustainable Perovskite Solar Cells

All solid-state solar cells based on organometal trihalide perovskite absorbers have already achieved distinguished power conversion efficiency (PCE) to 26.1% and further improvements are expected up to 27%. Now, the research on perovskite solar cells (PSCs) has been moving toward commercialization. To facilitate commercialization of these great solar cells, some technical issues such as long-term stability, large scale fabrication process, Pb-related hazardous materials, and environmentally-burdened toxic solvent-based process need to be solved.This talk is dealing with our recent efforts to facilitate commercialization of perovskite solar cells. For examples, we introduce a recycling technology of perovskite solar cells, which covers the regeneration process of Pb contained perovskite layer as well as recycling process of Au electrodes and transparent conducting oxide glass [1, 2]. Also, novel strategies for recycling toxic solvents such as DFM, used in fabricating PSCs are introduced, which is critical to realize close loop recycling process of PSCs. Finally, recent studies for achieving high efficiency PSC using ecofriendly solvent are demonstrated.

Development of a Controlled Humidity Differential Electrochemical Gas Monitoring System

Lithium-air batteries (LABs) represent a promising future battery technology due to their high energy density, although several challenges hinder them from achieving their theoretical performance. These challenges include clogging of the porous air cathode by insoluble discharge products and high overpotentials during cycling [1, 2]. A recent proposal to address these issues involves the reversible formation and oxidation of LiOH in nonaqueous LABs. Of course, LiOH-based LABs require a proton source to form LiOH from the electrochemical reaction of oxygen and lithium ions [3]; humidity in air is an obvious choice for the proton source, making the relative humidity of LAB feed gas an important parameter to control and monitor during LAB electrochemical analysis.For LABs, galvanostatic charge/discharge coupled with quantitative gas evolution/consumption measurement is essential to understand the electrochemical processes during battery operation. Here, we report an advanced operando pressure measurement system that allows the control and monitoring of humidity in the cell headspace while also tracing overall gas consumption and evolution. Our gas handling system generates humid air using a water-containing chamber with a temperature control vessel to generate water vapor. A mass flow controller mixes dry air with humid air to generate specific relative humidity and send it to the cell. Using various low-volume in-line sensors, our system can track headspace humidity, temperature, and pressure within a custom-modified Swagelok-type cell. The total headspace volume must be small (~mL) since gas consumption occurs on a μmol scale in our lab-scale cells. To minimize headspace and dead volume within the Swagelok-type cell, a digital humidity and temperature sensor with exceptional accuracy was integrated into a customized printed circuit board (PCB). This PCB is attached to the small dead-volume Tee connection. To control the humidity inside the cell and achieve sensor data simultaneously, all sensors in the monitoring system are controlled by a LabVIEW program (National Instruments). To show the utility of this new system, we will present analyses of nonaqueous and solid-state LAB cells that operate at various humidities and current rates, while employing various known 2 e- and 4 e- oxygen reduction catalysts.

A Rechargeable Solid-State Sodium-Oxygen Battery with Enhanced Energy Efficiency and Cycle Life

Sodium-oxygen (Na-O2) batteries offer a promising path for the advancement of high-energy-density inexpensive storage systems to replace current state of the art Li-based batteries owing to the natural abundance and low-cost Na metal. Despite numerous studies to improve the performance of liquid-based electrolyte Na-O2 batteries, this technology suffers from poor cycle life, electrolyte stability issues, and limited choice of cell design as well as growing safety concerns associated with liquid electrolytes. Recently, solid electrolytes received a great attention to substitute traditional liquid electrolytes used in Na-O2 batteries, due to their ability of improving safety and energy density. However, low ionic conductivity and high impedance in contact with the anode and cathode remain as major challenges for the development suitable solid-state electrolyte for Na-O2 batteries.In addressing these challenges, we recently have established a solid-state Na-O2 battery cell that comprises a highly conductive composite polymer-ceramic solid electrolyte with a conductivity of 0.7 mS/cm. This solid electrolyte works in synergy with vanadium phosphide (VP) nanoparticles, serving as oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalysts at the cathode and Na metal anode for more than 500 reversible charge-discharge cycles at a capacity of 1000 mAh/g, achieving a low polarization gap of approximately 20 mV in the first cycle. Various electrochemical and physicochemical characterization techniques, such as Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), differential electrochemical mass spectrometry (DEMS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), were employed to gain insight into the cell chemistry and solid-state electrolyte role in the formation and decomposition of sodium oxides components such as superoxide (NaO2), peroxide (Na2O2). The findings of this study underscore the significance of proper cell component design and possible mechanisms in solid-state Na-O2 battery technologies. This research represents a promising avenue in advancing energy conversion and storage systems, showcasing the potential of solid-state batteries with enhanced safety and performance characteristics.

