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(a) Cyclic voltammograms of SS316 support, NO, and annealed LNO-M. The number of cycles is in parentheses, (b) discharge curves for the annealed LNO-M and LNO-1/10 samples, (c) rate performance of annealed LNO-M and LNO-1/10 samples. Discharge curves for points situated in dotted rectangle are presented in Figure 13b.
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Lithium nickelate (LiNiO 2) and materials based on it are attractive positive electrode materials for lithium-ion batteries, owing to their large capacity. In this paper, the results of atomic layer deposition (ALD) of lithium-nickel-silicon oxide thin films using lithium hexamethyldisilazide (LiHMDS) and bis(cyclopentadienyl) nickel (II) (NiCp 2)...
Citations
... 34 Adsorption of water molecules leading to the formation of LiOH on the surface of the particles can also be another possible reason as the Li 1s core spectra would exhibit binding energy values (54.9 eV) in such a case. 35 Considering the broad peak (~2 eV) for Li 1s, it is inferred that the surface of all the cathodes is mostly covered with carbonate and hydroxide species. This effect of adsorbed species is very prominent in O1s spectra of both NP and NF samples. ...
High energy density Ni‐rich layered oxide cathodes LiNi 0.83 Co 0.12 Mn 0.05− x Al x O 2 ( x = 0 [NMC], 0.025 [NMCA], 0.05 [NCA]) are fabricated in two different microstructural forms: (i) nanoparticles (NP) and (ii) nanofibers (NF), to evaluate the morphology and compositional effect on the electrochemical properties using same precursors, with the latter fabricated by electrospinning process. Although all the cathodes exhibit a similar crystal structure as confirmed using X‐ray diffraction and Raman spectroscopy, the contrasting difference is observed in their electrochemical properties. XRD and XPS analyses indicate a higher amount of cationic disorder for the NP cathodes compared to their NF counterparts. Nanofibrous Ni‐rich layered oxide cathodes exhibit higher discharge capacities at all C‐rates in comparison to NP cathodes. When cycled at 1C‐rate for 100 cycles, capacity retention of 81% is observed for NCA‐NF, which is superior to all cathodes. Voltage decay as a function of the charge–discharge cycle is found to be low (0.2 mV/cycle) for nanofibrous cathodes compared to 1.5 mV/cycle for NP cathodes. The good rate capability and cyclic stability of nanofibrous Ni‐rich layered oxide cathodes are attributed to a shorter pathway of Li ⁺ diffusion and a large proportion of the active surface area.
... Both XPS and energydispersive x-ray spectroscopy (EDS) are used to detect the presence of elements in different materials 38 . However, the former technique provides information on the elemental composition of materials and differentiates the oxidation states of the elements 61 , by taking measurements within a few atomic layers usually from the top 1-10 nm on the surface, the latter method can determine the bulk composition of the elements with excitation volumes as deep as 3 µm deep into the sample 55 . ...
Preparation and characterization of nanostructured thin films have been reported by many researchers. X-ray photoelectron spectroscopy (XPS) method has been used over few decades in different fields such as superconductor, semiconductor, metallurgy and catalysis. In this work, elemental oxidation state, electronic state, chemical structure and chemical composition were investigated for metal sulfide, metal selenide, metal oxide and metal telluride films. Evaluation of binding energy for the obtained samples was reported. XPS spectra showed that annealing treatment has a very strong effect on the composition of the films. The elemental oxidation state and electronic state were strongly dependent on the specific experimental conditions.
... 47 However, the impediments of this technique to growing Li-containing cathode films consist of (i) lack of lithium-containing precursors with high vapor pressure, (ii) surface-limiting interference of water as a counter reagent, (iii) undesired high mobility of Li + at high temperatures required for deposition (200°C-300°C), and (iv) low deposition rates, all of these considerably diminish its attractiveness and efficiency. 3,48 Alternatively, 3D printing has emerged as a powerful and costsaving approach to partially address the drawbacks of other methods. 49,50 It enables the fabrication of 3D LIMBs with flexible dimensions and well-controlled geometries without the need for templates, both at the component (electrodes and current collectors) and packaging level. ...
