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Comparison of the volumetric and gravimetric energy density of solid-state thin-film batteries (SSTFBs) with other batteries [333-335].
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All-solid-state batteries (SSBs) are one of the most fascinating next-generation energy storage systems that can provide improved energy density and safety for a wide range of applications from portable electronics to electric vehicles. The development of SSBs was accelerated by the discovery of new materials and the design of nanostructures. In pa...
Citations
... For instance, engineered thin films with high conductivity enable the development of more efficient batteries, such as solid-state batteries. These offer enhancements in energy density, battery life, charging speed, and safety, among other benefits (Moitzheim et al., 2019;Yang et al., 2020). ...
Utilizing radio frequency magnetron sputtering, we successfully fabricated nickel oxide thin films with different thickness (from 80 to 270 nm), and conducted an in‐depth examination of their structural, morphological, optical, and electrical properties. The crystal structure and surface roughness were determined using x‐ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD analyses showed that the films were composed of cubic nickel oxide, exhibiting a notable orientation along the (200) direction. This crystal texture partially increased when the film thickness reached 270 nm. In addition, a direct correlation between film thickness and crystallite size was observed, with the latter increasing as the former did. AFM analysis provided insights into the surface morphology, revealing metrics like the bearing area, 3D surfaces intersections, and statistical properties of surface height. These insights underscore the relationship between film thickness and surface properties, which in turn influence the overall electrical, and prominently, optical properties of the films. Employing transmittance UV–visible spectroscopy, we characterized the optical behavior of these films, noting a proportional increase in refractive index with film thickness. Additionally, resistivity was observed to increase concomitantly with film thickness. In conclusion, the deposition process's film thickness acts as a pivotal parameter for fine‐tuning the structural, morphological, and optical properties of nickel oxide thin films. This knowledge paves the way for optimizing nickel oxide‐based devices across various applications.
Research Highlights
We synthesized and characterized of p‐type semiconducting NiO thin films sputtered on substrates by using RF magnetron sputtering with different thickness.
Advanced crystalline structures and fractal features extracted from XRD and AFM analysis.
The 2D and 3D surface analysis of the samples indicates a complex structure with an imperfect self‐similarity that suggests a multifractal structure.
We represented graphically the relative representation of higher geometric objects in the AFM image.
We attributed the optical and electrical properties of the samples to the crystallite size, and the concurrent reduction in oxygen vacancies and crystalline defects within the films.
... Superionic materials possess a solid atomic matrix that includes one or more species of mobile atoms, which become dispersed at the phase transition temperature. The interest in studying such materials comes from their potential applications in solid-state batteries, and fuel cells because of their extraordinarily high ionic conductivity at supercritical temperatures [12][13][14][15][16][17][18][19]. ...
Copper and silver tetraiodomercurates (Cu2HgI4, Ag2HgI4) are thermochromic materials whose color changes result from a crystalline phase transition, affecting their electrical and thermal conductivities. Both materials, defined as superionic solids, are solid electrolytes where the metallic cations are the charge carriers in the higher temperature phase, which occurs at 50 °C for Ag2HgI4 and at 69 °C for Cu2HgI4. In this work, we present the thermal characterization of these materials by measuring the thermal diffusivity as a function of temperature, intending to elucidate the influence of randomly moving cations on thermal transport and their interactions with the phonons produced in the anion sublattice. The electrical conductivity characterization enabled us to contrast their different behavior as the phase transition occurs due to temperature changes. Thermal and electrical transport performance characterization of these materials opens the possibility of using them in different applications, such as solid-state batteries, optical devices for recording media, active materials for thermally controlled systems, temperature sensing devices, and fillers for manufacturing smart composites, among many others.
... Furthermore, they have little effect on the environment and human health as they are used in cosmetics. Figure 2 shows that titanium oxide has various crystal structures and that the bandgap changes depending on the crystal structures [4]. In this study, we analyzed a photocatalytic effect on the absorption wavelength produced by the differential crystal structure only by controlling the primary particle shape without adding other elements. ...
... Furthermore, we constructed the integrated battery system by fabricating the photoactive thin-film electrode and evaluating its characteristics. Purpose Figure 2 shows that titanium oxide has various crystal structures and that the bandgap changes depending on the crystal structures [4]. In this study, we analyzed a photocatalytic effect on the absorption wavelength produced by the differential crystal structure only by controlling the primary particle shape without adding other elements. ...
