Prussian white

  • 文章类型: Journal Article
    由于其成本效益,丰富的资源,和合适的工作潜力,钠离子电池有望成为电网储能领域的领先技术。然而,钠离子电池仍然面临挑战,包括与低能量密度和受限循环性能相关的问题。在这项研究中,提出了一种由普鲁士白/KetjenBlack/MXene(TK-PW)组成的自支撑电极。在TK-PW电极中,MXene层涂覆有普鲁士白色纳米颗粒和具有高电导率的KetjenBlack,有利于Na+快速动态,有效缓解电极膨胀。值得注意的是,电极制备方法简单,经济高效,实现大规模生产。电化学测试表明,TK-PW电极在200次循环后保留了74.9%的容量,1000mA·g-1时放电容量为69.7mAh·g-1。此外,建造了一个完整的细胞,采用硬碳阳极和TK-PW阴极来验证TK-PW电极的实际应用潜力。
    Due to their cost-effectiveness, abundant resources, and suitable working potential, sodium-ion batteries are anticipated to establish themselves as a leading technology in the realm of grid energy storage. However, sodium-ion batteries still encounter challenges, including issues related to low energy density and constrained cycling performance. In this study, a self-supported electrode composed of Prussian white/KetjenBlack/MXene (TK-PW) is proposed. In the TK-PW electrode, the MXene layer is coated with Prussian white nanoparticles and KetjenBlack with high conductivity, which is conducive to rapid Na+ dynamics and effectively alleviates the expansion of the electrode. Notably, the electrode preparation method is uncomplicated and economically efficient, enabling large-scale production. Electrochemical testing demonstrates that the TK-PW electrode retains 74.9% of capacity after 200 cycles, with a discharge capacity of 69.7 mAh·g-1 at 1000 mA·g-1. Furthermore, a full cell is constructed, employing a hard carbon anode and TK-PW cathode to validate the practical application potential of the TK-PW electrode.
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  • 文章类型: Journal Article
    普鲁士白(PW)是最有前途的候选作为钠离子电池(SIB)的阴极之一,因为它的高理论容量,优异的速率性能,生产成本低。然而,PW材料在长期循环期间遭受严重的容量衰减。在这项工作中,在PW阴极上设计了一个坚固的阴极电解质界面(CEI),采用甲苯基二苯基磷酸酯(CDP)和己二腈(ADN)作为电解质添加剂。CDP和ADN具有比其他溶剂更高的最高占据分子轨道能级(HOMO),导致CDP和ADN优先分解,从而在PW阴极上原位构建富含无机物的CEI层。受益于这个CEI层,在长循环过程中有效抑制了PW的降解。Na||PW电池实现了出色的循环性能,在1400次循环后的容量保留率为85.62%。本文提出的这项工作为通过电解质改性提高PW的循环性能提供了可行的策略。
    Prussian white (PW) is one of the most promising candidates as a cathode for sodium-ion batteries (SIBs) because of its high theoretical capacity, excellent rate performance, and low production cost. However, PW materials suffer severe capacity decay during long-term cycling. In this work, a robust cathode electrolyte interface (CEI) is designed on the PW cathode by employing cresyl diphenyl phosphate (CDP) and adiponitrile (ADN) as electrolyte additives. CDP and ADN possess higher highest occupied molecular orbital energy levels (HOMO) than other solvents, leading to the preferential decomposition of CDP and ADN to construct an inorganics-rich CEI layer in situ on the PW cathode. Benefiting from this CEI layer, the degradation of PW is effectively inhibited during the long cycling. The Na||PW cell achieves an excellent cycling performance with a capacity retention of 85.62% after 1400 cycles. This work presented here provides a feasible strategy for improving the cycling performance of PW by electrolyte modification.
