Li-ion Diffusion Coefficient Research Articles

Ti3C2Tx MXene coated 3D ordered macroporous germanium anodes for Li-ion batteries with enhanced cycling stability and fast Li-ion mobility

The current trend in electronic device development and electric vehicle technology has resulted in A growing need for negative electrode materials that possess high capacity and quick Li-ion transport properties. Ge-based materials are considered the very promising candidates owing to their high theoretical capacity and facile alloying reaction with Li. In order to enhance the rate of Li-ion diffusion and account for the volume change of over 300 %, a Ti3C2Tx MXene coated 3D ordered macroporous germanium (3DOM Ge@MXene) structure was successfully developed. The 3DOM Ge@MXene provides a 1490 mAh g−1 initial reversible capacity at 0.32 A g−1. Additionally, after 100 cycles, it displays a consistent cycling ability of 1034 mAh g−1. The MXene coating also improves the material's Li-ion rapid transfer performance, with Li-ion diffusion coefficient of 1.35 × 10−10 cm2s−1 for anodic and 2.2 × 10−10 cm2s−1 for cathodic.

Mechano-thermochemical preparation of nanostructured (FeCoNiCr/Mn)3O4 high and medium entropy oxides: Structural, microstructural, magnetic and Li-ion storage characterization

Mechano-thermochemical synthesis of (FeCoNiCrMn)3O4 high-entropy oxide (HEO) and (FeCoNiCr)3O4 medium-entropy oxide (MEO), and their structural, microstructural, magnetic, surface and electrochemical characteristics are investigated. Ball milling substantially reduces crystalline sizes of oxide precursors, causing their partial solid-state dissolution, driving the rapid formation of HEO and MEO during the subsequent thermal treatment. Nanostructured HEO prepared at 900 °C (HEO-900) comprises single-phase octahedral crystals mostly within the range 60–80 nm, while MEO-900 crystals (80–120 nm) exhibit a greater degree of agglomeration. The contribution of oxygen vacancies to total surface oxygen in MEO-900 (20.6 %) is lower than that of HEO-900 (27.6 %). HEO-900 exhibits a superior reversible Li-ion storage capacity of 1050.6 mAh/g after 300 cycles at 100 mA/g, outperforming MEO-900. However, at the higher current density of 500 mA/g, MEO-900 shows superior performance, with a reversible capacity of 432.2 mAh/g (70.3 % retention) after 750 cycles. The charge transfer resistance of fresh HEO-900 (359.0 Ω) is greater than that of MEO-900 (241.4 Ω), and the average Li-ion diffusion coefficient in HEO-900 (10-13.3 cm2 s−1) is lower than that on MEO-900 at (10-13.1 cm2 s−1) due to the greater structural complexity of the former. Full cells incorporating HEO-900 and MEO-900 anodes with LiFePO4 cathode demonstrate an energy density of 296.4 and 274.6 Wh kg−1, respectively. The saturation magnetization of HEO-900 and MEO-900 is significantly high at 33.98 and 33.80 emu/g, respectively, enabling the easy magnetic recovery of electrodes made from these compounds in spent LIBs.

Structure, Composition and Electrochemical Properties of Disordered Rock-Salt LiCoO2 Thin Films Prepared by Ion Beam Assisted Deposition

Ion beam assisted deposition is a method used to deposit thin films while irradiating the growing film with an ion beam. This technique is known to be effective in crystallization and orientation control at low temperatures. In this study, LiCoO2 (LCO) thin films were prepared at temperatures below 100 °C using ion beam assisted pulsed laser deposition. The structure, composition, and electrochemical properties of these films were characterized. The results indicated that LCO thin films with a disordered rock salt structure and triaxial orientation were successfully grown on polycrystalline aluminum and quartz glass substrates using ion beam assisted deposition. Furthermore, the diffusion coefficient of Li ions and the charge/discharge capacity were significantly improved compared to LCO thin films with a disordered rock salt structure prepared without the ion beam assisted process.

Activating Redox Kinetics of Li2S via Cu+, I- Co-Doping Toward High-Performance All-Solid-State Lithium Sulfide-Based Batteries.