... Furthermore, they have little the environment and human health as they are used in cosmetics. Figure 2 shows that titanium oxide has various crystal structures and bandgap changes depending on the crystal structures [4]. In this study, we an photocatalytic effect on the absorption wavelength produced by the differentia structure only by controlling the primary particle shape without adding other e Furthermore, we constructed the integrated battery system by fabricating the pho thin-film electrode and evaluating its characteristics. ...
... However, there are a number of specifications that the substance employed as a solid electrolyte should have; At room temperature, the ionic conductivity should be more than 10 −4 Scm −1 , the electronic conductivity should be negligible with a high ionic transference number, and the material should have electrochemical stability. The solid electrolytes can fulfill the aforementioned specifications including the NASICON, perovskite, garnet, sulfide, anti-perovskite, and LiPON types, etc. [5][6][7][8] The most suitable Li-ion conductor for Li-ion diffusion is LiTi 2 (PO 4 ) 3 (LTP) among all NASICON-type Li-ion conductors. R-3c space group and rhombohedral symmetry characterize its crystal structure as NASICON-type. ...
LATP ceramic electrolytes have been prepared by sintering combinations of LATP powder and CeO2 nano-powder. The phase formation of LiTi2(PO4)3 (LTP) and the secondary phase formation of the fine CePO4 particles scattered in LATP ceramics were confirmed by powder X-ray diffraction. The morphology of ceramic sample was studied using scanning electron microscopy. The elemental distribution was investigated using energy-dispersive X-ray spectroscopy. The CeO2 addition improves the electrical conductivity. CeO2 nano-powder added LATP ceramics with 3 wt% CeO2 sintered at 800°C for 1h have a high ionic conductivity of 0.56 mS.cm-1 at room temperature with an activation energy of 0.15 eV.
... [9,10]. In addition, Ta-doped LLZO thin film have been already demonstrated to disclose remarkable improvement in the lithium-ion conductivity compared to bulks, thanks (a) to the reduction of the diffusion thickness to nanoscale dimensions and (b) to the minimization of 0D-1D defects and grain boundaries [11]. On the other hand, the instability of LLZO in ambient air with the formation of LiOH and Li 2 CO 3 strongly impairs its ionic conductivity the surface of LLZO particles. ...
The production of thin films has been extensively studied due to their unique properties that make them highly useful in a wide range of scientific and technological applications. Obtaining thin films with well-defined stoichiometry and crystallinity is a challenging task, especially when dealing with materials of complex stoichiometry. Among diverse methodologies for the manufacture of thin films, pulsed laser deposition (PLD) stands out as a versatile technique for producing crystalline films with complex chemical compositions. In this study, nanosecond PLD was employed to manufacture thin films of Ta-doped Li7La3Zr2O12 (LLZTO), a garnet-like oxide that has been proposed as solid electrolyte for Li-ion solid state batteries. Two distinct deposition atmospheres were investigated: vacuum conditions at 10−3 Pa and an oxygen-enriched environment with 10 Pa of O2 gas buffer. To mitigate lithium losses during deposition, a minor addition of lithium oxide was incorporated into the target. The effects of deposition atmosphere and the impact of post-deposition annealing on the structural, compositional, and morphological properties of LLZTO thin films were analysed through a multi-technique approach. The results suggest deposition under oxygen pressure led to the growth of compact, crystalline films characterized by homogenous elemental distribution across the surface and throughout the film’s depth. These films closely resemble the composition of the target LLZTO material, offering valuable insights for the fabrication of high-quality complex oxide thin films.
... reactions with the substrate [59]. One sequence of the deposition of films by ALD is made up of four stages: (1) pumping of the first precursor into the chamber to allow the formation of a monolayer, (2) purging of the reaction chamber to remove the reaction by-products, (3) pumping of the second precursor to into the chamber to allow the formation of a wanted layer, and (4) further purge of the reaction chamber [59][60][61]. ...
... reactions with the substrate [59]. One sequence of the deposition of films by ALD is made up of four stages: (1) pumping of the first precursor into the chamber to allow the formation of a monolayer, (2) purging of the reaction chamber to remove the reaction by-products, (3) pumping of the second precursor to into the chamber to allow the formation of a wanted layer, and (4) further purge of the reaction chamber [59][60][61]. A schematic of typical ALD cycle consisting of two half-cycles is shown in Figure 7.7. ...
... With the continuous advancements, TFLBs have become a promising power supplier for many devices owing to their compact size, flexibility, and impressive energy density [18][19][20][21]. Some of the most promising applications of TFLIBs include [22,23]: ...
