Multi-electron Reactions Research Articles

Defective Nb2C MXene Cocatalyst on TiO2 Microsphere for Enhanced Photocatalytic CO2 Conversion to Methane.

Sustainable and scalable solar-energy-driven CO2 conversion into fuels requires earth-abundant and stable photocatalysts. In this work, a defective Nb2C MXene as a cocatalyst and TiO2 microspheres as photo-absorbers, constructed via a coulombic force-driven self-assembly, is synthesized. Such photocatalyst, at an optimized loading of defective Nb2C MXene (5% def-Nb2C/TiO2), exhibits a CH4 production rate of 7.23µmolg-1h-1, which is 3.8 times higher than that of TiO2. The Schottky junction at the interface improves charge transfer from TiO2 to defective Nb2C MXene and the electron-rich feature (nearly free electron states) enables multielectron reaction of CO2, which apparently leads to high activity and selectivity to CH4 (sel. 99.5%) production. Moreover, DFT calculation demonstrates that the Fermi level (EF) of defective Nb2C MXene (-0.3V vs NHE) is more positive than that of Nb2C MXene (-1.0V vs NHE), implying a strong capacity to accept photogenerated electrons and enhance carrier lifetime. This work gives a direction to modify the earth-abundant MXene family as cocatalysts to build high-performance photocatalysts for energy production.

Perovskite Cathodes for Aqueous and Organic Iodine Batteries Operating Under One and Two Electrons Redox Modes.

Although conversion-type iodine-based batteries are considered promising for energy storage systems, stable electrode materials are scarce, especially for high-performance multi-electron reactions. The use of tin-based iodine-rich 2D Dion-Jacobson (DJ) ODASnI4 (ODA: 1,8-octanediamine) perovskite materials as cathode materials for iodine-based batteries is suggested. As a proof of concept, organic lithium-perovskite and aqueous zinc-perovskite batteries are fabricated and they can be operated based on the conventional one-electron and advanced two-electron transfer modes. The active elemental iodine in the perovskite cathode provides capacity through a reversible I- /I+ redox pair conversion at full depth, and the rapid electron injection/extraction leads to excellent reaction kinetics. Consequently, high discharge plateaus (1.71V vs Zn2+ /Zn; 3.41V vs Li+ /Li), large capacity (421 mAh g-1 I ), and a low decay rate (1.74mVmAh-1 g-1 I ) are achieved for lithium and zinc ion batteries, respectively. This study demonstrates the promising potential of perovskite materials for high-performance metal-iodine batteries. Their reactions based on the two-electron transfer mechanism shed light on similar battery systems aiming for decent operational stability and high energy density.

Electrolyte pH and operating potential: critical factors regulating the anodic oxidation and zinc storage mechanisms in aqueous zinc ion battery

The complicated multi-electron reactions and electrochemical/chemical evolution of vanadium oxides in zinc ion batteries make the detailed reaction mechanism difficult to understand. Here, we show that these reactions can be easily interpreted from the reliable potential–V-species (electrochemical) and pH–V-species (chemical) relationships. A systematic investigation of several low-valence vanadium oxides (V6O13, VO2, and V2O3) is conducted to study the detailed reaction mechanisms upon the anodic oxidation and routine zinc storage process. Vanadium oxides are thermodynamically converted to layered zinc pyrovanadate Zn3V2O7(OH)2·2H2O (ZVOH) in a certain range of pH (4.0–8.5) and operating potential following the VOx oxidation →V-species dissolution →ZVOH precipitation processes. The establishment of pH–V-species and potential–V-species relationships can well explain the reaction mechanisms not only in anodic oxidation but also in routine zinc insertion/extraction processes with the combination of electrochemical and chemical reactions. Moreover, due to the favorable open and stable crystal framework and unique Zn2+ storage mechanism, the obtained ZVOH exhibits a highly improved capacity of 492.7 mAh/g within the voltage window of 0.3–1.4 V. Our work highlights the critical roles of operating potential and electrolyte pH in zinc ion battery and offers new knowledge and practices for its commercialization.

Unravelling Twin Topotactic/Nontopotactic Reactive TiSe2 Cathodes for Aqueous Batteries.