All-solid-state lithium sulfide-based batteries (ASSLSBs) have drawn much attention due to their intrinsic safety and excellent performance in overcoming the polysulfide shuttle effect. However, the sluggish kinetics of Li2S cathode severely impede commercial utilization. Here, a Cu+, I- co-doping strategy is employed to activate the kinetics of Li2S to construct high-performance ASSLSBs. The electronic conductivity and Li-ion diffusion coefficient of the co-doped Li2S are increased by five and two orders of magnitude, respectively. Cu+ as a redox medium greatly improves the reaction kinetics, which is supported by ex situ X-ray photoelectron spectroscopy. Density functional theory calculation (DFT) shows that Cu+, I- co-doping reduces the Li-ions diffusion energy barrier. The co-doped Li2S exhibits a remarkable improvement in capacity (1165.23 mAh g-1 (6.65 times that of pristine Li2S) at 0.02 C and 592.75 mAh g-1 at 2 C), and excellent cycling stability (84.58% capacity retention after 6200 cycles at 2 C) at room temperature. Moreover, an ASSLSB, fabricated with a lithium-free (Si─C) anode, obtains a high specific capacity of 1082.7 mAh g-1 at 0.05 C and 97% capacity retention after 400 cycles at 0.5 C. This work provides a broad prospect for the development of ASSLSBs with practical energy density exceeding that of traditional lithium-ion batteries.

Influence of Transition-Metal Order of LNMO Spinel on the Li Ion Diffusion

Cathode materials contribute a substantial portion to the weight, cost, and environmentally sustainability of LIBs. A key strategy to enhance energy density at reduced cost and improved sustainability is to develop more cost-effective, cobalt-free, higher-energy-density alternatives. Among the Co-free electrode cathode chemistries, the LiNi0.5Mn1.5O4 (LNMO) spinel stands out as most promising. It exhibits a high specific energy density of 650 Wh/kg, attributed to its elevated operating voltage of approximately 4.7 V vs. Li+/Li. Furthermore, LNMO is more thermally stable than NMC and has high ionic conductivity. However, LNMO suffers from rapid capacity decay leading to short battery life, and high-voltage electrolytes that are resistant to decomposition at the higher operating voltages are required.LNMO forms two phases depending on the ordering of transition metals (TM). In the disordered phase, Ni and Mn ions are randomly distributed on the 16d sites of the Fd3̅m cubic unit cell, whereas in the ordered phase, the which Ni and Mn atoms occupy 4b sites and 12d sites of the P4332 cubic cell, respectively. In this work, the impact of TM ordering on fundamental parameters such as the unit cell size, electrode expansion, and Li-ion diffusion coefficients at different states of charge were explored using techniques such as in-operando x-ray diffraction, in-situ dilatometry, galvanostatic intermittent titration technique, and electrochemical impedance spectroscopy. The electrodes for these studies were prepared using both PVDF and water-based binders such as CMC in order to gain key insights into the effect of aqueous electrode processing on the Li+-ion transport parameters, interface resistances, and electrode expansion during cycling.

Effect of Mo6+ induced valence changes of transition metal ions in Mn-rich layered cathode materials on electrochemical performance

Layered cathode materials for lithium-ion batteries have been extensively investigated; however, comparatively scant attention has been paid to Mn-rich layered cathode materials. Herein, LiNi0.5Mn0.5O2 cathode materials are doped to investigate the effect of doping elements on the electrochemical properties of Mn-rich layered cathodes. XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), and SQUID (superconducting quantum interference device) results reveal that Mo doping affects the electrochemical properties of the cathode materials by changing the valence state of transition metal ions. Due to the Mo6+ ions doping, a large proportion of Mn3+ ions present in LiNi0.5Mn0.5O2 were converted to Mn4+ ions, which alleviated the Jahn-Teller effect and reduced the elongated Mn-O octahedra, thus increasing the Li layer spacing and facilitating Li+ diffusion. Therefore, 1 % Mo-doped cathode exhibits a significantly improved Li-ion diffusion coefficient and superior rate performance with a specific discharge capacity of 103 mAh·g−1 at 5C. Meanwhile, the cathode materials significantly improve cycling performance due to the reduction in the amount of Mn3+. The current study provides guidelines for the modification of Mn-rich layered cathodes in the future.

Can Electrochemical Impedance Spectroscopy be Replaced by Direct Current Techniques in Battery Diagnosis?

