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1.
Strong blue colouration has been induced in rf sputtered thin films of WO3 by electrochemical injection of H+, Li+, and Ag+ ions from various solid and liquid electrolytes. Electrical conductivity and optical properties of the coloured films are reported. Comparison of these properties with those of single crystal tungsten bronzes of equivalent composition is made. Evidence, electrical and optical, for a non-uniform distribution of injected ions produced by relatively fast diffusion down grain boundaries in these polycrystalline WO3 films is presented. A model for the optical absorption consisting of two components, due to (i) conduction electron intra-band transitions (in states close to crystalline surfaces) and (ii) transitions from unionized donor states to the conduction band (in the grain boundary phase), is tentatively proposed.  相似文献   

2.
The effects of molybdenum [Mo] doping on the electrochromic behavior of spray pyrolised tungsten trioxide [WO3] thin films have been studied. It has been observed that the color-bleaching kinetics, coloration efficiency, and stability of electrochromic WO3 films are closely related to molybdenum doping concentration, apart from their microstructure and crystallinity. While a nominal 6.0 at.% molybdenum doping produces best electrochromic response in WO3 films, the electrochemical stability is highest when the nominal concentration of molybdenum is about 2.0 at.%. The improved electrochromic behavior of the Mo doped WO3 films has been explained from the improved H+ ion diffusion coefficient in the films during coloration and decoloration process.  相似文献   

3.
《Ceramics International》2021,47(23):32570-32578
Herein, vertically aligned Al:WO3 nanoplate arrays were directly grown on ITO glass by a facile electrodeposition method and annealed in an argon atmosphere at 450 °C for 2h. Besides, this study reports the influence of Al doping on the electrochromic properties of WO3 film in detail. Electrochromic properties such as cyclic voltammetry, chronoamperometry and optical transmittance were analyzed by protonic insertion/extraction in the 1 M LiClO4/propylene carbonate as an electrolyte. The noticeable reversible color changing from transparent to the blue can be realized under the potential bias of ±1.0 V. XRD studies show that the produces films have highly crystalline structure. The EDS results clearly confirm the incorporation of Al element into the WO3 network. From the optical absorption measurement, direct band gap energies are calculated as 3.62 and 3.34 eV for the WO3 and the Al:WO3, respectively. Compared to the as-prepared WO3, the Al:WO3 film exhibits outstanding electrochromic performance, including wide optical modulation (55.9%), high coloration efficiency (148.1 cm2C-1), quick reaction kinetics (1.23 s and 1.01 s for colored and bleaching times, respectively), good rate capability and cycle durability at a wavelength of 632.8 nm. EIS measurements based on a charge-transfer resistance reveal that the dramatic improvement in the electrochemically active surface is achieved in the Al:WO3 film. The increase of active surface facilitates transport kinetics for electron and ion intercalation/deintercalation within the porous metal oxide to enhance coloration efficiency. Comparatively energy levels of the WO3 and the Al:WO3 electrochromic films are also represented. From the Mott-Schottky studies, it is estimated that the donor concentration of the films is of the order of 1020 cm−3. Taken together, these results not only provide important insight into a promising electrode for electrochromic displays applications, but also offer an economic and effective strategy for manufacturing of other doped metal oxide films.  相似文献   

4.
Optically variable windows (smart windows), which control the transmission of light into buildings and vehicles, are of interest both for the control of solar heat load and for privacy applications. Such windows are likely to utilize electrochromic technology to achieve optical control. An electrochromic device consisting of a cathodically colouring tungsten trioxide (WO3) film, an anodically colouring Prussian blue (PB) film, and a polymer electrolyte was made. The polymer electrolyte was prepared from polyvinyl alcohol doped with H3PO4 and KH2PO4 to accommodate the conduction of both H+ and K+ ions. The electrochromic WO3 and PB films functioned in a complementary way such that the device was coloured or bleached by the application of –0.5 V or +0.5 V (WO3 films vs PB film), respectively. The spectral characteristics of the coloured device confirmed the complementary colouration of WO3 and PB in the device.  相似文献   