Titanium selenide (TiSe2 ), a model transition metal chalcogenide material, typically relies on topotactic ion intercalation/deintercalation to achieve stable ion storage with minimal disruption of the transport pathways but has restricted capacity (<130 mAh g-1 ). Developing novel energy storage mechanisms beyond conventional intercalation to break capacity limits in TiSe2 cathodes is essential yet challenging. Herein, the ion storage properties of TiSe2 are revisited and an unusual thermodynamically stable twin topotactic/nontopotactic Cu2+ accommodation mechanism for aqueous batteries is unraveled. In situ synchrotron X-ray diffraction and ex situ microscopy jointly demonstrated that topotactic intercalation sustained the ion transport framework, nontopotactic conversion involved localized multielectron reactions, and these two parallel reactions are miraculously intertwined in nanoscale space. Comprehensive experimental and theoretical results suggested that the twin-reaction mechanism significantly improved the electron transfer ability, and the reserved intercalated TiSe2 structure anchored the reduced titanium monomers with high affinity and promoted efficient charge transfer to synergistically enhance the capacity and reversibility. Consequently, TiSe2 nanoflake cathodes delivered a never-before-achieved capacity of 275.9 mAh g-1 at 0.1 A g-1 , 93.5% capacity retention over 1000 cycles, and endow hybrid batteries (TiSe2 -Cu||Zn) with a stable energy supply of 181.34Wh kg-1 at 2339.81W kg-1 , offering a promising model for aqueous ion storage.

Activating three electron reaction in sodium vanadium ferric phosphate toward high energy density for Na-ion batteries

Na3V2(PO4)3 (NVP) with a robust sodium superionic conductor (NASICON) structure and high voltage platform has been regarded as one of the most prospective cathode materials for sodium-ion batteries (SIBs). Nevertheless, the increasing demand for energy density encourages us to activate multielectron reactions in NVP-based materials to achieve higher voltage/capacity to meet the challenge of commercialization of SIBs. Herein, NASICON-structured Na3V2−xFex(PO4)3 [NVP-Fe(x)] has been developed through a solid state reaction. The introduction of Fe3+ successfully activates high-voltage-platform redox couple of V4+/V5+ in Na3V2−xFex(PO4)3 and thus achieves three-electron redox reactions, resulting in significantly enhanced energy density (417.3 Wh kg−1) and superhigh initial capacity (166.4 mA h g−1 at 1 C). This work excites the generation of three-electron redox reactions in Fe3+-doped NVP for the first time, providing an important guidance for designing high-energy-density polyanionic materials for sodium storage by inducing multielectron redox reactions.

Stable multi-electron reaction stimulated by W doping VS4 for enhancing magnesium storage performance

Rechargeable magnesium batteries (RMBs) hold promise for offering higher volumetric energy density and safety features, attracting increasing research interest as the next post lithium-ion batteries. Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs. Herein, multi-electron reaction occurred in VS4 by simple W doping strategy. W doping induces valence of partial V as V2+ and V3+ in VS4 structure, and then stimulates electrochemical reaction involving multi-electrons in 0.5% W-V-S. The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process. The fabricated 0.5% W-V-S delivers higher specific capacity (149.3 mA h g−1 at 50 mA g−1, which is 1.6 times higher than that of VS4), superior rate capability (76 mA h g−1 at 1000 mA g−1), and stable cycling performance (1500 cycles with capacity retention ratio of 93.8%). Besides that, pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique (GITT) further confirms the enhanced Mg2+ storage kinetics during such multi-electron involved electrochemical reaction process. Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.

Manipulating the microstructure of Na2TiV(PO4)3 for aqueous Na ion storage

Polyanionic materials are among the most promising candidates as electrochemically active materials in sodium-ion secondary batteries, yet designing structures facilitating ion diffusion and electron transfer for electrodes that operate on multi-electron redox reactions proves both intriguing and challenging. In this study, we examine the electrochemical properties of mixed-polyanion Na2VTi(PO4)3/NaVP2O7, pure Na2VTi(PO4)3, and disordered Na2VTi(PO4)3 in an aqueous electrolyte. The former two polyanionic phosphates achieve an ultrahigh capacity (195.68 mAh g−1 at 0.2 A g−1) through three-sodium storage, whereas the disordered phosphate stores charge via a capacitive mechanism. Experimental tests and first-principle calculations demonstrate that enhancing the occupancy of asymmetric Na in the lattice establishes a new pathway for Na+ ions transport and narrows the band gap for electron transfer. Our work gives an insight into the local chemical environment of polyanionic phosphates composed of complex microstructures and provides a feasible strategy for obtaining electrode materials with exceptional performance.