Li-ion microbatteries are the frontline candidates to fulfill the requirements of powering miniature autonomous devices. However, it still remains challenging to attain the required energy densities of > 0.3mWh/cm-2µm-1 in a planar configuration. To overcome this limitation, 3D architectures of LIMBs have been proposed. However, most deposition techniques are poorly compatible with 3D architectures because they limit the choice of current collectors and selective deposition of the active materials. Electrodeposition was suggested as an alternative for rapidly and reproducibly depositing active materials under mild conditions, and with controlled properties. However, despite the huge potential, electrodeposition remains underexplored for LIMB cathode materials, partly due to challenges associated with the electrodeposition of Li-ion phases. Herein, we review advances in the electrodeposition of Li-ion cathode materials with the main focus set on the direct, one-step deposition of electrochemically active phases. We highlight the merits of electrodeposition over other methods and discuss the various classes of reported materials, including layered transition metal oxides, vanadates, spinel, and olivines. We offer a perspective on the future advances for the adoption of electrodeposition processes for the fabrication of microbatteries to pave the way for future research on the electrodeposition of cathode materials.
... The most intense peaks belong to Ni2P 3/2 and Ni2P 1/2 agrees with the reported values of NiO and the peak appeared at ~284 eV corresponds to C-C and C-H ligands of nickel precursor. Thus, the film contains predominantly NiO however other residues are also present in less amount [55,57]. Basic characterization in Fig. 1 reveal that ~26-27 nm thick uniform NiO thin films can be grown using ALD as desired. ...
Alternate methods for deposition of electrochromic metal oxide thin films need to be explored to obtain an optimized one while designing solid state hybrid or all-inorganic electrochromic device. To continue this quest, electrochromic performance from a hybrid electrochromic device obtaining using plasma assisted atomic layer deposition (ALD) grown nickel oxide (NiO) thin film and viologen has been studied. A few tens of nanometers thick films of NiO were deposited first on silicon to optimize the deposition parameters prior to depositing on Fluorine-doped Tin Oxide (FTO)/glass substrates for fabricating the device. The structural and morphological properties of as-prepared films were analyzed by scanning electron spectroscopy (SEM), x-ray diffraction (XRD), Raman spectroscopy and x-ray photo electron spectroscopy (XPS) techniques. Thereafter, a solid state organic-inorganic hybrid electrochromic device was fabricated using Nickel oxide (NiO) and ethyl viologen (EV). The device changes its color between transparent and blue states under the potential window of ±1.7 V while taking less than 2s for toggling between the two-colored states. The device also exhibits an impressive electrochromic behavior with coloration efficiency of 118cm 2 /C, contrast ratio of 21% and a good cycle life/stability. The ALD grown films appeared to have advantage over other methods as it yields an atomically smooth and crack-less nano film so that proper power utilization take place for color switching. All these results open a new way to the fabrication of inorganic component to fabricate high-performance hybrid solid state electrochromic devices.
... According to the accuracy and dependability results of LiO, these interface states often cause a bias shift and frequency dispersion in electrical conductivity, which makes frequency dependent electrical and dielectric characteristics highly significant. [7,8]. ...
... One of the methods for improving LIB's operation conditions is the creation of a stable cathode structure. The promising way to obtain stable structures for thin-film batteries is synthesis of a multilayer system using the atomic layer deposition (ALD) method followed by heat treatment [7]. The ALD method involves the cyclic repetition of self-limiting controlled reactions of the gas phase reagent with the substrate surface, which allows the structure to be obtained with uniform chemical composition and the required thickness over the entire surface, even with high roughness [8]. ...
... However, it was found that the coatings also contain traces of substrate elements and an insignificant concentration gradient of Ni and Co in addition to Ni-rich crystallites. Thence, in the present work, the annealing time was reduced to 1 min to prevent decomposition into Ni-rich and Co-rich zones [9], a Cr buffer layer was added between the cathode and current collector to prevent intense diffusion of substrate elements [7]. ...