5.
Lithium-sulfur (Li–S) batteries are attractive due to their high theoretical energy density. However, conventional Li–S batteries with liquid electrolytes undergo polysulfide shuttle-effect and lithium dendrite formation during charge/discharge process, leading to poor electrochemical performance and safety issues. Garnet type Li7La3Zr2O12 (LLZO) solid-state electrolyte (SSE) restricts the penetration of polysulfides and exhibits high ionic conductivity at room temperature (RT). Herein, Li6.5La3Zr1.5Nb0.5O12 (LLZNO) ceramic electrolyte using Li3PO4 (LPO) as sintering aids (LLZNO-LPO) is prepared by the rapid sintering method and is applied to construct a shuttle-effect free solid-state Li–S battery. The SSE displays high conductive pure cubic-LLZO phase; during the rapid sintering, LPO melts and junctions the voids between the grains, thus improves Li+ conductivity. As a result, the LLZNO-LPO ceramic electrolyte with Li+ conductivity of 4.3 × 10?4 S cm?1 and high critical current density (CCD) of 1.2 mA cm?2 is obtained at RT. The Li–S solid-state battery which utilizes LLZNO-LPO ceramic electrolyte can deliver an initial discharge capacity of 943 mA h·g?1 and 602 mA h·g?1 retention after 60 cycles. In the same time, the initial coulombic efficiency is as high as 99.5%, indicating that the SSE can effectively block the polysulfide shuttle towards the Li anode and fulfill a shuttle-free Li–S battery.  相似文献   

6.
Electrochromic tungsten oxide thin films, obtained by vacuum evaporation, were studied before and after heat treatment between 25 and 250°C for 2 h in air. Electrochromic properties were investigated in acid electrolyte by simultaneous measurements of the electrical and optical parameters. A.c. complex impedance techniques and voltammetry were used to characterize the films from an electrical point of view. We observed an enhancement of the electrochromic response times during both coloration and bleaching after heat treatment carried out between 150 and 220°C. This phenomenon was associated with a decrease of the ohmic drop in the electrode and a continuous variation of the impedance diagrams of these electrochromic electrodes. Moreover, we observed that the diffusion coefficient of H+ ions into WO3, obtained on colored thin films, increased as the electrochromic kinetics increased.  相似文献   

7.
In this work, a reasonable strategy for the construction of Li2ZnTi3O8@Na2WO4 composite was employed to promote the Li storage performances of Li2ZnTi3O8. The Li2ZnTi3O8@Na2WO4 composites (5, 10, and 15 wt%) were then prepared by a solution dispersion method. The introduction of Na2WO4 does not change the structures of the samples and they show similar morphologies with particle sizes from 100 to 200 nm. Suitable amount of Na2WO4 modification effectively improves the electrochemical performance of Li2ZnTi3O8. Li2ZnTi3O8@Na2WO4 composites (0, 5, 10, and 15 wt%) deliver the discharge/charge capacities of 137.4/136.4, 164.2/162.3, 189.2/188.1, and 154.5/153.3 mAh g?1 at 0.5 A g?1 after 100 cycles, respectively. Li2ZnTi3O8@Na2WO4 composites (10 wt%) has the highest reversible capacities among all samples. The Na2WO4 shell with an excellent electronic conductivity can reduce electrode polarization, decrease the charge transfer resistance, enhance the Li-ion diffusion coefficient of Li2ZnTi3O8, and then improve the electrochemical kinetics of composites. In addition, the formation of Ti–O bonds at the interface can be helpful for the stabilization of the composite, being beneficial for the improvement of their cycling stabilities. These results reveal that Na2WO4 coating is a facile and effective strategy to promote the Li storage performance of Li2ZnTi3O8.  相似文献   

8.
Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm2and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiOx/LiPON/WO3/ITO and ITO/NiOx/LiPON/WO3/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiOx/LiPON/WO3/ITO), the ECD with the IAI top electrode (ITO/NiOx/LiPON/WO3/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.  相似文献   