Facile construction of ZnWO4/ZnO porous nanoplates on reduced graphene oxide for superior lithium storage

Zinc tungstate (ZnWO4) shows great promise as an anode material for lithium-ion batteries (LIBs) owing to its reversible multi-electron redox reactions and high theoretical capacity. Nevertheless, the low conductivity and big strain during cycling can lead to the inferior electrochemical properties of the ZnWO4 anode, hindering its practical application. Herein, we report a novel composite with ZnWO4/ZnO porous nanoplates in-situ constructed on reduced graphene oxide (rGO) by a metal–organic framework template strategy. The nanoplates with good porosity are composed of nanoparticles and nanorods, providing a short Li+-diffusion distance and plentiful Li+ storage active sites. The introduction of rGO can accelerate charge transfer and reinforce structural stability. As a result of these advantages, the ZnWO4/ZnO/rGO composite as LIBs anode delivers a high reversible capacity of 811 mAh g after 100 cycles at 200 mA g−1, excellent rate capability (437 mAh g at 5000 mA g−1), and good long cycling stability (485 mAh g after 500 cycles at 2000 mA g−1). Notably, the rate capability of the composite far precedes the previously reported ZnWO4-based anodes. This work provides an efficient approach for designing and fabricating advanced metal tungstate-based anodes for high-performance LIBs.

MAX, MXene, or MX: What Are They and Which One Is Better?

The fast ever-growing interest in transition metal carbonitrides (MXenes) for energy and catalysis is undermined by the undesirable multi-surficial terminations, which severely limit their applications. In contrast, considering the intriguing and tunable electronic structure, rich surface active sites, and high thermal durability, termination-free MXene (MX) hosts a huge possibility for catalysis. As such, recent advances in the evolution from MAX to MXene, and then to MX are overviewed and compared briefly, before concentrating on the unique future of MX in multi-heterogeneous catalysis. This work also looks beyond the fundamental properties of MX and discusses the potential of such materials for applications in multi-electron redox reactions. It is convinced that the potential success of MX in future catalysis is promising. Further extension toward high entropy and single-atom modifications will consolidate the leading position of MX in catalysis.

Efficient reduction of CO2 to C2 hydrocarbons by tandem nonthermal plasma and photocatalysis

CO2 photoreduction to hydrocarbons is a carbon-neutral technology for renewable energy. However, this strategy is challenged by the thermodynamic stability of CO2 and the low efficiency of multi-photoelectron utilization. In this paper, tandem nonthermal plasma and photocatalysis were used to effectively improve the efficiency of CO2 reduction to C2. We first activated CO2 by nonthermal plasma technology (NTP) and then converted the activated CO2 into C2 products by Cd0.8Zn0.2S/In2O3 photocatalyst with a special nanostructure. Without the addition of any sacrificial agent, the C2 yield of the catalyst reached 0.382 μmol h−1, which is one of the highest performances to date. In situ experimental and computational studies show that CO2+ activated by NTP has higher π orbital and HUMO levels of lone pair electrons and promotes the reduction of CO2+ by injecting electrons into the vacant orbital of the active site of Zn. At the same time, the unique structure of Cd0.8Zn0.2S/In2O3 photocatalyst can extend the life of charge through the optical field enhancement effect, and then react with the CO2+ intermediates generated by NTP technology to promote the coupling of C-C bonds, and finally promote the photocatalytic multi-electron reaction to produce C2 hydrocarbons.