Electrochemical impedance spectroscopy (EIS), a conventional and alternating-current-(AC)-based technique for impedance measurement, is commonly used in battery diagnosis. However, it requires expensive equipment and demanding operating conditions and is complex and model-dependent in data analysis. Recently, novel direct current (DC) analytics have emerged as an alternative to EIS. They are simple yet powerful, being capable of revealing impedance information that traditionally could only be obtained through EIS and determining Li-ion diffusion coefficient. Besides, a complete EIS spectrum can be predicted based on constant current charging curves in the support of machine learning methods. This work highlights the similarities and discrepancies between DC techniques and EIS in the electrochemical analysis of Li-ion batteries. Looking ahead, DC techniques may be a promising substitute for EIS in future battery diagnosis, requiring simplified equipment while offering a deep understanding of battery impedance and its underlying electrochemical processes.

Order-disorder structural engineering of vanadium oxide anode: Balancing ionic and electronic dynamic for fast-charging aqueous Li-ion battery

Fast-charging aqueous lithium-ion batteries (ALIBs) are considered as promising energy storage devices because of their non-flammability and environmentally friendly characteristics. However, how to balance the ionic and electronic dynamics for fast charging reactions remains a significant challenge under the current research status. Here, the order-disorder structural engineering strategy is adopted to resolve this issue, considering the difference between ion and electron transportation in the crystalline and amorphous phases, respectively. Vanadium oxide anodes were developed with optimized ionic and electronic dynamics by using an organic-inorganic hybrid material as a precursor along with refined regulation on the calcination temperature and time. This facile and large-scale extendable approach harnesses the benefits of the order-disorder structure to optimize Li+ storage efficiency and facilitate the high reversibility of Li-ion during fast charging. Consequently, the order-disorder V2O5-based full cell with LiMn2O4 as a cathode exhibits high specific capacity (262.71 mAh g−1, 89.35 % of the theoretical capacity of V2O5), high energy density (166.04 Wh kg−1), fast Li-ion diffusion coefficient (7.34×10−5 cm2 s−1) and fast-charging performance (only 6 min achieves 82.84 % of initial state-of-charge capacity). This work explores the ionic and electronic dynamic of ordered-disorder structure and offers new insights into the development of fast-charging metal ion batteries.

Exploring Li-Ion Transport Properties of Li3TiCl6: A Machine Learning Molecular Dynamics Study

We performed large-scale molecular dynamics simulations based on a machine-learning force field (MLFF) to investigate the Li-ion transport mechanism in cation-disordered Li3TiCl6 cathode at six different temperatures, ranging from 25°C to 100°C. In this work, deep neural network method and data generated by ab − initio molecular dynamics (AIMD) simulations were deployed to build a high-fidelity MLFF. Radial distribution functions, Li-ion mean square displacements (MSD), diffusion coefficients, ionic conductivity, activation energy, and crystallographic direction-dependent migration barriers were calculated and compared with corresponding AIMD and experimental data to benchmark the accuracy of the MLFF. From MSD analysis, we captured both the self and distinct parts of Li-ion dynamics. The latter reveals that the Li-ions are involved in anti-correlation motion that was rarely reported for solid-state materials. Similarly, the self and distinct parts of Li-ion dynamics were used to determine Haven’s ratio to describe the Li-ion transport mechanism in Li3TiCl6. Obtained trajectory from molecular dynamics infers that the Li-ion transportation is mainly through interstitial hopping which was confirmed by intra- and inter-layer Li-ion displacement with respect to simulation time. Ionic conductivity (1.06 mS/cm) and activation energy (0.29eV) calculated by our simulation are highly comparable with that of experimental values. Overall, the combination of machine-learning methods and AIMD simulations explains the intricate electrochemical properties of the Li3TiCl6 cathode with remarkably reduced computational time. Thus, our work strongly suggests that the deep neural network-based MLFF could be a promising method for large-scale complex materials.

Electrochemical performances of Ni-rich and Li-rich blended cathodes for Li-ion batteries

Herein, the effect of the blending ratio on the capacity, energy density, and cycling performance of Ni-rich (LiNi0.8Co0.1Mn0.1O2) (NCM) and Li-rich (Li7/6Mn1/2Ni1/6Co1/6O2) (LR) cathode materials was investigated. The optimally blended cathode exhibited capacity retentions of 80.7% and 76.9% after 200 cycles at 25 °C within 2–4.6 V and 100 cycles at 55 °C within 2–4.5 V, respectively, showing higher cycling stability and flatter voltage decline than pure NCM and pure LR cathodes. Additionally, the optimized cathode exhibited the smallest increase in charge-transfer resistance (Rct) and highest Li-ion diffusion coefficient (DLi+) among all tested samples after high-temperature cycling. This study highlights the unique electrochemical properties of blended cathode materials and demonstrates their high structural stability in Li-ion batteries (LIBs).