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  • 文章类型: Journal Article
    铁基普鲁士白(PW)是有前途的钠离子电池阴极之一,由于其高容量和低成本。然而,PW的实际应用受到空气稳定性差的阻碍。金属氧化物涂层已被证明是提高电极材料空气稳定性的有效途径。然而,目标电极材料通常需要溶解在水溶液中以获得前体复合材料,然后在金属氧化物涂覆过程中在高温下煅烧,由于钠浸出到水中并在高温下热分解,可能会破坏PW的相结构。在这项工作中,我们提出了一种利用乙醇作为溶剂和温和的后处理温度在PW上构建ZnO表面层的简便方法。ZnO涂层有效地增强了PW的空气稳定性,并诱导了PW上稳定界面的形成。PW-5重量%ZnO-E(在30天后暴露于60%湿度的空气中)阴极在200次循环后在1°C表现出比PW-E(54%)高得多的容量保持率(94.1%)。这项工作为PW的进一步应用奠定了坚实的基础。
    Iron-based Prussian white (PW) is one of the promising cathodes for sodium-ion batteries, owing to its high capacity and low cost. However, the practical application of PW is hindered by its poor air stability. The metal-oxide coating has been proven to be an effective way to improve the air stability of electrode materials. Whereas, the target electrode materials conventionally need to be dissolved in the aqueous solution to obtain precursor composites and subsequently calcined at a high temperature during the metal-oxide coating process, which could destroy the phase structure of PW as a result of the sodium leaching into the water and thermal decomposition at the high temperature. In this work, we propose a facile method to construct a ZnO surface layer on PW by utilizing ethanol as a solvent and a mild post-treatment temperature. The ZnO coating layer effectively enhances the air stability of PW and induces the formation of the stable interface on PW. The PW-5 wt % ZnO-E (exposed in 60% humidity air after 30 days) cathode demonstrates a much higher capacity retention (94.1%) at 1 C after 200 cycles than that of PW-E (54%). This work lays a solid foundation for further application of PW.
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  • 文章类型: Journal Article
    高熵方法应用于单斜态普鲁士白(PW)Na离子阴极,以解决电化学循环时不利的多能级相变问题,导致稳定性差和容量衰减。合成了一系列Mn基样品,其中多达六个金属物种共享N配位位置。发现组成为Na1.65Mn0.4Fe0.12Ni0.12Cu0.12Co0.12Cd0.12[Fe(CN)6]0.92□0.08的材料具有优于中/低熵和常规单金属PWs的循环性。我们也报告,我们第一次认识到,在电池运行期间,高对称性晶体结构对于高熵PW可能是有利的。形成焓的计算比较表明,组成较不复杂的材料容易发生相变,这会对循环性能产生负面影响。基于来自互补表征技术的数据,提出了Na插入/提取后无序PW结构稳定性改善的内在机理,即抑制相变和减缓气体析出的双重作用。
    The high-entropy approach is applied to monoclinic Prussian White (PW) Na-ion cathodes to address the issue of unfavorable multilevel phase transitions upon electrochemical cycling, leading to poor stability and capacity decay. A series of Mn-based samples with up to six metal species sharing the N-coordinated positions was synthesized. The material of composition Na1.65 Mn0.4 Fe0.12 Ni0.12 Cu0.12 Co0.12 Cd0.12 [Fe(CN)6 ]0.92 □0.08  ⋅ 1.09H2 O was found to exhibit superior cyclability over medium/low-entropy and conventional single-metal PWs. We also report, to our knowledge for the first time, that a high-symmetry crystal structure may be advantageous for high-entropy PWs during battery operation. Computational comparisons of the formation enthalpy demonstrate that the compositionally less complex materials are prone to phase transitions, which negatively affect cycling performance. Based on data from complementary characterization techniques, an intrinsic mechanism for the stability improvement of the disordered PW structure upon Na+ insertion/extraction is proposed, namely the dual effect of suppression of phase transitions and mitigation of gas evolution.
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  • 文章类型: Journal Article
    普鲁士白(PW)由于其低成本和高理论容量而被认为是钾离子电池(KIBs)的有前途的正极材料。然而,PW的高含水量和结构缺陷以及严格的合成条件导致其循环性能不理想和比容量低,阻碍其实际应用。在这里,提出了一种模板占用约简方法,以MIL-88B(Fe)为自模板剂,KI为还原剂,制备出缺陷和含水量低的富KPW。此外,分层多孔纺锤状形态可以从前体继承,提供足够的活性位点并减少离子扩散路径。因此,当用作KIB阴极材料时,纺锤形PW(K1.72Fe[Fe(CN)6]0.96·0.342H2O)表现出显著的储钾性能。值得注意的是,由纺锤形PW阴极和石墨阳极组装的全电池表现出〜216.7Whkg-1的大能量密度,证明了其在储能系统中的巨大潜力。
    Prussian white (PW) is considered as a promising cathode material for potassium-ion batteries (KIBs) due to its low cost and high theoretical capacity. However, the high water content and structural defects and the strict synthesis conditions of PW lead to its unsatisfactory cycling performance and low specific capacity, hindering its practical applications. Herein, a template-engaged reduction method is proposed, using MIL-88B(Fe) as a self-template and KI as the reducing agent to prepare K-rich PW with low defects and water content. Furthermore, the hierarchical porous spindle-like morphology can be inherited from the precursor, furnishing sufficient active sites and reducing the ion diffusion path. Consequently, when applied as a KIB cathode material, spindle-like PW (K1.72Fe[Fe(CN)6]0.96·0.342H2O) manifested remarkable potassium storage properties. Notably, a full cell assembled by the spindle-like PW cathode and graphite anode exhibited a large energy density of ∼216.7 Wh kg-1, demonstrating its huge potential for energy storage systems.