The ultralong Mo4O11 nanoribbons: Ultrasonic synthesis and topotactic transformation toward high-performance sodium-ion batteries

The design and synthesis of two-dimensional layered transitional metal oxides (TMOs) have been of great interest for their potential application in sodium-ion batteries (SIBs), due to the advantages such as multivalent ions and tunable interlayer spacing. However, achieving a well-defined crystal structural topology and geometric morphology in TMOs still remains a significant challenge, particularly in tailoring their polyhedral structures. Herein, the ultralong Mo4O11 nanoribbons (Mo4O11-NR) were prepared by a simple aniline-assisted sonochemical method for the first time. The resulting nanoribbons possess a unique tunnel structure and exhibit topologically frustrated arrangements of MoO6 octahedra and MoO4 tetrahedra. When used as anodes for SIBs, multielectron redox reactions of Mo4O11-NR allow for high-capacity energy storage. The buffered volume expansion of the nanoribbons accommodates the strain that occurs during cycling, thereby boosting cycling stability. The topologically frustrated arrangements of the polyhedra further contribute to the efficient storage and transfer of ions and electrons. As a result, Mo4O11-NR anode achieves a reversible specific capacity of 101 mA h g−1 after 2,000 cycles, when subjected to a high current density of 5 A g−1. This exceptional performance highlights the potential of Mo4O11-NR material as an advanced anode material for high-power devices.

CO2 photoreduction with high selectivity of C2H4 production on conjugated microporous polymer with Cu single atoms

Selective conversion of CO2 to fuels and chemicals has been considered one of the key challenges in the photocatalytic CO2 reduction reaction. The multi-electron reduction reaction requires the design of photocatalysts that can adsorb CO2 and transfer electrons. Herein, Cu single atoms are confined in a conjugated microporous polymer (CMP) to construct Cun@CMP photocatalyst for CO2 reduction to produce C2H4 and CH4. By adjusting Cu loading, Cu0.012@CMP exhibited a high performance with production yields of 236.81 μmol·g−1·h−1 for C2H4, and 78.2 % selectivity for C2H4 formation. DFT calculations displayed the band structure and confirmed Cu–N together with characterization. The in situ DRIFTS revealed *CH2 and *C2H4 as key reaction intermediates to form CH4 and C2H4, respectively. The synergy effect in Cu single-atoms and CMP contributed greatly to C–C coupling and interfacial charge transfer, thus achieving excellent activity for conversion of CO2 to C1/C2. This work highlights the potential for constructing Cu single atoms on CMP to produce highly selective C2H4.

Reversible Multielectron Redox Chemistry in a NASICON-Type Cathode toward High-Energy-Density and Long-Life Sodium-Ion Full Batteries.

Na-superionic-conductor (NASICON)-type cathodes (e.g., Na3 V2 (PO4 )3 ) have attracted extensive attention due to their open and robust framework, fast Na+ mobility, and superior thermal stability. To commercialize sodium-ion batteries (SIBs), higher energy density and lower cost requirements are urgently needed for NASICON-type cathodes. Herein, Na3.5 V1.5 Fe0.5 (PO4 )3 (NVFP) is designed by an Fe-substitution strategy, which not only reduces the exorbitant cost of vanadium, but also realizes high-voltage multielectron reactions. The NVFP cathode can deliver extraordinary capacity (148.2mAhg-1 ), and decent cycling durability up to 84% after 10000 cycles at 100 C. In situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy characterizations reveal reversible structural evolution and redox processes (Fe2+ /Fe3+ , V3+ /V4+ , and V4+ /V5+ ) during electrochemical reactions. The low ionic-migration energy barrier and ideal Na+ -diffusion kinetics are elucidated by density functional theory calculations. Combined with electron paramagnetic resonance spectroscopy, Fe with unpaired electrons in the 3d orbital is inseparable from the higher-valence redox activation. More competitively, coupling with a hard carbon (HC) anode, HC//NVFP full cells demonstrate high-rate capability and long-duration cycling lifespan (3000stable cycles at 50 C), along with material-level energy density up to 304Whkg-1 . The present work can provide new perspectives to accelerate the commercialization of SIBs.

Nano-Ni/Co-PBA as high-performance cathode material for aqueous sodium-ion batteries

Prussian blue analogues (PBAs) are reliable and promising cathode materials for aqueous sodium-ion batteries (ASIBs) owing to their open three-dimensional frameworks, outstanding stability, and low production costs. However, PBAs containing only a single type of transition-metal ion often have limited charge-storage capacities in aqueous systems. This study reports the first example of K0.11Ni0.39Co0.79[Fe(CN)6]·2.04H2O nanoparticles (Ni/Co-PBA) being used as a high-capacity cathode material for ASIBs. Owing to multi-electron redox reactions involving Co and Fe ions, Ni/Co-PBA has an initial capacity of 65 mAh g−1 and a capacity retention rate of 80% after 1000 cycles at 1.0 A g−1, indicating its outstanding cycle performance and capacity retention. Ex-situ x-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and the galvanostatic intermittent titration technique were used to analyze the redox mechanisms and kinetics of Ni/Co-PBA. Ni/Co-PBA-based ASIBs are among the most promising energy-storage technologies for large-scale fixed energy-storage systems because of their outstanding electrochemical performance, low costs, and high efficiency.