... Lithium tert-butoxide (LiOtBu, 97%, Sigma-Aldrich, Burlington, MA, United States), bis(cyclopentadienyl)nickel (II) (Ni(Cp) 2 ; 99%, Dalchem, Nizhny Novgorod, Russia) and bis(cyclopentadienyl)cobalt (II) (Co (Cp) 2 ; 99%, Dalchem, Nizhny Novgorod, Russia) were used as lithium, nickel, and cobalt precursors, respectively. The deposition conditions were chosen based on previous studies [7,16]. The obtained multilayer structure was annealed at 800 • C for 1 min in the air [9]. ...
Thin-film Li-ion batteries produced by precise thickness control atomic layer deposition (ALD) method are promising, safe, and high-energy density sources for miniature devices. The paper presents a detailed analysis of the multilayer thin film cathode for microbatteries. Structures were obtained by combining several technological parameters to increase capacity, uniformity, and lifetime. The protective function of a nano-sized coating was demonstrated. The influence of coating application on cathode capacity was explained. The studied structure consists of Ni-rich cathode layer modified with an amorphous Li-Ta-O functional layer on a steel substrate with a Cr coating. The cathode and the functional layer were obtained by the ALD multilayer approach followed by heat treatment at 800 °C for a minute. According to XPS and TEM data, the composition of the cathode after annealing was LiNi0.7Co0.3O2 well-defined structure without separation into Ni-rich and Co-rich layers, with texturing of crystallite pillars and with the absence of Fe. The Li-Ta-O films have a slight chemical composition gradient from Li3Ta1.2O4 on the surface to Ta1.7O5 in bulk. The electrochemical characterization showed that combining the functional layer and cathode heat treatment preserves the electrochemical capacity (32 µAh·µm⁻¹·cm⁻²) and increases Coulomb efficiency.
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... LIBs can overheat and could explode. [10][11][12][13] Continuous studies together with development have improved the technology of the battery up to a point in which credible and safe LIBs are officially integrated into solar panels and windmills as well as hybrid electrics and EVs. Nevertheless, technological safety remains a worry because there is still not enough service life and the cost is very much high. ...
... However, the ALD process is the most promising of the aforementioned processes, and it is focused on the chemical reactions that self-terminate between the solid state's surface species and precursor (volatile). 11 The self-limiting characteristic of ALD supports homogenous coatings and conformational growth on the surfaces of porous, planar, as well as high-aspect structures. 12,13 Also, ALD can effectively control film composition and thickness with better precision. ...
Lithium‐ion battery (LIB) systems provide a very promising range of power supply systems for diverse applications like electric vehicles, hybrid plug‐in electric vehicles, grid storage systems, and microelectronics. Nevertheless, the features of lithium‐ion batteries (LIBs), which include energy density and power, cycle lifetime, safety, as well as cost, must be enhanced in order to achieve all these feasible applications. Atomic layer deposition (ALD), as a result of its unique benefits above other thin‐film methods of deposition, emerges as a very useful approach for use in improving the efficiency of LIBs. This review summarizes ALD's advanced successes in designing new nanostructured solid‐state electrolytes and electrode materials, as well as the adjustment of the interfaces of electrodes and electrolytes through the application of surface coatings for the avoidance of undesirable side reactions to attain maximum adequate performance of the electrode. Also covered are ideas for the potential advancement of ALD studies and technology for the applications of LIBs. This review paper is anticipated to furnish researchers within the LIB and ALD fields with valuable information that would encourage much more extensive research on the use of ALD to produce new generation LIBs. This review presents the recent advancements in electrode materials as well as some new electrode fabrication processes for Li‐ion batteries. Certain prospective materials with improved electrochemical performance have also been reported, along with a review of the recent precursors utilized for the ALD of battery materials. The efficiency of the ALD process in providing sufficient solutions to the problems associated with the utilization of Lithium‐ion batteries is also discussed. ALD process for lithium‐ion batteries
... The uniform deposition of electrode materials on 3D objects and high-aspect-ratio structures is possible using atomic-layer deposition (ALD) [3]. However, the difficulties of obtaining the final crystal structure of cathode materials synthesized by ALD at 200-300 • C are required to use additional heat treatment (HT) [4]. Using this approach, LiCoO 2 [5], Li x Mn 2 O 4 [6], Li-Ni-O/Li-Ni-Si-O [7] cathodes were obtained. ...