In-situ texturing hollow carbon host anchored with Fe single atoms accelerating solid-phase redox for Li-Se batteries

Se-based cathodes have caught tremendous attention owing to their comparable volumetric capacity and better electronic conductivity to S cathodes. However, its low utilization ratio and sluggish redox kinetics due to the high reaction barrier of solid-phase transformation from Se to Li2Se limit its practical application. Herein, an in-situ texturing hollow carbon host by gas–solid interface reaction anchored with Fe single-atomic catalyst is designed and prepared for advanced Li-Se batteries. This Se host presents high pore volume of 1.49 cm3 g−1, Fe single atom content of 1.53 wt%, and its specific structure protects single-atomic catalyst from the destructive reaction environment, thus balancing catalytic activity and durability. After Se loading by reduction of H2SeO3, this homogenous Se-based cathode delivers a superior rate capacity of 431.3 mA h g−1 at 4C, and great discharge capacity of 301.8 mA h g−1 after 1000 cycles at 10C, with high Li-ion diffusion coefficient and capacitance-contributed ratio. The distribution of relaxation times analysis verifies solid-phase transformation mechanism of this cathode and density functional theory calculations confirm the adsorption and bidirectionally catalysis effect of Fe single-atomic catalyst. This work provides a new strategy to prepare high-efficient Se cathode associated with non-noble metal single atoms for high-performance Li-Se batteries.

Facile Synthesis and Electrochemical Analysis of Zn-Doped V2O5 Anode Materials for High-Rate Li Storage

The surging demand for Li rechargeable batteries with high energy densities and rapid rate capability has propelled research on materials that can replace the conventional anode materials like graphite. Vanadium pentoxides (V2O5) have emerged as promising anode candidates owing to their excellent rate capability. Specifically, V2O5 allows the electrochemical prelithiation process, in which three Li-ions can be inserted to form Li3V2O5, followed by reversible insertion and extraction of two Li-ions. Nevertheless, the unsatisfactory Li-ion diffusion coefficients and electrical conductivities of these materials remain major drawbacks. Here, we propose a Zn-doped V2O5 anode, fabricated using a two-step sol–gel method, for high-rate Li-ion batteries. Zn was incorporated into V2O5 to enhance the Li-ion transport kinetics through the electrode. The crystal structure (orthorhombic) of Zn-doped V2O5 was identified by X-ray diffraction analysis, and the Zn doping was confirmed by X-ray photoelectron microscopy. The effect of Zn doping was thoroughly examined using various analytical methods, such as cyclic voltammetry and galvanostatic intermittent titration technique. The Zn-doped V2O5 electrode exhibited remarkable cycling durability, enduring for 1000 cycles, while retaining an enhanced capacity, even under a high rate of 2C.

Collapsed N&S dual-doped carbon nanocages as high-density anode for ultrahigh volumetric performance of Li-ion batteries

Compact lithium-ion batteries for miniaturized devices require high-volumetric-performance anodes. Either the graphite with high density or the porous nanocarbons with high gravimetric performance is limited in volumetric performance. Herein, we construct a series of anode materials, i.e. the collapsed carbon nanocages with different dopants, by capillarity compression, which achieves a high density of ∼0.97 g cm−3 but remains abundant micropores with increased active sites and enlarged interlayer distance. The N&S dual-doping redistributes the charges of sp2 carbon to an optimal status, leading to the high Li-ion capacity, meanwhile facilitates the wettability at the electrode/electrolyte interface, leading to the enhanced Li-ion diffusion coefficient. Accordingly, the collapsed N&S dual-doped carbon nanocages (cNSCNC) anode exhibits a record-high volumetric capacity of 1578 mAh cm−3 at 0.1 A g−1, excellent rate capability and cycling stability, thus achieving an ultrahigh volumetric energy density of 1087 Wh L−1 at 120 W L−1 for the cNSCNC//LiFePO4 full cell.

Endogenous Interfacial Mo-C/N-Mo-S Bonding Regulates the Active Mo Sites for Maximized Li+ Storage Areal Capacity.