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  • 文章类型: Journal Article
    普鲁士白(PW)被认为是钠离子电池最有前途的正极材料之一,因为它具有大的离子扩散通道,低晶格应变,容易准备,无毒,和低成本。目前,对PW的研究主要集中在优化材料的结构,以适应周围环境,而在极端温度下的实际应用较少。在这个聚光灯下,我们打算在内在可行性和发展前景方面提供我们在开发宽温度下工作的PW阴极材料方面取得的进展。这些发现为促进PW在极端条件下的实际生存能力提供了方向。
    Prussian white (PW) is considered one of the most promising cathode materials for sodium-ion batteries because of its large ion diffusion channels, low lattice strain, facile preparation, nontoxicity, and low cost. At present, research on PW mainly focuses on optimizing the material\'s structures for the ambient environment yet less on its practical application under extreme temperatures. In this Spotlight, we intend to offer progress we have made in developing PW cathode materials working over wide temperatures in terms of intrinsic feasibility and development prospects. These findings provide a direction to promote the practical viability of PW under extreme conditions.
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  • 文章类型: Journal Article
    在本文中,通过用普鲁士蓝(玻璃|FTO|PB)层修饰掺氟氧化锡涂层的载玻片(玻璃|FTO)来形成电化学无氯(FCL)传感器。玻璃|FTO|PB传感器具有从1.7到99.2μmolL-1的FCL的宽线性检测范围,灵敏度为〜0.8µAcm-2μmol-1L,对FCL具有高选择性。然而,ClO3-,ClO4-和NO3-离子仅引起可忽略的安培响应,这对于现实生活中的样品分析非常有益,因为这些离子通常存在于氯处理的水中。此外,在这项工作中,对部分还原的PB进行了基于光吸收测量的研究,以表征PB对FCL的催化活性,并研究将PB用于FCL的光学检测的可能性。
    In this paper, an electrochemical free chlorine (FCL) sensor was formed by modifying a fluorine-doped tin oxide-coated glass slide (glass|FTO) with a layer of Prussian blue (glass|FTO|PB). The glass|FTO|PB sensor exhibited a wide linear detection range from 1.7 to 99.2 μmol L-1 of FCL with a sensitivity of ~0.8 µA cm-2 μmol-1 L and showed high selectivity for FCL. However, ClO3-, ClO4- and NO3- ions have induced only a negligible amperometric response that is highly beneficial for a real-life sample analysis as these ions are commonly found in chlorine-treated water. Moreover, in this work, optical absorption measurement-based investigations of partially reduced PB were carried out as a means to characterize PB catalytic activity towards FCL and to investigate the possibility of applying PB for the optical detection of FCL.
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  • 文章类型: Journal Article
    近年来,柔性电致变色器件因其在智能多功能电致变色储能器件和可穿戴智能电子产品中的巨大潜力而受到广泛关注。在这里,通过结合普鲁士白色@MnO2复合电极(PWM)和溅射制成的WO3电极,我们提出了一种无机柔性Li基电致变色储能器件(EESD)。普鲁士白和MnO2的协同作用对EESD的储能和电致变色性能均有积极作用。其能级可以通过透射光谱和色度差来量化,其充放电过程可以通过特殊波长的光调制实时监测。具体来说,EESD可以承受10,000次循环伏安循环,在宽电压窗口(-2至2.5V)下没有明显降解,并在510nm处具有35%的光学调制实现了高着色效率(77.6cm2/C)。在储能性能方面,EESD表现出优异的体积能量/功率密度(1.25Wcm-3/13.2mWhcm-3)和显著的稳定性,在超过4000次循环后具有接近98.3%的电容保持率和99.4%的库仑效率。可以在不同的光谱区域中可视化其充电和放电程度。对于在蓝光区域(450-480nm)中的充电,存在40%的透射率变化,对于在红光区域(620-750nm)中的放电,存在45%的透射率变化。基于它的多色属性,电荷状态的定量指标是通过存储或释放电荷时实时色度变化的线性依赖性来实现的。~11mC/cm2存储的电荷容量可以导致色度差ΔE值增加~11,而~7mC/cm2放电容量可导致ΔE值增加~4。这项工作提供了一种有效的策略来开发便携式多色集成EESD,以实现高性能和长稳定性。
    Flexible electrochromic devices have attracted considerable attention in recent years due to their great potential in smart multifunction electrochromic energy storage devices and wearable intelligent electronics. Herein, we present an inorganic flexible Li-based electrochromic energy storage device (EESD) by combining a Prussian white@MnO2-composited electrode (PWM) and sputtering-made WO3 electrode. The synergistic effect of Prussian white and MnO2 plays a positive role both in energy storage and electrochromic property of the EESD. Its energy level can be quantified by the transmittance spectrum and chrominance difference, and its charging-discharging process can be monitored