Core-shell Electrode Research Articles

Doping Effects of Sulfur and Electrochemical Energy Storage of CuO@S-NiV LDH Core–Shell Electrode

Doping Effects of Sulfur and Electrochemical Energy Storage of CuO@S-NiV LDH Core–Shell Electrode

A facile one-step route to synthesize of novel porous reduced graphene oxide@nickel sulfide (rGO@Ni3S2) core shell nanostructures for high-performance supercapacitor electrodes

In the last decade, there has been significant interest in the use of supercapacitors with high power density and cycle stability in a wide range of applications. Graphene-based hybrid electrodes are considered a very promising option for supercapacitors owing to the synergistic effects they exhibit. In this study, we provide a novel and efficient method for synthesising a core-shell nanocomposite consisting of reduced graphene oxide (rGO) wrapped around nickel sulphide (Ni3S2) using a one-step hydrothermal process. The resulting rGO@Ni3S2 composite exhibits excellent performance as a supercapacitor electrode while also being cost-effective. As a promising supercapacitor electrode, a relatively high specific capacitance of 1052.5 Fg−1 at current density of 1 Ag−1 in 1 mol.L−1 KOH aqueous solution, along with good cycling stability (with a 94.5 % retention rate after 10,000 cycles) were demonstrated for the rGO@Ni3S2 core shell composite electrode. In addition, excellent electrochemical performances were also demonstrated for the asymmetric supercapacitor (ASC) by using rGO@Ni3S2 as the cathode and activated carbon, respectively. The fabricated ASC showed with a high energy density of 61.9 Whkg−1 at the power density of 585.7 W kg−1. Such high performance of rGO@Ni3S2 core shell electrode can enrich the prospects for future practical applications in energy storage.

Enhanced ultraviolet photodetection with Ag nanoparticle-decorated ZnO nanowires and core-shell electrodes

Our study presents the synthesis and characterization of one-dimensional (1-D) zinc oxide (ZnO) nanorod (NR) arrays via low-temperature hydrothermal synthesis, followed by surface modification with silver nanoparticles (Ag NPs). Silver nanowires (AgNWs) are potential alternatives to indium-tin oxide, but their poor stability in atmospheric conditions poses a challenge. To address this, we developed ultrathin Ag/ZnO core-shell structured nanowire networks for ultraviolet-photodetectors (UV-PDs). This cost-effective solution process yielded high transmission (77 %) and low sheet resistance (8.3 Ω/sq). We comprehensively investigated surface morphology, crystalline nature, elemental composition, optical properties, and electrical performance of both synthesized nanorod arrays and NW networks. The UV photodetector exhibited a rise time of approximately 1.35 s and a decay time of 8.01 s, both faster than pristine AgNW electrodes. Additionally, the dark current decreased from 9 nA to 3.5 nA after incorporating Ag/ZnO, accompanied by a significant improvement in photocurrent. These results highlight a promising approach for high-performance UV photodetectors, leveraging the stability and conductivity of Ag/ZnO core-shell NW networks.

Mechanical Failure of Core-Shell Cathode Particles: The Effects of Concentration-Dependent Material Properties and Phase Field Fracture Modelling