... Remote oxygen plasma was the oxidizing agent. Deposition conditions were based on previous studies [4,7]. Heat treatment was set at 800 • C for 5 min under an air [4]. ...
... Deposition conditions were based on previous studies [4,7]. Heat treatment was set at 800 • C for 5 min under an air [4]. ...
Temperature conditions are significant for the crystal structure formation of prospective cathode materials, determining their further performance and cycle life. The paper presents the results of a detailed analysis of the multilayer thin films before and after heat treatment. The investigated multilayer structures consist of a two-layer system of an amorphous nickel-doped Li-O layer and a NiO⋅CoO layer obtained by atomic-layer deposi-tion on Si substrate. It was shown that annealing at 800 • C for 5 min is sufficient to form a crystalline film with energy favorable spherical-like Li-Ni-CoO structures on the surface with a size of 50-150 nm. Chemical mapping after heat treatment using EDX showed the formation of Ni-rich (spherical-like structures) and CoO intermediate layers. The electron energy loss spectroscopy results confirm the presence of Li in the top Ni-rich layer and are embedded in its crystalline structure. X-ray and electron diffraction showed a polycrystalline cathode structure of lithium-containing nickel and cobalt oxides.
... The total plasma pulse time was 19.5 s (Ar purge during 0.5 s with flow rate 40 sccm; Ar and O 2 plasma purge during 14 s with flow rate 90 sccm; Ar purge during 5 s with flow rate 40 sccm). Deposition conditions were based on our previous studies devoted to ALD of nickel oxide and Al 2 O 3 [18,27]. NAO thin films were synthesized using supercycles' scheme consisting of reagents pairs (x*[NiCp 2 -O 2 plasma] + y*TMA-O 2 plasma), where x/y were 1/25, 1/50, and 1/75. ...
Thin-film solid-state lithium-ion batteries (SSLIBs) are promising power supplies for small-scale electronics, particularly for Internet of Things (IoT) devices, sensors, microchips, and others. Transition metal oxides have potential for application in SSLIBs due to their high theoretical capacity. In this work, films of mixed nickel and aluminum oxides (NAO) were obtained at a temperature of 300 ℃ by plasma-assisted atomic layer deposition (ALD). The growth rates of the films turned out to be higher than the expected ones calculated from the growth rates of monoxide films. The increase in the growth rates is presumably associated with the chemosorption of a larger number of reagent molecules on the film surface during the alternation of reagent pairs during the ALD. High growth per cycle values of alumina lead to higher aluminum content and lower density of NAO films. The phase composition of NAO 50/1 and 75/1 films corresponds to the cubic NiO (Fm-3 m) space group. NAO films have a uniform surface dotted with round and fragmented particles. The electrochemical properties of the obtained films were studied by the cyclic voltammetry and cyclic charge–discharge tests at discharge currents from 0.5 to 60C. With an 80-fold increase in the discharge current, the electrode capacity decreased by 30%. It was shown the presence of aluminum in certain concentrations slows down the growth of pseudocapacitance by 20–28% and does not significantly affect the Coulomb efficiency of the films obtained.
... The intensity of W 4f signals does not increase significantly with increasing etching times ( Figure S5a,b), indicating that a homogeneous distribution of the W element exists in the structure, thus confirming the doping role of tungsten at the optimum photoelectrode. 35 The EPR spectrum in Figure S6 shows weak signals centered at g = 4.2759 and around g = 2.0012 at room temperature. These signals are attributed to the high-spin Fe 3+ (S 5/2 ) and low-spin Fe 3+ (S 1/2 ), respectively. ...