Active sites, mass loading, and Li-ion diffusion coefficient are the benchmarks for boosting the areal capacity and storage capability of electrode materials for lithium-ion batteries. However, simultaneously modulating these criteria to achieve high areal capacity in LIBs remains challenging. Herein, MoS2 is considered as a suitable electroactive host material for reversible Li-ion storage and establish an endogenous multi-heterojunction strategy with interfacial Mo-C/N-Mo-S coordination bonding that enables the concurrent regulation of these benchmarks. This strategy involves architecting 3D integrated conductive nanostructured frameworks composed of Mo2C-MoN@MoS2 on carbon cloth (denoted as C/MMMS) and refining the sluggish kinetics in the MoS2-based anodes. Benefiting from the rich hetero-interface active sites, optimized Li adsorption energy, and low diffusion barrier, C/MMMS reaches a mass loading of 12.11mgcm-2 and showcases high areal capacity and remarkable rate capability of 9.6mAhcm-2@0.4mAcm-2 and 2.7mAhcm-2@6.0mA cm-2, respectively, alongside excellent stability after 500 electrochemical cycles. Moreover, this work not only affirms the outstanding performance of the optimized C/MMMS as an anode material for supercapacitors, underscoring its bifunctionality but also offers valuable insight into developing endogenous transition metal compound electrodes with high mass loading for the next-generation high areal capacity energy storage devices.

Preparation of SnO2@graphite Anode based on the Oriented Deposition Methodology with Superior Electrode Behavior for Li Ion Battery

AbstractSnO2‐based anode materials are deemed to be one of the most prospective anode materials for Li ion batteries (LIBs) with higher theoretical capacity as compared to conventional graphite. However, the weak electrical conduction and large volume expansion limit its application in eVeryday life. Here, a simple and low‐cost oriented deposition methodology is developed to prepare SnO2@graphite composite, which is obtained based on the redox reaction mechanism between SnSO4 and graphite. SnO2 nanoparticles are uniformly anchored on the carbon layer of graphite. The close anchoring of SnO2 in graphite effectively inhibits the volume expansion of SnO2 during lithiation/delithiation processes, and good combination state between them guarantees the excellent electrical conductivity of the composite. As anode for LIBs, SnO2@graphite electrode delivers superior reversible capacity and provides an improved rate capability compared to graphite electrode. Benefiting from the tight combination of SnO2 and graphite, the Li ion diffusion coefficient of SnO2@graphite electrode is almost twice that of graphite electrode. Pairing with LiFePO4 cathode, the SnO2@graphite/LiFePO4 full cell exhibits higher energy/power densities by comparison with graphite/LiFePO4. Besides, this advanced SnO2@graphite composite material with superior anode behavior can be mass produced by the reported methodology.

High Li-ion diffusion coefficient in LiMn1.5Ni0.5O4 thin films for all-solid Li-ion battery applications

Among various choices of high-performance cathode materials, Ni substituted LiMn2O4 spinel LiMn1.5Ni0.5O4 (LMNO) has proved to be one of the solutions to yield a high-performance and high-energy density material, which can operate at a higher potential window. This study explores the high diffusion coefficient and electrochemical performance at wide current rates of LMNO thin films with less than 50 nm thickness, fabricated on SrTiO3 and SS substrates by the pulsed laser deposition method. The LMNO film with less thickness and the performance without binder and conducting carbon widen the Li-ion path and decrease diffusion length, resulting a higher diffusion coefficient on the order of 10−5 to 10−6 cm2/s, which is several orders higher than the previously obtained reports for bulk counterpart. The cycling stability and rate capability at different current densities of LMNO thin film electrodes are further investigated. Charge–discharge profile at varying current rates of 5, 10, 15, 20, 25, 50, 75, 100, and 125 mA/cm2 is obtained for 500 cycles. The as fabricated film shows a stable profile for 500 cycles with 1.3 and 2.3 μA h/cm2 areal discharge capacity at 25 and 5 mA current rates, respectively. Electrode interfacial properties of LMNO film (before and after cycles) are analyzed using impedance technique. This study indicates that the LMNO thin films can be employed as a cathode layer for fabricating the all-solid thin film batteries for energy applications.