The use of core-shell cathode particles in lithium-ion batteries is an attractive approach to enhancing energy density whilst retaining lifetime, through reducing undesired reactions at the electrode-electrolyte interface and limiting the volume change of the electrode particles. However, mechanical failure through the fracture and debonding of the core-shell interface is a major challenge. In this work, we employ a coupled finite-element model to predict and mitigate the mechanical failure of core-shell cathode structures, taking as example a particle of NMC811 (core) coated with NMC111 (shell). In particular, we focus on two aspects:The first one involves the assumptions of material properties as inputs of the model. The material properties are often considered constant by battery modelling researchers, yet these parameters can vary significantly during charge/discharge. For example, experiments have unveiled a three-orders-of-magnitude drop in the diffusion coefficient of NMC materials during discharge [1]. Here, we incorporate material properties obtained from experimental data, including concentration-dependent diffusion coefficient obtained from GITT measurement and partial molar volume derived from in situ X-ray diffraction data. Our results indicate that when assuming a concentration-dependent partial molar volume, the maximum values of tensile hoop stress in the shell are nearly three times lower than those predicted with constant average properties, diminishing the likelihood of fracture.When accounting for concentration-dependent diffusion coefficient, large concentration gradient is observed near the outer surface of the core due to reduced lithium mobility at high states of lithiation, hindering full electrode capacity utilisation. The significant concentration gradient and capacity underutilisation align with direct observations from experiments [2]. Notably, these phenomena cannot be captured in modelling if assuming constant diffusion coefficient. These findings offer new perspectives on the performance and design of core-shell electrode particles. Safe design maps in terms of core size and shell thickness to mitigate fracture and debonding are obtained.The second focus of this work is the utilisation of phase field fracture model in predicting cracking behaviours within the core-shell particle. Phase field modelling provides a continuous representation of cracks, enabling the tracking of complex cracking patterns [3]. We predict cracking behaviors caused by volume changes during charge/discharge, as well as inaccessible capacity and newly created active surface area caused by cracking. Our multiphyics model can hopefully act as a catalyst, accelerating the development process of the core-shell structured cathode particles and shortening the time to market of advanced batteries with extended lifetime.

Core-shell engineering of titanium-based anodes toward enhanced electrochemical lithium/sodium storage performance: a review

Titanium-based materials, including titanium dioxide, alkali-titanium oxides, titanium phosphates/oxyphosphates, titanium-based MXenes, and some other complex titanium compounds, have been regarded as promising anode candidates for Li/Na ion batteries, due to their advantages of good stability, high safety, low cost, and easy synthesis. However, poor electrical conductivity, high work potential, and low output capacity largely hinder the practical applications. Core-shell structure has been widely reported as an effective way to address these problems, and tremendous efforts have been made toward this direction. In this review, we offer an overview of core-shell titanium-based anode engineering for highly efficient and stable Li/Na ion batteries. The review presents the recent progresses and challenges in materials discovery, structure design, and electrode engineering, and highlights the advantages and drawbacks of a series of core-shell engineering strategies. In detail, the material structure, morphology, and composition of various core-shell nanocomposites are reviewed; the structure-activity-stability relationship between core-shell electrodes and electrochemical properties is discussed; the effective strategies for core-shell engineering are summarized, and the development prospects of titanium-based anodes are proposed. We anticipate that this review could provide a systematic understanding of core-shell engineering design of high-performance titanium-based anodes.

Synergistic Manganese Cobalt Phosphide core-shell for the Electrochemical Detection of Methyl Parathion in Food Sample

The development of a robust electrocatalyst for the electrochemical sensor for hazardous pesticides will reduce its effects on the ecosystem. Herein, we synthesized the robust manganese cobalt phosphide (MnCoP) - Core-shell as an electrochemical sensor for the determination of hazardous pesticide methyl parathion (MP). The MnCoP- Core-shell was prepared with the sustainable self-template route can help with the larger surface area. The Core-shell structure of MnCoP possesses a higher active surface area which increases the electrocatalytic performance and is utilized to improve the electrochemical MP reduction with the synergism of the core and shell structure. Remarkably, it realizes the higher sensitivity (0.014 μA μM−1 cm−2) of MnCoP- Core-shell/GCE achieves towards MP with lower limit of detection (LoD 50 nM) and exceptional recovery rate of MP in vegetable samples are achieved with the differential pulse voltammetry (DPV) technique. The MnCoP- Core-shell electrode reserved their superior electrochemical performances with high reproducibility and repeatability. This prominent activity of the MnCoP core-shell towards the MP in real sample analysis, makes it a promising electrochemical sensor for the detection of MP.

