Experimental and computational optimization of Prussian blue analogues as high-performance cathodes for sodium-ion batteries:A review

In this review,we discuss the electrochemical properties of Prussian blue(PB)for Na^(+)storage by combining structural engineering and electrolyte modifications.We integrated experimental data and density functional theory(DFT)in sodium-ion battery(SIB)research to refine the atomic arrangements and crystal lattices and introduce substitutions and dopants.These changes affect the lattice stability,intercalation,electronic and ionic conductivities,and electrochemical performance.We unraveled the intricate structure-electrochemical behavior relationship by combining experimental data with computational models,including first-principles calculations.This holistic approach identified techniques for optimizing PB and Prussian blue analog(PBA)structu ral properties for SIBs.We also discuss the tuning of electrolytes by systematically adjusting their composition,concentration,and additives using a combination of molecular dynamics(MD)simulations and DFT computations.Our review offers a comprehensive assessment of strategies for enhancing the electrochemical properties of PB and PBAs through structural engineering and electrolyte modifications,combining experimental insights with advanced computational simulations,and paving the way for next-generation energy storage systems.

Progress on Transition Metal Ions Dissolution Suppression Strategies in Prussian Blue Analogs for Aqueous Sodium-/Potassium-Ion Batteries

Aqueous sodium-ion batteries(ASIBs)and aqueous potassium-ion batteries(APIBs)present significant potential for large-scale energy storage due to their cost-effectiveness,safety,and environmental compatibility.Nonetheless,the intricate energy storage mechanisms in aqueous electrolytes place stringent require-ments on the host materials.Prussian blue analogs(PBAs),with their open three-dimensional framework and facile synthesis,stand out as leading candidates for aqueous energy storage.However,PBAs possess a swift capacity fade and limited cycle longevity,for their structural integrity is compromised by the pronounced dis-solution of transition metal(TM)ions in the aqueous milieu.This manuscript provides an exhaustive review of the recent advancements concerning PBAs in ASIBs and APIBs.The dissolution mechanisms of TM ions in PBAs,informed by their structural attributes and redox processes,are thoroughly examined.Moreover,this study delves into innovative design tactics to alleviate the dissolution issue of TM ions.In conclusion,the paper consolidates various strategies for suppressing the dissolution of TM ions in PBAs and posits avenues for prospective exploration of high-safety aqueous sodium-/potassium-ion batteries.

Magnetization of mixed ferri-ferrimagnets composed of Prussian blue analogs A1_xA2_(1-x)B

The magnetization of ternary metal Prussian blue analogues AlxA21-xB, formed by three different sublattices A1, A2 and B, is studied by using the effective-field theory with self-spin correlations. Effects of the mole fraction x, the anisotropy and the transverse magnetic field on the magnetization are discussed.

Fully fluorinated hybrid zeolite imidazole/Prussian blue analogs with combined advantages for efficient oxygen evolution reaction

Hybrid metal-organic framework(MOF)derivatives play a significant role in the novel catalyst development in energy conversion reactions.Here,we demonstrated the low-temperature fully fluorinated zeolitic imidazole framework(ZIF)coupled with a three-dimensional open framework Prussian blue analog(PBA)with combined advantages for electrocatalytic oxygen evolution reaction(OER)in water splitting reaction.The spectroscopic analysis and the electrochemical studies revealed the combined advantages of efficient electronic effect and active site synergism.Because of good conductivity improvement by Ndoped carbon derived from ZIF and the high electrochemical surface area and active site exposure from PBA derivatives,good catalytic performance was obtained on the optimal catalyst of Co Ni ZIF/Co Fe-PBAF-300,which required a low overpotential of 250 m V to reach 10 m A/cm^(2)loaded on the glassy carbon electrode,with Tafel slope of 47.4 m V/dec,and very high dynamic and steady stability.In addition,the multi-component with the mixed structure from highly polar metal fluorides promoted the easy formation of the active phase as revealed by the post-sample analysis.The current results showed a novel composite catalyst materials development from the hybrid MOF derivatives,which would be promising in the electrolysis of water oxidation reactions and energy-relevant catalysis reactions.