Integrating Polymer Electrolytes-Based Thick Composite Cathodes in All-Polymer Solid-State Lithium Metal Batteries

High energy density solid-state batteries require high areal loading composite cathodes (>4 mAh/cm2). However, increasing the cathode loading or thickness can introduce additional challenges apart from the expected rate capability limitations, which are much less pronounced in low loading or thin composite cathodes. These include greater volume changes during cycling at the cell level, which can introduce stresses at the various interfaces. While there are many successful reports showing long-term stable cycling of high loading composite cathode in all-inorganic solid-state cells, these cells are typically cycled under high pressures (>10 MPa), which may be impractical to commercialize. Such high pressures can alleviate the interfacial contact loss issues generated due to volume changes during cycling. Polymer electrolytes are non-rigid and can potentially accommodate strains to maintain contact at the interfaces during cycling, given sufficient adhesion. In this work, we will show some of the design strategies that were implemented to alleviate the contact loss issue at the polymer electrolyte separator/composite cathode interface in order to achieve stable cycling with thick polymer electrolyte-based composite cathodes in coil-cell configuration. Nickel-rich NMC (LiNixMnyCozO2) cathodes (NMC811 or 622) were used as the active materials. Since polymer electrolytes are known to be unstable with high voltage cathodes such as NMCs, the contribution of oxidative instability to the overall capacity decay will also be discussed by comparing two polymer electrolytes with different oxidative stability (a PEO-based dual-ion polymer electrolyte, and a single-ion 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 (Simon Thompson, Program Manager). A part of this research was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC for the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. The SEM in this work was performed and supported at the Center for Nanophase Materials Sciences in Oak Ridge National Lab, a DOE Office of Science user facility.

Giant dielectric ceramic of Li0.3Ti0.02Ni0.68O with abundant oxygen vacancies enabling high lithium-ion conductivity in composite solid-state electrolyte

The low ionic conductivity of composite solid-state electrolytes due to the lack of free Li-ions and Li dendrite growth induced by the low transference number seriously hinder their application. Herein, we find that the giant dielectric ceramic of Li0.3Ti0.02Ni0.68O (LTNO) with ultra-high dielectric constant can greatly promote the dissociation of Li salt to generate abundant movable Li-ions and realize a high room-temperature ionic conductivity (4.09 × 10–4 S cm−1) as well as a low activation energy (0.16 eV). The oxygen vacancies on the surface of LTNO can effectively immobilize the anions to achieve a high Li transference number (0.61). Furthermore, the enhanced dielectric properties of the composite electrolyte induce homogenous Li plating/stripping to suppress the growth of Li dendrites. As a result, the Li||Li symmetric cells exhibit long lifespan of 2400 h and 1150 h at 0.1 mA cm−2 and 0.2 mA cm−2, respectively. The Li||LiNi0.8Co0.1Mn0.1O2 solid-state full cells show a high capacity retention of 83% after 430 cycles at 2C. This work highlights the critical role of high dielectric property and oxygen defects of fillers in composite solid-state electrolytes, and provides a demonstration for the application of giant dielectric materials in solid-state Li metal batteries.

“Unveiling marigold assembled micro flowers of tungsten oxide towards solid-state flexible pouch and coin cell supercapacitors”

Marigold analogues micro flowers of tungsten oxide (WO3) have been grown in thin film form through simple and cost-effective solution chemistry approach on stainless steel substrate. Aqueous precursor involving WO4-2 ions agglomerated as self-sacrificing template growing initially into the nano-petal, followed by self-assembly; leading to marigold analogues micro flower surface architecture. This enthralling morphology motivated us not only to fabricate supercapacitive electrode but also to design complete solid-state supercapacitor devices in dual configurations: flexible pouch cell and coin cell. Interestingly, both devices even in symmetric configuration yields remarkable potential window of 1.82 V when sandwiched by gel inclusive of Li+ ions dispersed in non-conducting polyvinyl alcohol matrix. Solid-state flexible pouch cell and coin cell delivered specific capacitances of 103.98 ± 3.59 and 30.09 ± 1.03 F/g respectively at a scan rate of 5 mV/s. Assembled electrode, coin-cell and flexible pouch-cells have been well assessed in-depth through specific capacitances using cyclic voltammetry and galvanostatic charge discharge, diffusive and capacitive contributions, mechanical bending tests, electrochemical active surface area, and electrochemical impedance analysis. Practical applicability has been demonstrated for designed flexible pouch cell to run small fan and light emitting diode panel whereas coin cell to run light emitting diode panel.