Introducing Ce into the interface of NiCo LDH@PBAs to build multi core–shell electrode with superior stability of supercapacitor

Core-shell electrodes have been used in many fields, however, the poor conductivity caused by the weak interfacial interaction limits the practical application of the composites. Herein, a novel multi core–shell material (NiCo-Ce@PBAs) used as electrode in supercapacitor is prepared using Ce as bridge to connect the core (NiCo LDH) and shell (NiCo PBAs). Benefiting from the gradient orbital coupling of 2p-4f-π derived from O-Ce-C≡N unit sites in NiCo-Ce@PBAs, the composite shows enhanced covalency and determines to delocalize the electronic expansion in the interaction. Besides, the redox pair of Ce3+-Ce4+ also makes great contribution to expedite the charge transfer as well as enhancing the binding energies of metals in core and shell. Overall, the optimized core–shell electrodes show excellent electrochemical performance with high area-specific capacitance of 1847 F g−1 at 1 A g−1, which is much higher than that of LDH-based electrodes ever reported. In addition, the electrode is found better cyclic performance than the others (95.7 % even after 10,000 cycles), which is due to the fact that the special 4f empty orbits can store partial electrons, thus decreasing the polarization phenomenon. It also shows great practical application when using commercial activated carbon as cathode. This work illustrates a new strategy to construct core–shell electrodes with strong interfacial interaction as well as revealing the important role of orbital theory in the design of multi core–shell electrodes.

Influence of concentration-dependent material properties on the fracture and debonding of electrode particles with core–shell structure

Core–shell electrode particle designs offer a route to improved lithium-ion battery performance. However, they are susceptible to mechanical damage such as fracture and debonding, which can significantly reduce their lifetime. Using a coupled finite element model, we explore the impacts of diffusion-induced stresses on the failure mechanisms of an exemplar system with an NMC811 core and an NMC111 shell. In particular, we systematically compare the implications of assuming constant material properties against using Li concentration-dependent diffusion coefficient and partial molar volume. With constant material properties, our results show that smaller cores with thinner shells avoid debonding and fracture regimes. When factoring in a concentration-dependent partial molar volume, the maximum values of tensile hoop stress in the shell are found to be significantly lower than those predicted with constant properties, reducing the likelihood of fracture. Furthermore, with a concentration-dependent diffusion coefficient, significant barriers to full electrode utilisation are observed due to reduced lithium mobility at high states of lithiation. This provides a possible explanation for the reduced accessible capacity observed in experiments. Shell thickness is found to be the dominant factor in precluding structural integrity once the concentration dependency is accounted for. These findings shed new light on the performance and effective design of core–shell electrode particles.

Regulating core-shell interfacial interaction by oxygen bridging for enhancing electrochemical performance

It is crucial to design core-shell materials with interfacial interaction, which enhances their electrical conductivity, structural stability, and facilitates efficient charge transfer at the interface. In this study, two core-shell electrodes NC-O-PBA (NC: nickel cobalt layered double hydroxides, O-bridged core-shell materials) and LCCH@Ni(OH)2@PBA (LCCH: linear cobalt carbonate hydroxides, PBA: prussian blue analogs) were fabricated via interfacial contrast strategy to investigate the optimization function of oxygen at core-shell interface. Results show that as-prepared NC-O-PBA with high oxygen content creates an ideal condition for the formation of oxygen bridging. Moreover, the NC-O-PBA promotes a strong bond cooperation between core (NiCo-LDH) and shell (NiCo PBAs). The unit in PBAs can partly coordinate with the oxygen (from hydroxyl groups and interlayer ions in LDH), thus forming a strong interfacial coordination bonding between LDH and PBAs (Ni/Co(LDH)-O-CN(PBAs) or Ni/Co(LDH)-O-Ni/Co(PBAs)). Subsequently, NC-O-PBA electrode presents a high capacity of 1040.6 F g−1 at 1 A g−1 and a retention rate of 87.5% at 1500 cycles of 3 A g−1, much higher than LCCH@Ni(OH)2@PBA (462.4 F g−1 and 41.26%). Finally, in-situ Raman results demonstrated the enhanced Faraday redox reaction of NC-O-PBA. This interfacial contrast strategy and oxygen-bridged approach provide a novel idea for the development of high-performance core-shell electrode materials and facilitate deeper insights into mechanism.