The design and synthesis of Prussian blue analogs as a sustainable cathode for sodium-ion batteries

Sodium-ion batteries(SIBs)present great appeal in various energy storage systems,especifically for stationary grid storage,on account of the abundance of sources and low cost.Unfortunately,the commercialization of SIBs is mainly limited by available electrode materials,especially for the cathodes.Prussian blue analogs(PBAs),emerge as a promising alternative for their structural feasibility in the application of SIBs.Decreasing the defects(vacancies and coordinated water)is an effective strategy to achieve superior electrochemical performance during the synthetic processes.Herein,we summarize crystal structures,synthetic methods,electrochemical mechanisms,and the influences of synthesis conditions of PBAs in detail.This comprehensive overview on the current research progresses of PBAs will give guides and directions to solve the existing problems for their application in SIBs.

Polymorphic cerium-based Prussian blue derivatives with in situ growing CNT/Co heterojunctions for enhanced microwave absorption via polarization and magnetization

In this paper,the structure evolution of cerium cobaltohexanoate(Ce[Co(CN)6],Ce-Co Prussian blue analog(PBA))has been realized by solvent catalysis at room temperature.The hexagonal bipyramidal microcrystals of Ce-Co PBA can be gradually transformed into dendrites by different proportions of ethanol(EtOH)and water.At the same time,the porous dendrites CeO_(2)/Co@carbon nanotub(CNT)with oxygen-rich vacancies(OVs)can be obtained by annealing Ce-Co PBA at 700℃.The microstructure study shows that carbon nanotubes will be catalyzed after annealing at high temperature,and the cobalt metal particles encapsulated in carbon nanotubes will be anchored in the matrix,regulating the impedance matching and multi-polarization suppression of the material,and its unique structure,vacancies,and strong interface effect make the material exhibit excellent electromagnetic wave(EMW)absorption performance.When the matching thickness is 2.5 mm,the minimum reflection loss(RLmin)of the composite is-51.68 dB,and the effective absorption bandwidth(RL<-10 dB)is 7.76 GHz.These results show that the prepared CeO_(2)/Co@CNT composite has excellent EMW absorption properties.It is expected to be a candidate material for EMW absorption.

Enhanced conductivity and stability of Prussian blue cathodes in sodium-ion batteries by surface vapor-phase molecular selfassembly

With many merits such as facile synthesis,economy,and relatively high theoretical capacity,Prussian blue analogs(PBAs)are considered promising cathode materials for sodium-ion batteries(SIBs).However,their practical applications still suffer from a low actual specific capacity and inferior stability owing to the imperfect crystallinity,irreversible phase transition,and low intrinsic conductivity.Herein,a surface-modification technique for vapor-phase molecular self-assembly was developed to prepare Fe-based PBAs,specifically sodium iron hexacyanoferrate(NaFeHCF),with a uniform conductive polymer protective layer of polypyrrole(PPy)on the surface,resulting in NaFeHCF@PPy.The incorporation of a PPy protective layer not only improves the electronic conductivity of NaFeHCF@PPy,but also effectively mitigates the dissolution of Fe-ions during cycling.Specifically,this advanced vapor-phase technique avoids Fe^(2+)oxidation and Na^(+)loss during liquid-phase surface modification.The NaFeHCF@PPy exhibited a remarkably enhanced cycling performance,with capacity retentions of 85.6%and 69.1%over 500 and 1000 cycles,respectively,at 200 mA/g,along with a superior rate performance up to 5 A/g(fast kinetics).Additionally,by adopting this strategy for Mn-based PBAs(NaMnHCF@PPy),we further demonstrated the universality of this method for PBA cathodes in SIBs.

普鲁士蓝类钠离子电池正极材料导电性研究进展

发展具有快充性能(即超高倍率性能)的钠离子电池是目前储能领域研究的重点和热点。普鲁士蓝及其类似物(PBAs)具有有利于钠离子储存和扩散的开放式三维骨架结构,已经被证明作为钠离子电池正极材料具有巨大的潜力。然而,目前所制备的PBAs大多数存在结构缺陷和结晶水,以及其本身较差的电子电导率,导致其倍率性能不理想。本文针对PBAs导电性差的问题,从离子导电和电子导电两个方面进行讨论,首先分析了PBAs中结构缺陷以及结晶水的存在对离子导电的影响以及其本身价键结构对电子电导的影响。综述了近期对于提高PBAs导电性的相关研究:①改变晶体结构,通过减少PBAs晶体内部缺陷及结晶水,从而降低钠离子迁移距离及减少阻碍;②设计特殊的PBAs晶体结构,能有效减少钠离子传输路径;③采用复合导电材料,能构建新的电子运输途径。最后对提高PBAs导电性的三种策略进行了总结和展望,指出应该在优化PBAs结构的基础上,复合导电材料,同时增强离子电导和电子电导,以期达到最佳的倍率性能。