9.
Ta‐doped cubic phase Li7La3Zr2O12 (LLZ) lithium garnet received considerable attention in recent times as prospective electrolyte for all‐solid‐state lithium battery. Although the conductivity has been improved by stabilizing the cubic phase with the Ta5+ doping for Zr4+ in LLZ, the density of the pellet was found to be relatively poor with large amount of pores. In addition to the high Li+ conductivity, density is also an essential parameter for the successful application of LLZ as solid electrolyte membrane in all‐solid‐state lithium battery. Systematic investigations carried out through this work indicated that the optimal Li concentration of 6.4 (i.e., Li6.4La3Zr1.4Ta0.6O12) is required to obtain phase pure, relatively dense and high Li+ conductive cubic phase in Li7?xLa3Zr2?xTaxO12 solid solutions. Effort has been also made in this work to enhance the density and Li+ conductivity of Li6.4La3Zr1.4Ta0.6O12 further through the Li4SiO4 addition. A maximized room‐temperature (33°C) total (bulk + grain boundary) Li+ conductivity of 3.7 × 10?4 S/cm and maximized relative density of 94% was observed for Li6.4La3Zr1.4Ta0.6O12 added with 1 wt% of Li4SiO4.  相似文献   

10.
《Ceramics International》2021,47(22):31122-31129
Tungsten bronze has attracted global attention for its applications in near-infrared (NIR)-shielding windows. Here, alkali metal tungsten bronze (MxWO3, M = one or two types of Li, Na, and K)-doped glasses are prepared by a simple melt-quenching method. Their structure and properties were characterized by XRD, Raman spectroscopy, XPS and UV–Vis–NIR spectrophotometry. The effects of M on their structure and the NIR shielding performance are investigated. The LiF sample has the best NIR shielding performance, but its visible transmittance is sacrificed due to its low quality. The glasses containing mixed Li+ and K+ cooperate to form a high-quality Li+/K+-codoped tungsten bronze, while the glasses containing mixed Li+ and Na+ compete for limited tungsten resources to form Li+- and Na+-doped tungsten bronzes separately. The research here is helpful for understanding the role of different alkali metal ions in bulk energy-saving glass and is hugely significant for the guidance of the future applications of energy-saving glass without films.  相似文献   

11.
The nano-crystalline Li0.5La0.5TiO3 (LLTO) was prepared as an electrolyte material for lithium-ion batteries. The effect of Ag+ ion doping in three different concentrations were investigated: Ag0.1Li0.4La0.5TiO3, Ag0.3Li0.2La0.5TiO3, and Ag0.5La0.5TiO3 along with Li0.5La0.5TiO3. The prepared pure and Ag+ doped LLTO were subjected for structural, morphological, electrical and optical characterizations. The cubic superlattice structure of LLTO nano-powder was altered due to the Ag+ substitution tending towards a tetragonal phase. Increasing Ag+ substitution a complete tetragonal phase occurs in Ag0.5La0.5TiO3. The average particle size of the prepared ceramic electrolyte ranged between 80 nm and 120 nm. The photoluminescence study reveals that the LLTO and Ag doped LLTO gives a blue emission peak. The size effect on grain and grain boundary resistance was observed and reported. With Ag+ substitution, the conductivity got decreased due to the impedance caused by Ag+ ions in the conducting path of Li+ ion. Among all the samples, Ag0.5La0.5TiO3 shows maximum conductivity of the order of 10?3 S cm?1.  相似文献   

12.
Li7La3Zr2O12 (LLZO) has been reported to react in humid air to form Li2CO3 on the surface, which decreases ionic conductivity. To study the reaction mechanism, 0.5‐mol Ta‐doped LLZO (0.5Ta–LLZO) pellets are exposed in dry (humidity ~5%) and humid air (humidity ~80%) for 6 weeks, respectively. After exposure in humid air, the formation of Li2CO3 on the pellet surface is confirmed experimentally and the room‐temperature ionic conductivity is found to drop from 6.45×10?4 S cm?1 to 3.61×10?4 S cm?1. Whereas for the 0.5Ta–LLZO samples exposed in dry air, the amount of formed Li2CO3 is much less and the ionic conductivity barely decreases. To further clarify the reaction mechanism of 0.5Ta–LLZO pellets with moisture, we decouple the reactions between 0.5Ta–LLZO with water and CO2 by immersing 0.5Ta–LLZO pellets in deionized water for 1 week and then exposing them to ambient air for another week. After immersion in deionized water, Li+/H+ exchange occurs and LiOH H2O forms on the surface, which is a necessary intermediate step for the Li2CO3 formation. Based on these observations, a reaction model is proposed and discussed.  相似文献   