Bifunctional CuO@CoV layered double hydroxide (LDH) core–shell heterostructure for electrochemical energy storage and electrocatalysis

The state-of-the-art designing and development of materials is an inevitable prior step for an effective solution regarding energy resources. In the context of supercapacitors (SCs) and electrocatalysis, it remains a challenge to fabricate electrode materials with high specific capacitance, high conductivity and lower overpotential. Here, a core–shell structure is prepared via a facile two-step electrodeposition method using CuO core and electrodeposited binary CoV LDH as the shell and used as a SC electrode and an electrocatalyst. For comparison, the CuO and Cu@CoV LDH electrodes are also prepared using a similar method. The CuO@CoV LDH core–shell electrode exhibits an areal capacitance of 206 mF cm−2 accompanied by an excellent stability of 88 % over 5000 cycles at a current density of 10 mA cm−2. This areal capacitance is far better than that obtained for CuO (49 mF cm−2) and Cu@CoV LDH (58 mF cm−2) electrodes. The symmetric device is fabricated using core–shell heterostructure demonstrating an energy density of 62.8 mWh cm−2 and power density of 985 mW cm−2. Moreover, the CuO@CoV LDH core–shell structure demonstrates an excellent oxygen evolution reaction (OER) catalytic activity with an overpotential of 329 mV and a Tafel slope of 65 mV dec-1. This study opens a new route for the fabrication of CuO@CoV LDH core–shell structure via facile electrodeposition method for the electrochemical energy storage and catalytic activity.

High energy density pouch-type supercapacitor achieved by MOFs derived 3D hollow N-doped carbon with Fe2O3 and hierarchical CuCo2S4@NiFe-LDH core-shell nanostructures

The multicomponent rational control and distinctive architectural design of electrode materials remain critical factors for enhancing the energy density of supercapacitors. Herein, metal-organic framework (MOF)-derived three-dimensional (3D) hollow nitrogen-doped carbon (NHCs) with Fe2O3 core-shell composite negative electrode materials (NHCs@Fe2O3) were developed. In this framework, 1) the high specific surface area caused by the distinctive core-shell structure facilitated the electrolyte infiltration in the hollow skeleton, which shortened the ion transport path and enabled fast electron transfer; and 2) the synergistic effect of the nitrogen-containing groups of the hollow carbon and the reversible Faraday reaction of metal oxides increased the ratio of the pseudocapacitance. These phenomena were the primary reasons for the enhanced capacity of the core-shell electrode. Additionally, hierarchical CuCo2S4@layered double hydroxide (NiFe-LDH) nanobelt core-shell heterostructure arrays integrated on the nickel foam were used for the positive electrode materials. The asymmetric pouch-type supercapacitor assembled with NHCs@Fe2O3 (negative electrode) and CuCo2S4@NiFe-LDH (positive electrode) exhibited a high energy density of 68.6 W h kg–1 at a power density of 828.9 W kg–1. This work offers an effective strategy for fabricating multicomponent core-shell materials and optimizing the interactions between the components to enhance the electrochemical performance in energy storage applications.

Co-electrodeposition hybrid reduced graphene oxide and nickel-cobalt selenide nanosheets on silicon nanowires for high-performance supercapacitor