泡沫镍原位生长普鲁士蓝类似物构筑镍铁双金属氧化物催化剂的氧析出反应性能研究

开发高性能、低成本的氧析出反应(OER)催化剂对促进电解水制氢降低电耗、提高经济性具有重要意义。以导电泡沫镍为基底,采用冰水浴法原位生长镍铁普鲁士蓝类似物,氧化制备了镍铁双金属氧化物催化剂。分别采用X射线衍射、扫描电镜、高分辨率透射电镜和X射线光电子能谱方法对催化剂的物相组成、微观形貌和表面化学状态进行了表征,并采用电化学测试表征了催化剂的OER催化性能。结果表明,当氧化温度为200℃、氧化时间为2 h时,制备的催化剂中镍铁双金属氧化物高度分散在泡沫镍基底上,纳米颗粒最小,平均粒径为71 nm,可暴露的催化反应活性位点多,表现出最优的OER催化性能。该催化剂在1.0 mol/L的KOH电解液中,电流密度为10 mA/cm^(2)时,过电位仅为272 mV,并在电流密度为100 mA/cm^(2)时稳定运行了40 h,表现出优异的OER电化学稳定性。

Cu掺杂在钠离子电池正极中的研究进展

钠离子电池(SIBs)由于其原料丰富以及成本较低,被认为是最有前途的锂离子电池(LIBs)替代品之一,在过去的几年中吸引了人们的广泛关注。正极作为钠离子电池中不可分割的一部分,其性能对电池的稳定性以及使用寿命起着非常重要的作用。目前,常见的SIBs正极材料主要包括层状过渡金属氧化物、普鲁士蓝类似物、聚阴离子化合物等,这些电极材料容量较高、成本较低、对环境友好,但普遍存在导电性差、循环稳定性差、电池寿命短等缺点。为了改善SIBs性能,人们采用元素掺杂的方法来改变正极材料的晶格结构,增强SIBs的循环稳定性,延长电池寿命。Cu因具有良好的导电性且结构稳定而被人们广泛应用于元素掺杂研究。讨论了Cu掺杂对以上3种SIBs正极材料性能的影响,并总结了近年来Cu掺杂正极材料的设计制备及研究进展。

普鲁士蓝类似物衍生负极材料储钾电化学性能研究

通过常温离子交换制备出多孔普鲁士蓝类似物(FeZnCo-PB),然后高温退火处理获得衍生材料(FeZnCoPB-500),并将其作为钾离子电池负极极材料。对目标产物进行了SEM、TEM、XRD、BET表征,研究了FeZnCo-PB-500电极材料的形貌和结构。FeZnCo-PB-500负极材料展现出优异的储钾性能(长循环稳定性和高倍率性能)。在100和1000 mA/g的电流密度下,FeZnCo-PB-500电极分别循环200圈和400圈后可逆容量还能分别达到236 mAh/g和151 mAh/g。

对苯二酚在掺Cu(Ⅱ)类普鲁士蓝膜修饰电极上的电化学行为研究

采用循环伏安法在普鲁士蓝膜中掺杂cu2＋，制得掺cu（Ⅱ）类普鲁士蓝膜（cu—PB膜）。利用循环伏安法、库仑分析法和电化学阻抗法对cu—PB膜进行电化学表征，结果显示cu。’进入普鲁士蓝的内部结构，取代了其中的高自旋铁。该cu（Ⅱ）类普鲁士蓝膜对对苯二酚具有明显的电催化作用，电极反应过程是扩散控制的准可逆过程，在5．0×10-5～1．0×10mol·L-1范围内，还原峰电流与对苯二酚浓度呈良好的线性关系，检出限为1．0×10-6mol·L-1。计算了对苯二酚在cu—PB膜修饰电极上电极过程的动力学参数。

Prussian blue with intrinsic heme-like structure as peroxidase mimic

Despite the intrinsic peroxidase-like activity of Prussian blue nanopartides （PBNPs）, their enzyme-mimic mechanism has been scarcely investigated to date. Herein, we probed the catalytic site of PBNPs for the first time, by comparing their peroxidase-like activity with that of a series of Prussian blue analogs （PBAs） in which Fe atoms were replaced by Co, Ni, and Cu. The PBNPs exhibited the highest maximal reaction velocity （1.941 μM·s^-1）, which was at least 13 times higher than that of the PBAs, demonstrating that the peroxidase-like properties of PBNPs could be ascribed to the FeNx （x=4-6） instead of the FeC6 units. Notably, the PBNPs/H2O2 couple also showed much higher oxidizability than .OH radicals produced from the Fenton reaction, implying that a high active Fe（W）=O intermediate might be formed in the FeNx units. This study can thus pave the way for the wider application of PBNPs in biomimetic reactions.