An Ion Exchange Membrane-Free, Ultrastable Zinc-Iodine Battery Enabled by Functionalized Graphene Electrodes

Global warming requires a shift in the energy economy towards renewable energy sources, such as solar and wind energy, to meet the ever-increasing worldwide energy demand while having lesser negative impact on the environment. The integration of such sustainable energy resources into the existing infrastructure, however, is challenging due to their fluctuations and intermittences requiring the development of efficient (intermediate) energy storage systems. The ultimate goal for these systems pertains to high performance, durability, safety, facile scalability, cost, and environmental-friendliness. The aqueous rechargeable zinc-iodine (Zn-I2) battery is promising due to the high theoretical capacities of Zn (820 mAh gZn -1) and I2 (211 mA h gI2 -1) along with the very high solubilities in aqueous media. Other advantages include the abundance of the electrode materials and the safety of the aqueous electrolyte. The high energy density of aqueous zinc-based batteries is a result of the multi-electron redox reactions and the low electrochemical potential of Zn (-0.763 V vs. RHE) in mildly acidic electrolytes such as in a Zn-I2 battery. In addition, compared to other alkali metals such as lithium, sodium, and potassium, metallic Zn is relatively stable in an aqueous environment over a wide temperature range.Several challenges need to be addressed for Zn-I2 batteries to be competitive; namely, self-discharge, sluggish kinetics, low practical energy density, as well as the dendrite formation on the Zn anode. In this work, we design a high-performance Zn-I2 battery with an unusual long-term stability which is based on a novel design of electrodes and electrolyte. In detail, a three-dimensional functionalized graphene cathode facilitates the iodide redox reactions and also immobilizes dissolved polyiodides; thus, suppressing the detrimental shuttling effect. Furthermore, we design a composite anode made of Zn coated with a film of reduced graphene oxide. This modification significantly enhances the performance and stabilizes the anode during repeated Zn stripping/plating preventing dendrite formation. The electrolyte is formulated in a way that, along with the graphene-based cathode, allows for the utilization of an economical glass fiber separator instead of the commonly employed ion-exchange membranes, which are expensive and have relatively high ohmic resistances. Our novel Zn-I2 battery design exhibit high current efficiencies of nearly 100%, along with stable specific capacities of 257, 186, 150, 84 mAh g-1 at corresponding current densities of 1, 2, 5, 10 A g-1. Furthermore, a long-term capacity retention of 96.7% at 5 A g-1 over 2000 cycles is achieved, outperforming most comparable aqueous batteries.

Effects of surface chlorine atoms on charge distribution and reaction barriers for photocatalytic CO2 reduction

Photocatalytic CO2 reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues. However, the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions. Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products. In this study, we aim to regulate the surface electronic structure of Bi2WO6 by doping surface chlorine atoms to achieve effective photocatalytic CO2 reduction. Surface Cl atoms can enhance the absorption ability of light, affect its energy band structure and promote charge separation. Combined with DFT calculations, it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H2O and CO2, but also lower the formation energy barrier of intermediate products to generate more intermediate ∗COOH, thus facilitating CO production. Overall, this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO2 reduction activity of a layered structure Bi-based catalyst.

Graphitized Carbon-Coated Iron Fluoride Nanocavities for Enhanced Kinetics of Multielectron Cathode Conversion Reactions.