Due to inherent compatibility with IC technology, 3D silicon is prone to build a skeleton for the energy storage electrodes. Herein, a unique 3D hierarchical core-shell electrode was first developed with silicon nanowire arrays (SiNWs), metal selenide (TMSe) and reduced graphene oxide (RGO) nanosheets, where SiNWs decorated with Ni particles (Si/Ni) served as the conductive core and co-electrodeposited hybrid nickel-cobalt selenide (NCSe) and RGO nanosheets (NCSe-RG) functioned as the high capacitive outer shell. Owing to the synergy effect between NCSe and RGO, high-speed electron transport channels of Si/Ni, and abundant electroactive sites of porous NCSe layer, the synthesized Si/Ni/NCSe-RG electrode delivered a large capacitance of 2268 F g−1 (1973 mF cm−2) at 1 A g−1 which was higher than most reported silicon-based electrodes, and an excellent rapid-charging capability (1540 F g−1 at 30 A g−1). Furthermore, a solid asymmetric supercapacitor (SC) was prepared by using Si/Ni/NCSe-RG as the positive electrode, demonstrating an excellent energy density of 53.23 Wh kg−1 at the power density of 800 W kg−1. Our results suggest that high-performance SC electrodes can be engineered with TMSe and 3D silicon with a simple and time-saving method.

Corrosion-engineered NiMnFe(OH)x@NiMn/TP core–shell electrode for anion exchange membrane water electrolyzers

Exploring cost-effective and highly efficient electrodes is crucial for realizing future renewable energy systems for anion exchange membrane water electrolyzers (AEMWE). There are two half-reactions that occur during water electrolysis, and the development of an effective electrode for the sluggish oxygen evolution reaction (OER) is considered as a key aspect of the half-reaction. In this study, a ternary metal hydroxides electrode was fabricated using a two-step (electrodeposition and corrosion engineering) process. The hydrogen bubble templating electrodeposition enabled the control of the morphology from a dense film to a porous coral-like electrode. Furthermore, Fe was introduced to the electrode to form a core–shell structure via corrosion engineering. The OER catalytic activities of the electrodes were compared in a half-cell, and the results indicated that the optimized electrode required values of 322 mV at 50 mA cm−2. Additionally, stability test was conducted at 100 mA cm−2 for 12 h, and the results indicated that the variation ratio was observed at 1.90 mV h−1. The optimized NiMnFe(OH)x@NiMn/TP was utilized into a membrane electrode assembly (MEA) as an anode, and the catalytic activity of the anode was tested in a single-cell of AEMWE, and it exhibited a current density of 1.5 A cm−2 at 2.02 Vcell and maintained its performance for more than 50 h.

Effect of TiO2-SiO2 composite films on the performance of perovskite solar cells

Nano-TiO2 semiconductor film has the characteristics of high porosity and large specific surface area. However, there is much surface state in the TiO2 semiconductor film, and its energy level is in the band gap, which forms a local state with traps, restricts the movement of electrons in the film, and causes serious electron recombination. In this paper, the TiO2 surface is covered with a wide band gap semiconductor SiO2 in the electron transport layer of the perovskite solar cell. A core-shell electrode is formed to inhibit electron recombination and improve efficiency of perovskite solar cells.

A novel non-enzymatic electrochemical sensor based on NiS/Co3S4@h-Ni NWs core-shell electrode for glucose detection in human serum

To obtain a non-enzymatic electrochemical sensor with good performance such as sensitivity, selectivity, and stability, fine-tuning and rational design of the electrocatalytic material are essential. In this study, a novel catalyst (NiS/Co3S4@h-Ni NWs) with a hierarchical core-shell structure was synthesized in two steps to be used as a non-enzymatic electrode for glucose detection. First, hierarchical nickel nanowires, h-Ni NWs (the core), were prepared by the reduction of Ni2+ ions by hydrazine N2H4, and then the h-Ni NWs are covered with NiS/Co3S4 (the shell) by the hydrothermal method. The resulting NiS/Co3S4@h-Ni NWs showed a core-shell structure with abundant nanotides on the surface and good crystallinity. The prepared sensor exhibited two linearity ranges in the glucose concentration ranges of 0.001–6.57 mM and 6.57–13.32 mM with a sensitivity of 1171.9 μA mM−1 cm−2 and 316.5 μA mM−1.cm−2, respectively, and with a low detection limit of 0.13 μM (S/N = 3) due to its developed core-shell structure that provides excellent conductivity, an efficient mesoporous network, and suitable channels for rapid ion/electron transfer for electrocatalytic activity. In addition, the sensor also showed exceptional selectivity against coexistence interference, good long-term stability, reproducibility, and repeatability. All these excellent results show that the prepared NiS/Co3S4@h-Ni NWs catalyst can be a promising electrode material for glucose detection.