2,4,6-三硝基苯酚在掺杂了铕(Ⅲ)离子的类普鲁士蓝膜修饰的玻碳电极上的电催化还原反应

摘要：制备了用掺杂铕（111）离子的类普鲁士蓝膜修饰的玻碳电极，并研究了2，4，6-三硝基苯酚在此修饰电极上的电化学行为。试验结果表明：与裸玻碳电极相比，2，4，6-三硝基苯酚在此修饰电极上的还原峰电流显著提高，还原电位大大降低，且工作曲线的线性范围明显增宽。在此基础上提出了-种高灵敏度直接测定2，4，6-三硝基苯酚的伏安测定法。在优化的条件下，测得特征还原峰的电流值与2，4，6-三硝基苯酚浓度在4．0×10-5～2．0×10-3mol·L-1及2．0×10-7～8．0×10-6mol·L-1范围内呈线性关系，方法的检出限（3σ）为6．0×10-8mol．L-1。以黄河水样作为基体，用标准加入法做回收试验，测得回收率在97．7％～103．3％之间。

新型配位Eu^(3+)离子掺杂类普鲁士蓝化学修饰电极的制备及其对抗坏血酸的检测

将Eu^(3+)离子分散于普鲁士蓝溶液中,制备Eu^(3+)离子掺杂类普鲁士蓝化学修饰电极,采用循环伏安法和交流阻抗技术对所制备电极进行电化学性能和稳定性测试,并通过修饰物的固体荧光光谱和拉曼光谱对其进行表征、分析。研究结果表明:Eu^(3+)已掺入到氰基桥联分子结构中,且该化学修饰电极制备简单,稳定性好,伏安响应比较优异。所制备的修饰电极对抗坏血酸的电化学氧化有很好的催化活性,催化氧化峰电流与其浓度在2.0×10^(-6)~2.0×10^(-3)mol/L范围内呈良好的线性关系,线性方程为Ip(μA)=1.4582C(μmol/L)+2.2576,R=0.9992(n=6);Ip(μA)=0.0031C(μmol/L)+1.4337,R=0.9998(n=6)。检出限为1.0×10^(-6)mol/L。

普鲁士蓝类似物及其衍生物在钾离子电池中的应用

由于不可再生能源资源有限,可再生能源的使用受环境影响较大,开发新一代能量储存与转换系统势在必行。钾离子电池因其能量密度高、成本低廉等优势极有可能成为下一代大型商业化储能系统,普鲁士蓝类似物以其开放的三维框架结构、快速脱嵌钾离子能力等优势受到极大关注,以其为模板合成的衍生物被广泛研究。本文通过对相关文献的调研,详细介绍钾离子电池和普鲁士蓝类似物及其衍生物的结构,总结钾离子电池和普鲁士蓝类似物及其衍生物的优势,综述了普鲁士蓝类似物及其衍生物在钾离子电池中的应用现状,就正负极材料性能展开详细的介绍。对于正极材料,主要介绍铁基、锰基、其他种类及部分取代普鲁士蓝类似物以及相关改性策略,重点分析了不同种类材料的充放电机理;对于负极材料,着重介绍了普鲁士蓝衍生物及新颖的合成方法、碳材料改性策略,并就其与传统的碳负极材料的优势与劣势进行了简要总结。综合分析表明,通过探究合成方法、采取部分取代、引入低维结构等策略,有望增强普鲁士蓝类似物及其衍生物在钾离子电池中的未来应用。