... Although serval reviews have recently been published to report the progress of TFLIBs [18][19][20][21], the majority of the reviews have been directed towards the recent progress in SSEs and electrode materials. Few reviews have discussed the advanced architecture design of TFLIBs to increase the energy density and reduce the manufacturing costs. ...
... Batteries 2023, 9, x FOR PEER REVIEW 6 of 51 Figure 2. Schematic diagram of TFLIBs and electrode/SSEs interface issues [21]. ...
All-solid-state batteries (ASSBs) are among the remarkable next-generation energy storage technologies for a broad range of applications, including (implantable) medical devices, portable electronic devices, (hybrid) electric vehicles, and even large-scale grid storage. All-solid-state thin film Li-ion batteries (TFLIBs) with an extended cycle life, broad temperature operation range, and minimal self-discharge rate are superior to bulk-type ASSBs and have attracted considerable attention. Compared with conventional batteries, stacking dense thin films reduces the Li-ion diffusion length, thereby improving the rate capability. It is vital to develop TFLIBs with higher energy density and stability. However, multiple challenges, such as interfacial instability, low volumetric energy density, and high manufacturing cost, still hinder the widespread application of TFLIBs. At present, many approaches, such as materials optimization and novel architecture design, have been explored to enhance the stability and energy density of TFLIBs. An overview of these discoveries and developments in TFLIBs is presented in this review, together with new insights into the intrinsic mechanisms of operation; this is of great value to the batteries research community and facilitates further improvements in batteries in the near future.
... However, current solid electrolytes, that typically possess low ionic conductivity, cannot meet the required current density, especially for heavy-duty applications requiring high power [3,4]. Therefore, the finding of inorganic solid electrolytes with high ionic conductivity, and good chemical stability in contact with the electrodes is very useful [5]. Among the promising inorganic solid electrolytes for SLIBs, perovskite-type lithium lanthanum titanium oxides La 2/3−x Li 3x TiO 3 (abbreviated as LLTO) have attracted considerable attention from researchers because of its high Li-ion conductivity, which can theoretically reach about 1 × 10 −3 Scm −1 , at room temperature. ...
... Therefore, the total ionic conductivity for the polycrystalline LLTO samples is reduced to the order of 10 −5 Scm −1 [6]. The research results also show that the lithium-ion conductivity of LLTO ceramics depends on the crystal structure and microstructure [6][7][8], the concentration of lithium-ion and the A-site vacancies [6,7,9,10], the chemical homogeneity [5,11], the sizes of grain and grain boundaries [12,13] and material density [3]. The influence of these factors on the electrical conductivity of LLTO can be adjusted through the methods of initial LLTO powder preparation, temperature, time and sintering procedure [3,5,7,[14][15][16][17][18]. ...
... The research results also show that the lithium-ion conductivity of LLTO ceramics depends on the crystal structure and microstructure [6][7][8], the concentration of lithium-ion and the A-site vacancies [6,7,9,10], the chemical homogeneity [5,11], the sizes of grain and grain boundaries [12,13] and material density [3]. The influence of these factors on the electrical conductivity of LLTO can be adjusted through the methods of initial LLTO powder preparation, temperature, time and sintering procedure [3,5,7,[14][15][16][17][18]. Therefore, preparation technology has always played an important role to obtain LLTO ceramics with desired properties. ...
In this work, La(2/3)-xLi3xTiO3 (LLTO) dense ceramic samples have been prepared by high-energy ball milling and spark plasma sintering (SPS) route. The crystal structures, microstructures of the samples were characterized by X-ray powder diffraction, FE-SEM, and their Li-ion conductive properties investigated by AC impedance spectroscopy. At 21 oC, the LLTO ceramic samples possessed the grain conductivity and grain boundary/total conductivity of σg = 8.3×10-4 S cm-1 and σgb = 2.3×10-5 S cm-1, respectively. In the research temperature range from 21 oC to 120 oC, the mechanism of ion conduction is thermally activated. The activation energies for grain and grain boundary conductivities are Eag = 0.26 eV and Eagb = 0.43 eV, respectively. Keywords: High energy mechanical milling, LLTO ceramics, Spark plasma sintering, Lithium ionic conductivity, Impedance Classification numbers: 81.05.Je, 81.20.Ev, 72.20.-i, 61.72.Mm, 82.47.Aa, 84.37.+q
... Generally, adding the Ni concentration increases the capacity and decreases the expense, but it decreases the structural and thermal stability. However, significant obstacles exist, such as the low ionic conductivity of solid electrolytes and the destabilization of the interface [12]. Research findings show that replacing Ti 4+ with other ions can stabilize the electrolyte and enhance the performance of cathodes [13,14], but make the ionic conductivity decrease [15]. ...