Preparation of sulfur vacancy modified NiCo2S4@NiCoS2 core-shell electrode material and its application in asymmetric supercapacitors

Nickel-cobalt based bimetallic sulfide has attracted much attention as positive electrode materials for supercapacitors due to its microstructure designability. However, charge storage occurs mostly on the surface of the material, which limits the full utilization of the active material inside. Here, rich sulfur vacancies modified NiCo2S4@NiCoS2 (Vs-NiCo2S4@NiCoS2) core-shell structures are grown tightly on a nickel foam substrate and prepared as positive material for supercapacitors. The rich sulfur vacancies in the Vs-NiCo2S4 "core" increase the electrochemical active sites and electron transport rates, while the amorphous NiCoS2 "shell" facilitates the rapid diffusion of ions. The results show that Vs-NiCo2S4@NiCoS2 core-shell structure has a specific capacitance of 3200 F g−1, achieving the effect of "1 + 1>2". The excellent electrochemical performance is attributed to the surface/interface modification of rich sulfur vacancies and the synergistic effect induced by heterogeneous core-shell boundaries. Moreover, the asymmetric supercapacitor Vs-NiCo2S4@NiCoS2//AC exhibits an energy density of 46.3 Wh kg−1 and a power density of 799.8 W kg−1, as well as excellent cyclic stability (nearly 80% capacity retention after 10,000 cycles). This work provides a new idea and strategy for core-shell structure design of nickel-cobalt sulfide electrode materials combined with surface/interface modification.

High-Activity 2D/2D Core–Shell Structure to NiMoO4-Based Electrodes for Electrochemical Energy Storage

The limited reactive active sites on the surface of NiMoO4 electrodes are the main bottleneck, restricting the rate performance of the corresponding supercapacitors (SCs). However, it is still a difficult problem to improve the utilization of redox reaction sites by adjusting the interface of the nickel molybdate (NiMoO4) electrode. This study reports a two-dimensional (2D)/2D core-shell electrode on a carbon cloth (CC) with NiMoO4 nanosheets grown on NiFeZn-LDH nanosheets (NFZ@NMO/CC). The interface of the 2D/2D core-shell structure promotes the redox reaction by improving OH- adsorption and diffusion capacity (diffusion coefficient = 1.47 × 10-7 cm2 s-1) and increasing the electrochemical active surface area (ECSA = 737.5 mF cm-2), which are much larger than the pure NiMoO4 electrode (2.5 × 10-9 cm2 s-1 and 177.5 mF cm-2). The NFZ@NMO/CC electrode exhibits an excellent capacitance of 2864.4 F g-1 at 1 A g-1 and an outstanding rate performance (92%), which is 3.18 times and 1.9 times those of the NiMoO4 nanosheets (33%) and the NiFeZn-LDH nanosheets (57.14%), respectively. Additionally, an asymmetric SC was assembled with NFZ@NMO/CC as the anode and Zn metal-organic framework (MOF)-derived carbon nanosheet (CNS)/CC as the cathode, which exhibited superior energy and power densities (70 Wh kg-1 and 709 W kg-1) with good cycling capability.

Hierarchical 2D MnO2@1D mesoporous NiTiO3 core-shell hybrid structures for high-performance supercapattery electrodes: Theoretical and experimental investigations

Novel hybrid core–shell electrodes of 2D and 1D nanomaterials have the ability to effectively address the relatively lower specific energy of supercapacitors. Herein, we report the utilization of the core–shell structure of hierarchical 2D Manganese Dioxide (MnO2) nanoflakes and 1D Nickel Titanate (NiTiO3) (NTO) mesoporous rods as an efficient supercapacitor electrode providing an enormous surface area and more pathways for OH– ions diffusion. The two-step-chemically processed hybrid porous core–shell hetero-architecture of MnO2@NTO delivers a specific capacitance of 1054.7 F/g, specific power of 11879.87 W/kg, and specific energy of 36.23 Wh/kg. Furthermore, 85.3 % retention in capacitance is perceived after 5000 cycles without degradation in the surface morphological features. Complementary first principles density functional theory (DFT) calculations reveal synergistic interaction of MnO2 with NTO in the MnO2@NTO heterostructure, which improves the electrical conductivity.