镁离子电池正极材料的研究现状

石油和天然气等传统能源的过度消耗导致环境污染和能源危机日趋严重。因此,迫切需要开发环境友好、大规模且高效的储能装置来持续性地获取风能、太阳能等间歇性能源。而在各种储能技术中,二次电池因具有能量转换效率高、使用寿命长和成本低廉等优点而最具研发前景。与研究广泛的锂离子电池相比,镁离子电池理论上能够提供更多的电子,其容量是锂离子电池的2~3倍,且镁离子电池具有资源丰富、环境友好、无毒、价格低廉等优点,因此镁离子电池被认为是便携式设备和重载能源设备的一个有前途的候选产品。自2000年初一个成功的镁离子电池原型出现后,研究人员对镁离子电池展开了大量研究。但目前仍存在着一些问题严重阻碍了可充镁离子电池(RMBs)的商业化发展。由于Mg^(2+)具有高电荷密度、强的极化效应和缓慢的扩散动力学,开发出符合目前商业需求的正极材料仍是一个巨大挑战。RMBs正极材料主要包括过渡金属硫化物、过渡金属氧化物、聚阴离子型化合物和普鲁士蓝类似物等。过渡金属硫化物结构刚性较小,在充放电循环过程中不容易产生结构坍塌,但其存在离子捕获效应及缓慢的扩散动力学等缺陷。过渡金属氧化物具有比硫化物更高的电压,但该材料的结构刚性较大,循环性能差。具有介孔结构的聚阴离子型化合物有利于提高电池的电化学性能,但其导电性有待提高。具有开放可调结构的普鲁士蓝类似物有利于Mg^(2+)的快速脱嵌,但其与水性电解质的相容性较差。近年来,国内外对RMBs正极材料的研究报道显著增加,针对其存在的问题,研究人员主要从纳米化、结构调整、掺杂改性及包覆改性等方面进行材料的优化设计。本文主要对各种类的RMBs正极材料在国内外的研究状况进行了概括,包括其晶体结构、材料的研究现状及存在的问题,并分析了其未来面临的挑战,以期为合成高能量密度、高循环稳定性的RMBs正极材料提供参考。

Magnetic Behavior of Ferri-ferromagnetic Alloy in Presence of External Magnetic Field

混合 ferro-ferrimagnetic 合金与的磁性的行为( B b C c )由 Ising 组成的 y D 结构旋转 S = 1 ， S B = 5/2 ， S C = 2 ，并且 S D = 3/2 被有效的地理论的使用面对外部磁场调查。集中 b 的角色详细在这个系统被讨论。结果为 = 显示出那 0.4，仅仅当集中 b 在这个区域时 0.60 ≥ b 】 0.34 罐头含铁磁性的行为被看见。否则，合金显示出铁磁性的行为。

Trifunctional robust electrocatalysts based on 3D Fe/N-doped carbon nanocubes encapsulating Co4N nanoparticles for efficient battery-powered water electrolyzers

Herein,we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs,where Co_(4)N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize hierarchically structured Co_(4)N@Fe/N-C for rechargeable zinc-air batteries and overall water-splitting electrolyzers.As confirmed by theoretical and experimental results,the high intrinsic oxygen reduction reaction,oxygen evolution reaction,and hydrogen evolution reaction activities of Co_(4)N@Fe/N-C were attributed to the formation of the heterointerface and the modulated local electronic structure.Moreover,Co_(4)N@Fe/N-C induced improvement in these trifunctional electrocatalytic activities owing to the hierarchical hollow nanocube structure,uniform distribution of Co_(4)N,and conductive encapsulation by Fe/N-C.Thus,the rechargeable zinc-air battery with Co_(4)N@Fe/N-C delivers a high specific capacity of 789.9 mAh g^(-1) and stable voltage profiles over 500 cycles.Furthermore,the overall water electrolyzer with Co_(4)N@Fe/N-C achieved better durability and rate performance than that with the Pt/C and IrO2 catalysts,delivering a high Faradaic efficiency of 96.4%.Along with the great potential of the integrated water electrolyzer powered by a zinc-air battery for practical applications,therefore,the mechanistic understanding and active site identification provide valuable insights into the rational design of advanced multifunctional electrocatalysts for energy storage and conversion.

Copper Nitroprusside-Based Electrochemical Sensor for Detection of Tryptophan

This work presents a novel electrochemical approach for detecting tryptophan through its interaction with copper nitroprusside,which is synthesized using a simple chemical co-precipitation method.The utilization of the reduction reaction inherent to copper nitroprusside effectively exhibits high selectivity against common interferences present in urine,such as melatonin,lactate,cytosine,cytidine,urea,ascorbic acid,creatine,creatinine,tyrosine,glycine,alanine,arginine,and lysine.The method demonstrates two linear ranges:0.0-0.15 mmol/L and 0.15-2.0 mmol/L with the sensitivities of 119.7±0.2μA/(mmol/L)and 9.9±0.4μA/(mmol/L),respectively.The limit of detection(3S_(B)/m)was determined to be 5.5μmol/L.Application of the sensor in synthetic urine yielded the recovery of 103%±5%.