Various cathodes have been studied to obtain cathode materials with high energy density and are inexpensive and environmentally friendly. Ti4+ substitution is one strategy to achieve this. Ti4+ doping has been done on Co2+ to reduce the level of toxicity. The objective of this research was to look at the impact of Ti4+ substitution on LiNi0.8Mn0.1Co(0.1-x)TixO2 so that it can be used as a battery cathode. The samples were prepared by the solid-state reaction method using high energy milling (HEM) in a wet state using ethanol. The phase formation of the material was characterized using XRD, surface morphology was characterized using SEM, and electrical conductivity was characterized using LCR-Meter. The finding showed that the particles experienced agglomeration, with the average size of the primary particles ranging from 300-500 nm and the secondary particle sizes ranging from 1-3mm. The morphology of the sample shows polycrystals. The maximum electronic conductivity obtained was 2.3 x 10-5, 2.4 x 10-5, and 3.2 x 10-5 S/cm for x = 0.01, 0.02, and 0.03, respectively. Another impact is increasing the cell volume and conductivity. With this high electrical conductivity value, this material is suitable for use as a battery cathode.
... Transitioning to a solid-state battery (SSB) could improve LIB energy density, however, it remains a challenge to achieve high relative densities with current particle-based architectures. Solid-state-battery architectures are limited by high interfacial resistances and the need to mix active material slurries with solid electrolyte (SE) particles and inactive particles for stability [21][22][23][24][25][26][27][28]. Minimizing the number of interfaces between cathode particles and solid electrolytes can mitigate these resistances; however, particle-based architectures have an inherent trade-off between fewer interfaces and higher density [23,25]. ...
Creating thick electrodes with low porosity can dramatically increase the available energy in a single cell and decrease the number of electrode stacks needed in a full battery, which results in higher energy, lower cost, and easier to manufacture batteries. However, existing electrode architectures cannot simultaneously achieve thick electrodes with high active material volume fractions and good power. These particle-based architectures rely on electrolyte transport within the pores of the cathode to fully lithiate active material particles during discharge. As cathode solid volume fractions approach 100%, batteries experience electrolyte depletion which leads to inaccessible cathode reaction sites (see Fig. 1A). The additional theoretical capacity that comes from increased cathode density, therefore, is impractical if that energy cannot be fully extracted.
We combine experiments and simulations of high density and high thickness cathodes to understand the transport and performance trade-offs of LIBs as the cathode solid volume fraction approaches 100%, which we use to reveal the cathode properties needed to achieve high performance at high relative density and thickness. We use one- and two-dimensional simulations to compare the discharge performance of two cathode architectures, a traditional particle-based architecture and a continuous cathode architecture created via electrodeposition. In addition, a model with spaced diffusion-barriers explores the design space between these two architectures and elucidates the influence of increasing solid-diffusion length on discharge performance. We show that there is a large opportunity space for improved energy density at high relative densities by using new electrode manufacturing techniques to create continuous diffusion pathways and high diffusivities. Increasing the solid diffusion length from 4.78 µm to 55 µm in cathodes with high diffusivity leads to an increase in areal capacity (from 1.6 mAh/cm ² to 4.8 mAh/cm ² ) for a 110 µm thick, 95% dense LCO cathode discharged at a 1C rate.
We also apply concepts and designs from these models to simulate the discharge performance of thick, high-density lithium-ion batteries with solid electrolytes to motivate even higher energy battery architectures. When discharged at a 1C rate, solid-state batteries with traditional particle-based composite cathodes (110 µm thick) cannot extract any energy at volume fractions above 94%, while batteries with high-diffusivity continuous cathodes and no solid electrolyte in the cathode region can achieve 3.8 mAh/cm ² at 95% solid volume fraction. These new cathode architectures which contain no electrolyte in the cathode region can significantly improve the gravimetric energy density of solid-state lithium-ion batteries.
This work uses a comparative analysis of cathode architectures to explore the interdependent impact of solid volume fraction, solid-diffusivity, cathode thickness, and discharge rate on lithium-ion battery areal capacity. We should how a combination of high diffusivity and continuous solid-state diffusion pathways provides an exciting path for realizing ultra-dense and thick cathodes with high energy density.
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