Electrodeposited Lithiophilic Zn Thin Film on the Current Collector for Improved Cyclability of Anode-Free Lithium Metal Battery

Anode-free lithium metal batteries (AFMBs) are recently presented as the new generation of Li metal batteries benefiting high gravimetric and volumetric energy densities due to the zero excess lithium. However, poor electrochemical stability and maximum cyclability of around 40-50 cycles due to the zero excess Lithium prevent the AFLMBs to be functional1. Here, lithiophilic electrodeposited Zn thin film on the current collector is reported in order to decrease the lithium nucleation overpotential and improve the plating/stripping process during alloying and dealloying. Moreover, columbic efficiency is increased by applying more zinc coated on the cupper current collector and by providing a more hospitable site for Li nuclei to plate2. Due to the alloy formation of Li-Zn, more conformal Li growth on the current collector is provided and homogeneous Li distribution and smooth morphology are observed by SEM images. The cells in different zinc thin layer coating are cycled with different current densities as well as long-term cycling by galvanostatic cycling charge-discharge cycling. As a result, increasing the thin film thickness up to 1 micron significantly enhances the electrochemical stability of the cells such as higher columbic efficiency and cyclability, lower Li nucleation overpotential. Finally, the Li-ion chemical diffusion coefficients DLi, are evaluated by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) and the results are compared to each other3.References Maddukuri, S. et al. On the challenge of large energy storage by electrochemical devices. Electrochim Acta 354, 136771 (2020).Merso, S. K. et al. An in-situ formed bifunctional layer for suppressing Li dendrite growth and stabilizing the solid electrolyte interphase layer of anode free lithium metal batteries. J Energy Storage 56, 105955 (2022).Xie, J. et al. Determination of Li-ion diffusion coefficient in amorphous Zn and ZnO thin films prepared by radio frequency magnetron sputtering. Thin Solid Films 519, 3373–3377 (2011).

Predicting Ion Diffusion from the Shape of Potential Energy Landscapes.

We present an efficient method to compute diffusion coefficients of multiparticle systems with strong interactions directly from the geometry and topology of the potential energy field of the migrating particles. The approach is tested on Li-ion diffusion in crystalline inorganic solids, predicting Li-ion diffusion coefficients within 1 order of magnitude of molecular dynamics simulations at the same level of theory while being several orders of magnitude faster. The speed and transferability of our workflow make it well-suited for extensive and efficient screening studies of crystalline solid-state ion conductor candidates and promise to serve as a platform for diffusion prediction even up to the density functional level of theory.

Unlocking the Potential of Li-Rich Mn-Based Oxides for High-Rate Rechargeable Lithium-Ion Batteries.

Lithium-rich Mn-based oxides have gained significant attention worldwide as potential cathode materials for the next generation of high-energy density lithium-ion batteries. Nonetheless, the inferior rate capability and voltage decay issues present formidable challenges. Here, a Li-rich material equipped with quasi-three-dimensional (quasi-3D)Li-ion diffusion channels is initially synthesized by introducing twin structures with high Li-ion diffusion coefficients into the crystal and constructing a "bridge" between different Li-ion diffusion tunnels. The as-prepared material exhibits monodispersed micron-sized primary particles (MP), delivering a specific capacity of 303mAhg-1 at 0.1 C and an impressive capacity of 253mAhg-1 at 1 C. More importantly, the twin structure also serves as a "breakwater" to inhibit the migration of Mn ions and improve the overall structural stability, leading to cycling stability with 85% capacity retention at 1 Cafter 200 cycles. The proposed strategy of constructing quasi-3Dchannels in the layered Li-rich cathodes will open up new avenues for the research and development of other layered oxide cathodes, with potential applications in industry.

Surface morphology engineering of WO3 films for increasing Li ion insertion area in electrochromic supercapacitors (ECSCs)

Two different dry deposition methods were used to deposit electrode films with different surface morphologies in relation to the performance of electrochromic supercapacitors (ECSCs): direct current (DC) magnetron sputtering and the nanoparticle deposition system (NPDS). The NPDS method, which sprays powders onto the substrate using pressure differences, deposited WO3 film with its roughness of 36 nm and its thickness of 383 nm, while the sputtered WO3 film had its roughness of 3 nm and its thickness of 262 nm. Due to its dramatic difference in surface roughness, the NPDS-WO3 thin film had larger reaction surface area as well as Li-ion diffusion coefficient than those of sputtered-WO3 films. As a result, the ECSC device with NPDS-WO3 exhibited 19 % higher coloration efficiency with greater charge capacity compared to those with sputtered-WO3. However, the ECSC device with NPDS-WO3 showed different charge/discharge with trapped Li ions during the coloring(charging)/bleaching(discharge) processes respectively, leading to rapid degradation of the device. This research highlights the clear difference between its characteristics of the thin films fabricated using the NPDS vs. sputtering methods in relation to its surface roughness so that this study would be potentially beneficial in engineering various properties of ECSC devices.