As for the conversion-type iron fluoride (FeF3) cathode material with multielectron reactions for lithium-ion batteries (LIBs), sluggish reaction kinetics and low electrical conductivity pose certain limitations for the long-lasting reversible conversion processes. Herein, the three-dimensional porous nitrogen-doped carbon matrix in situ anchoring FeF3 nanocavities coated by graphitized carbon (FeF3/GC) are rationally prepared. Through the Kirkendall effect, the low-temperature fluorination of NF3 enables the resultant hollow FeF3 nanoparticles to possess a large number of lithium storage cavities and outer graphitized carbon structure, further effectively buffering the expansion of volume. The FeF3/GC cathode delivers a superior discharge capacity of 504.2 mAh g-1 after 1200 cycles at 1000 mA g-1, with a capacity decay rate of only 0.01% per cycle. Even at a rate of 5000 mA g-1, the composite cathode still delivers a discharge capacity of 309.6 mAh g-1. Impressively, the existence of graphitized carbon and the short Li+ diffusion length ensure fast electron/ion transfer, which significantly enhances the conversion reaction kinetics. This study aims to provide a promising strategy for the efficiency enhancement of multielectron cathode conversion reactions for LIBs.

High-Performance Lithium-Sulfur Batteries via Molecular Complexation.

Beyond lithium-ion technologies, lithium-sulfur batteries stand out because of their multielectron redox reactions and high theoretical specific energy (2500 Wh kg-1). However, the intrinsic irreversible transformation of soluble lithium polysulfides to solid short-chain sulfur species (Li2S2 and Li2S) and the associated large volume change of electrode materials significantly impair the long-term stability of the battery. Here we present a liquid sulfur electrode consisting of lithium thiophosphate complexes dissolved in organic solvents that enable the bonding and storage of discharge reaction products without precipitation. Insights garnered from coupled spectroscopic and density functional theory studies guide the complex molecular design, complexation mechanism, and associated electrochemical reaction mechanism. With the novel complexes as cathode materials, high specific capacity (1425 mAh g-1 at 0.2 C) and excellent cycling stability (80% retention after 400 cycles at 0.5 C) are achieved at room temperature. Moreover, the highly reversible all-liquid electrochemical conversion enables excellent low-temperature battery operability (>400 mAh g-1 at -40 °C and >200 mAh g-1 at -60 °C). This work opens new avenues to design and tailor the sulfur electrode for enhanced electrochemical performance across a wide operating temperature range.

Preparation of disodium terephthalate/multi-walled carbon nanotube composite as an anode material for sodium-ion batteries: Performance and mechanism

Compared with the scarce resources of lithium-ion batteries (LIBs), sodium-ion batteries have been attracting research attentions as an ideal carrier for large-scale energy storage systems due to their abundant raw material resources. Organic materials are gaining importance as SIB anodes due to their advantages of simple preparation method, recyclability, and multi-electron reactions. In this work, disodium terephthalate/multi-walled carbon nanotube (Na2TP/MWCNT) organic composite was prepared as SIB anode material by an anti-solvent method. Experimental results indicated that the optimum sodium storage can be achieved with 10 wt% MWCNT dosage, where reversible capacities reached 229.9 and 93.2 mA h/g at current densities 0.1 and 2C, respectively. The capacity remained 124.9 mA h/g after 50 cycles at 1C current density, which suggested that the composite could act as a candidate for sodium ion battery anodes.

Na4MnCr(PO4)3 with a Dual Conductive Network for Sodium‐Ion Batteries

AbstractNASICON (NAtrium Super Ionic CONductor)‐structured Na4MnCr(PO4)3 has attracted attention as a promising cathode for sodium‐ion batteries due to its high operating voltage and specific capacity contributed by multielectron reactions. Unfortunately, its intrinsic low electronic conductivity significantly hinders the release of specific capacity and rate capability, preventing its practical application. Herein, a carbon layer with dual conductive networks connected by chain‐like Ketjen black (KB) is built on the surface of Na4MnCr(PO4)3 material. This novel Na4MnCr(PO4)3/C@KB composite material exhibits improved rate capability of 61.2 mAh g−1 at 2 C compared to 19.5 mAh g−1 of Na4MnCr(PO4)3/C and high reversible capacity of 88.0 mAh g−1 at 1 C with 73% capacity retention after 100 cycles. The enhanced electrochemical performance can be ascribed to an increase of electronic conductivity enabled by the dual conductive 3D network construction and an adequate infiltration of electrolyte by substantial pores existence in carbon layer. A promising dual conductive network design strategy is demonstrated here for improving the performance of NASICON‐structured cathodes.