13.
Cubic phase garnet-type Li7La3Zr2O12 (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al2O3. The reported ionic conductivities were variable due to the complicated Al3+-Li+ substitution and LixAlOy segregation in Al-LLZO ceramics. This work prepared Li7?3xAlxLa3Zr2O12 (x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution, and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li+ ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO2 and LaAlO3 segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li+ ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li6.04Al0.32La3Zr2O12 ceramic delivers the optimum Li+ ion conductivity of 1.7 × 10?4 S cm?1 at 25 °C.  相似文献   

14.
《Ceramics International》2023,49(13):21729-21736
MoO3 is a kind of promising cathode material for lithium-ion batteries (LIBs), owing to its high specific capacity (279 mA h g−1) and layered structure. However, low electrical conductivity and sluggish reaction kinetics results in poor rate and Li-ions storage capability. The introduction of oxygen vacancies (OVs) can promote Li+ diffusion, and produce great electrical conductivity. Here, we report a strategy to synergize the merits of OVs by pulsed laser deposition (PLD) by adjusting oxygen partial pressures (2~20 Pa). The appropriate OVs concentration not only significantly approves electrochemical performance but also increases pseudocapacitance contribution. The Li-ion diffusion coefficient of MoO3−x is remarkably improved by one or two orders of magnitude compared with that of MoO3. Therefore, this facile and efficient strategy on OVs could afford a reference for other metal oxides for high-performance electrode materials.  相似文献   

15.
Garnet-type Li7La3Zr2O12 (LLZO) Li+ ion solid electrolyte is a promising candidate for next generation high-safety solid-state batteries. Ga-doped LLZO exhibits excellent Li+ ion conductivity, higher than 1 × 10?3 S cm?1. In this research, the doping amount of Ga, the calcination temperature of Ga-LLZO primary powders, the sintering conditions and the evolution of grains are explored to demonstrate the optimum parameters to obtain a highly conductive ceramics reproducibly via conventional solid-state reaction methods under ambient air sintering atmosphere. Cubic LLZO phase is obtained for Li6.4Ga0.2La3Zr2O12 powder calcined at low temperature 850 °C. In addition, ceramic pellets sintered at 1100 °C for 320 min using this powder have relative densities higher than 94% and conductivities higher than 1.2 × 10?3 S cm?1 at 25 °C.  相似文献   

16.
Pulsed laser deposition (PLD) was used to prepare tungsten trioxide (WO3) films on ITO substrates with a varying laser power density of 4.0–5.5 W/cm2. XPS indicated that when the laser power density decreased, the peak positions of the W 4f and O 1s orbits shifted slightly to low energy due to the difference in oxygen vacancies. As the laser power density decreased, W6+ gradually replaced the lattice position of O2?, increasing oxygen vacancies in the lattice. The transmittance modulated values (ΔT) were over 44% at 830 nm, indicating strong absorption by the WO3 thin films in the near-infrared ray. The switching time of the WO3 thin films between bleached states and coloured states decreased as the laser power density increased due to the amorphous structure, morphology, and lower oxygen deficiency at a high power density. The high ΔT and very fast switching time of tb (1.09 s) and tc (6.01 s) demonstrated the excellent electrochromic (EC) properties of the WO3 films prepared by PLD.  相似文献   

17.
Amorphous Li3PS4 films were synthesized by pulsed laser deposition (PLD) at room temperature using Li3PS4 targets with excess lithium and sulfur. Raman and X‐ray photoemission spectroscopies indicated that the Li3PS4 film synthesized with a stoichiometric amount of Li3PS4 target contained lithium‐deficient phases such as Li4P2S6, Li2?xS and sulfur due to composition deviation caused during the ablation process. The film synthesized with a 14% Li2S‐excess target (Li3.42PS4.21) contained fewer impurities, and exhibited a higher ionic conductivity of 5.3 × 10?4 S/cm at 298 K than the lithium‐deficient film (3.1 × 10?4 S/cm). The target composition is an important factor for the fabrication of highly conductive Li3PS4 films for electrolytes in thin‐film batteries.  相似文献   

