High-Entropy Engineering of Cubic SiP with Metallic Conductivity for Fast and Durable Li-Ion Batteries.

A cost-effective, scalable ball milling process is employed to synthesize the InGeSiP3 compound with a cubic ZnS structure, aiming to address the sluggish reaction kinetics of Si-based anodes for Lithium-ion batteries. Experimental measurements and first-principles calculations confirm that the synthesized InGeSiP3 exhibits significantly higher electronic conductivity, larger Li-ion diffusivity, and greater tolerance to volume change than its parent phases InGe (or Si)P2 or In (or Ge, or Si)P. These improvements stem from its elevated configurational entropy. Multiple characterizations validate that InGeSiP3 undergoes a reversible Li-storage mechanism that involves intercalation, followed by conversion and alloy reactions, resulting in a reversible capacity of 1733 mA h g-1 with an initial Coulombic efficiency of 90%. Moreover, the InGeSiP3-based electrodes exhibit exceptional cycling stability, retaining an 1121 mA h g-1 capacity with a retention rate of ≈87% after 1500 cycles at 2000 mA g-1 and remarkable high-rate capability, achieving 882 mA h g-1 at 10 000 mA g-1. Inspired by the distinctive characteristic of high entropy, the synthesis is extended to high entropy GaCu (or Zn)InGeSiP5, CuZnInGeSiP5, GaCuZnInGeSiP6, InGeSiP2S (or Se), and InGeSiPSSe. This endeavor overcomes the immiscibility of different metals and non-metals, paving the way for the electrochemical energy storage application of high-entropy silicon-phosphides.

Decomposition of methanol-d4 on Rh nanoclusters supported by thin-film Al2O3/NiAl(100) under near-ambient-pressure conditions.

The decomposition of methanol-d4 (CD3OD) on Rh nanoclusters grown by the deposition of Rh vapors onto an ordered thin film of Al2O3/NiAl(100) was studied, with various surface-probe techniques and largely under near-ambient-pressure (NAP) conditions. The results showed a superior reactivity of small Rh clusters (diameter < 1.5 nm) exposed to CD3OD at 5 × 10-3-0.1 mbar at 400 K; the gaseous production of CO and D2 from decomposed methanol-d4 per Rh surface site on the small Rh clusters with diameters of ∼1.1 nm was nearly 8 times that on large ones with diameters of ∼3.5 nm. The promotion of reactivity with decreased cluster size under NAP conditions was evidently greater than that under ultrahigh vacuum conditions. Moreover, the concentration of atomic carbon (C*; where * denotes adsorbate)-a key catalyst poisoner-yielded from the dissociation of CO* from dehydrogenated methanol-d4 was significantly smaller on small clusters (diameter < 1.5 nm). The NAP size effect on methanol-d4 decomposition involved the surface hydroxyl (OH*) from the little co-adsorbed water (H2O*) that was dissociated at a probability dependent on the cluster size. H2O* was more likely dissociated into OH* on small Rh clusters, by virtue of their more reactive d-band structure, and the OH* then effectively promoted the O-D cleavage of methanol-d4, as the rate-determining step, and thus the reaction probability; on the other hand, the OH* limited CO* dissociation on small Rh clusters via both adsorbate and lateral effects. These results suggest that the superior properties of small Rh clusters in both reactivity and anti-poisoning would persist and be highly applicable under "real-world" catalysis conditions.

Decomposition of methanol-d4 on a thin film of Al2O3/NiAl(100) under near-ambient-pressure conditions.

We have studied the decomposition of methanol-d4 on thin film Al2O3/NiAl(100) under near-ambient-pressure conditions, with varied surface-probe techniques and calculations based on density-functional theory. Methanol-d4 neither adsorbed nor reacted on Al2O3/NiAl(100) at 400 K under ultrahigh vacuum conditions, whereas they dehydrogenated, largely to methoxy-d3 (CD3O*, * denoting adsorbates) and formaldehyde-d2 (CD2O*), on the surface when the methanol-d4 partial pressure was increased to 10-3 mbar and above. The dehydrogenation was facilitated by hydroxyl (OH* or OD*) from the dissociation of little co-adsorbed water; a small fraction of CD2O* interacted further with OH* (OD*) to form, via intermediate CD2OOH* (CD2OOD*), formic acid (DCOOH* or DCOOD*). A few surface carbonates were also yielded, likely on the defect sites of Al2O3/NiAl(100). The results suggest that alumina not only supports metal clusters but also participates in reactions under realistic catalytic conditions. One may consider accordingly the multiple functions of alumina while designing ideal catalysts.