Correlating between the height of three-dimensional core-shell electrodes and ion transport for their electrochemical performance

The height of electrodes for in-situ grown 3D core-shell electrodes on a collector, which can directly affect the transport of electrolyte ions, is an important issue that needs to be concerned. Herein, nanocone Co2(OH)2CO3 (CCH) with different heights were synthesized as representative demos to explore the possible factors, including the height h, ion diffusion coefficient D, and Warburg coefficient σ for addressing the ion transport issue. A compromise balance between the height and ion diffusion coefficient was obtained after a series of dynamic analyses. The results showed that the optimal height of CCH can improve ion transport and shorten the charge transfer distance while avoiding stacking and curling. The best electrochemical performance renders the minimum Warburg and maximum ion diffusion coefficients. Furthermore, in-situ EIS and Raman showed that the active sites of CCH were the exposed Co in octahedral units, which can form linkage of octahedrally-electrolyte upon suitable cycling height can reveal more cations, thereby producing more extraordinary electrochemical performance. This work emphasizes the importance of ion diffusion behavior for electrochemical performance within electrodes. It gives a guide for constructing core-shell electrodes with a high electrochemical performance by engineering the microscopic height of materials.

One-step synthesis of novel core-shell bimetallic hexacyanoferrate for high performance sodium-storage cathode

• A one-step synthesis strategy is developed for preparing core-shell bimetallic hexacyanoferrate. • DFT calculations confirm that ordered-disorder induce the formation of core-shell structure. • The MnFeHCF@MnFeHCF exhibits a larger BET area, higher Na + content and lower Fe(CN) 6 vacancies. • The diffusion mechanism of Na + ions in both core-shell electrodes is discussed in detail. • The stability mechanism of NiHCF shell on the properties of FeHCF core is unraveled. Recently, the design of core-shell hierarchical architecture plays an important role in improving the electrochemical performance of Prussian blue analogue cathodes (PBAs). Unfortunately, the inconvenient stepwise preparation and the strict lattice-matching requirement have restricted the development of core-shell PBAs. Herein, we demonstrate a one-step synthesis strategy to synthesize core-shell manganese hexacyanoferrate (MnFeHCF@MnFeHCF) for the first time. And the formation mechanism of the core-shell hierarchical architecture is investigated by first-principles calculations. It is found that the as-obtained MnFeHCF@MnFeHCF act out the superior intrinsic natures, which not only can obtain a larger specific surface area and lower Fe(CN) 6 vacancies but also can activate more Na-storage sites. Compared with the manganese hexacyanoferrate (MnHCF), the iron hexacyanoferrate (FeHCF), and even the traditional core-shell nickel hexacyanoferrate (FeHCF@NiHCF) prepared by a stepwise method, the MnFeHCF@MnFeHCF demonstrates a superior rate performance, which achieves a high capacity of 131 mAh g −1 at 50 mA g −1 and delivers a considerable discharge capacity of about 100 mAh g −1 even at 1600 mA g −1 . Meantime, the capacity retention can reach up to nearly 80% after 500 cycles. The improved performances could be mainly originated from two aspects: on the one hand, Mn substitution is helpful to enhance the material conductivity; on the other hand, the core-shell structure with matched lattice parameters is more favorable to enhance the diffusion coefficient of sodium ions. Beside, the structural transformation of MnFeHCF@MnFeHCF upon the extraction/insertion of sodium ions is instrumental in releasing the interior stress and effectively maintaining the integrity of the crystal structure.