18.
《Ceramics International》2023,49(3):4290-4297
Li(Al1-xLix)SiO4-x (x = 0.005, 0.01, 0.015, and 0.02) ceramics were synthesized via a traditional solid phase reaction method with different sintering temperatures. To determine the positions occupied by Li+ in the lattice, the defect formation energies and total energies of various sites of LiAlSiO4 (LAS) occupied by Li+ were examined, and the energy of LAS systems were calculated using density functional theory of first-principle with the CASTEP module. The results demonstrated that the Al-sites occupied by Li+ had the lowest formation energies and total energy, so Li + should substitute Al3+. The impacts of replacing Al3+ with Li+ on the bulk density, sintering properties, phase composition, microstructure, and microwave dielectric properties of Li(Al1-xLix)SiO4-x (0 = x ≤ 0.02) ceramics were thoroughly studied. With Li+-doping, the sintering temperature decreased from 1300 °C (x = 0) to 1175 °C (x = 0.02), while the Q × f and τf values of LAS ceramics significantly increased. The Li(Al0.99Li0.01)SiO3.99 ceramic was fully sintered at 1250 °C for 10 h to obtain excellent microwave dielectric properties: εr = 3.49, Q × f = 51,358 GHz, and τf = ?51.48 × 10?6 °C?1.  相似文献   

19.
《Ceramics International》2021,47(24):34218-34224
An enhanced sol-gel combustion method was used to synthesize different porous Sc3+-doped Li3V2-xScx(PO4)3/C (x = 0.00, 0.05, 0.10 and 0.15) compounds. The substitution of Sc3+ into the V3+ sites of Li3V2-xScx(PO4)3/C expands the lattice volume along with the enlargement of Li+ diffusion channel, which is beneficial for Li+ transportation and ionic conductivity improvement. Besides, the Sc3+ doping content exhibits a great impact on the morphology of Li3V2-xScx(PO4)3/C composite. The pristine Li3V2(PO4)3/C are constituted of porous particles and nanorods, and the ratio of nanorods to particles can be controlled by adjusting the amount of Sc3+ doping since the ratio of nanorods to particles decreases with increasing Sc3+ doping content. When Sc3+ doping content increases to a certain level (x = 0.15, Li3V1.85Sc0.15(PO4)3/C), the nanorods are hardly seen. Li3V1.90Sc0.10(PO4)3/C with higher tapped density, better reversibility, smaller resistance and larger Li+ diffusion coefficient demonstrates outstanding rate performance and cyclic stability, together with high specific discharge capacities of 130.2 and 92.9 mAh g−1 at 0.5 and 20 C, respectively. Furthermore, a superior specific discharge capacity of 85.8 mAh g−1 was retained at 20 C following 1000 cycles. Overall, a novel approach for the preparation of high-performance Li3V2-xScx(PO4)3/C cathodes with different morphologies for lithium-ion batteries is provided.  相似文献   

20.
《Ceramics International》2019,45(13):15990-15995
With the increase in global challenges related to energy depletion, there is significant emphasis on studies involving next-generation optoelectronic applications such as smart windows and electronic displays. In particular, electrochromic devices (ECDs) have been identified as strategic innovations for energy-saving “smart windows” to address these challenges. Despite this increased level of attentions, ECDs have not yet attained broad commercial acceptance because of their limited electrochromic (EC) properties including coloration efficiency (CE,< 30.0 cm2/C) and switching speeds (> 10.0 s). To address these limitations, critical effort is required to enhance the EC properties by tuning the film structure and electronic structure of ECDs. In this study, we demonstrated the effect of nanocomposite structure of conductive metal oxides and WO3 EC films. Antimony-doped tin oxide nanoparticles (ATO NPs) were utilized because of their superior electrical conductivity and large band gap. To achieve the optimum addition amount of ATO NPs in EC films, we adjusted the amount as 0, 0.6, 1.2, 2.4 wt%. WO3 EC films with the optimum addition amount (1.2 wt%) of ATO NPs exhibited improved EC performance including both the switching speeds (5.4 s for the coloration speed and 2.4 s for the bleaching speed) and CE value (48.2 cm2/C). The enhancement of EC performance was attributed to the well-dispersed ATO NPs in the WO3 films that can effectively improve electrical conductivity via the formation of by forming preferred electron pathway. In addition, the large band gap of ATO NPs broadens the transmittance modulation of the EC layer which contributed to the increment of the CE value. Therefore, our results suggest a strategy to obtain the enhanced WO3 films with superior EC performances using conductive metal oxides nanocomposite structure.  相似文献   

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