in real time by optical modulation at special wavelength. Specifically, the EESD can endure a 10,000 times cyclic voltammetry cycle without obvious degradation at wide voltage windows (-2 to 2.5 V) and realize a high coloration efficiency (77.6 cm2/C) with 35% optical modulation at 510 nm. In terms of energy storage performance, the EESD demonstrates excellent volumetric energy/power density (1.25 W cm-3/13.2 mWh cm-3) and remarkable stability with close to 98.3% capacitance retention and 99.4% coulombic efficiency after more than 4000 cycles. Its charging and discharging degree can be visualized in different spectral regions. There are 40% transmittance change for charging in the blue light region (450-480 nm) and 45% transmittance change for discharging in the red light region (620-750 nm). Based on its multicolor property, a quantitative indicator of charge state is achieved by the linear dependence of real-time chrominance change as stored or released charge. The ∼11 mC/cm2 stored charge capacity can cause an ∼11 increase in chrominance difference ΔE value, while ∼7 mC/cm2 discharge capacity can cause a ΔE value increase of ∼4. This work provides an efficient strategy to develop portable multicolor-integrated EESDs toward high performance and long stability.
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  • 文章类型: Journal Article
    通过交流阻抗谱和直流电流-电压测量检查了通过电沉积方法获得的电阻开关普鲁士白(PW)薄膜的导电机理。使用电极尖端接触在Au上生长的PW,观察到稳健的单极电阻开关,电流变化高达三个数量级,高重复性,和再现性。此外,电阻抗谱表明,在建立较大的导电通道之前,电阻开关来自钾离子形成的小导电丝。伏安法和EIS测量均表明,电性能和导电丝的形成受到晶界中存在的缺陷和离子的影响。因此,PW是下一代ReRAM器件的潜在材料。
    The electrical conduction mechanism of resistive switching Prussian white (PW) thin films obtained by the electrodeposition method was examined by AC impedance spectroscopy and DC current-voltage measurements. Using an electrode tip to contact PW grown over Au, robust unipolar resistive switching was observed with a current change of up to three orders of magnitude, high repeatability, and reproducibility. Moreover, electrical impedance spectroscopy showed that the resistive switching comes from small conductive filaments formed by potassium ions before the establishment of larger conductive channels. Both voltammetry and EIS measurements suggest that the electrical properties and conductive filament formation are influenced by defects and ions present in the grain boundaries. Thus, PW is a potential material for the next generation of ReRAM devices.
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  • 文章类型: Journal Article
    普鲁士白(PW),由于成本低,容易合成,开放式结构,和快速离子提取/相互作用,引入到电致变色领域。通过表面水热法成功地在氧化铟锡(ITO)玻璃上生长了PW薄膜。令人印象深刻的是,PW膜表现出优异的电化学循环稳定性,在10000次循环中没有明显的衰减,并且具有149.3cm2C-1的高着色效率。该膜还在650-800nm的宽波长范围内提供大的光学透射对比度(超过70%)。此外,PW膜显示出快速的着色和漂白响应。这些结果表明PW是高性能电致变色材料的有希望的实用候选材料。
    Prussian white (PW), due to its low cost, easy synthesis, open structure, and fast ion extraction/interaction, is introduced to the electrochromic field. The PW films were successfully grown on indium tin oxide (ITO) glass by a facial hydrothermal method. Impressively, the PW film exhibits excellent electrochemical cycling stability without obvious decay over 10 000 cycles and a high coloration efficiency of 149.3 cm2 C-1. The film also provides the large optical transmittance contrast (over 70%) in a wide wavelength range of 650-800 nm. Furthermore, the PW film shows the rapid coloration and bleaching response. These results suggest that PW is a promising practical candidate of high-performance electrochromic material.
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