Unique (100) Surface Configuration Enables Promising Oxygen Reduction Performance for Pt3Co Nanodendrite Catalysts.

Selective exposure of active surfaces of Pt-based electrocatalysts has been demonstrated as an effective strategy to improve Pt utilization and promote oxygen reduction reaction (ORR) activity in fuel cell application. However, challenges remain in stabilizing those active surface structures, which often suffer undesirable degradation and poor durability along with surface passivation, metal dissolution, and agglomeration of Pt-based electrocatalysts. To overcome the aforementioned obstacles, we here demonstrate the unique (100) surface configuration enabling active and stable ORR performance for bimetallic Pt3Co nanodendrite structures. Using elaborate microscopy and spectroscopy characterization, it is revealed that the Co atoms are preferentially segregated and oxidized at the Pt3Co(100) surface. In situ X-ray absorption spectroscopy (XAS) shows that such (100) surface configuration prevents the oxygen chemisorption and oxide formation on active Pt during the ORR process. Thus, the Pt3Co nanodendrite catalyst shows not only a high ORR mass activity of 730 mA/mg at 0.9 V vs RHE, which is 6.6-fold higher than that of the Pt/C, but also impressively high stability with 98% current retention after the acceleration degradation test in acid media for 5000 cycles, far exceeding the Pt or Pt3Co nanoparticles. Density functional theory (DFT) calculation also confirms the lateral and structural effects from the segregated Co and oxides on the Pt3Co(100) surface in reducing the catalyst oxophilicity and the free energy for the formation of an OH intermediate in the ORR.

Single-Phase Ternary Compounds with a Disordered Lattice and Liquid Metal Phase for High-Performance Li-Ion Battery Anodes.

Si is considered as the promising anode materials for lithium-ion batteries (LIBs) owing to their high capacities of 4200 mAh g-1 and natural abundancy. However, severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications. To resolve the afore-mentioned problems, we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP2 compound, where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method. As confirmed by experimental and theoretical analyses, the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity, respectively, while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases. The resulting GaSiP2 electrodes delivered the high specific capacity of 1615 mAh g-1 and high initial Coulombic efficiency of 91%, while the graphite-modified GaSiP2 (GaSiP2@C) achieved 83% of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1. Furthermore, the LiNi0.8Co0.1Mn0.1O2//GaSiP2@C full cells achieved the high specific capacity of 1049 mAh g-1 after 100 cycles, paving a way for the rational design of high-performance LIB anode materials.

Probing the Roles of Indium Oxides on Copper Catalysts for Enhanced Selectivity during CO2-to-CO Electrochemical Reduction.

The electrochemical CO2 reduction reaction (CO2RR) provides an alternative protocol to producing industrial chemicals with renewable electricity sources, and the highly selective, durable, and economic catalysts should expedite CO2RR applications. Here, we demonstrate a composite Cu-In2O3 catalyst in which a trace amount of In2O3 decorated on Cu surface greatly improves the selectivity and stability for CO2-to-CO reduction as compared to the counterparts (Cu or In2O3), realizing a CO faradaic efficiency (FECO) of 95% at -0.7 V (vs RHE) and no obvious degradation within 7 h. In situ X-ray absorption spectroscopy reveals that In2O3 undergoes the redox reaction and preserves the metallic state of Cu during the CO2RR process. Strong electronic interaction and coupling occur at the Cu/In2O3 interface which serves as the active site for selective CO2RR. Theoretical calculation confirms the roles of In2O3 in preventing oxidation and altering the electronic structure of Cu to assist COOH* formation and demote CO* adsorption at the Cu/In2O3 interface.

A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides.

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na+ diffusion channels and complicated phase evolution during Na+ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi0.5Mn0.5-xSbxO2 (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na+ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na+ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g-1 at 0.2 C and 74.5 mAh g-1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

Unraveling the Nature and Role of Layered Cation Ordering in Cation-Disordered Rock-Salt Cathodes.

Cation-disordered rock salts (DRXs), a new class of cathode materials for Li-ion batteries, have attracted a great amount of attention in recent years due to their fascinatingly simple cubic structure, highly diverse composition, and great electrochemical performance. As cations in DRXs are randomly distributed in a long range, how the cations are spatially arranged is an intriguing question for the community of solid-state materials chemistry. In this work, we report the vibrational structure of a series of Mn- and Fe-based DRXs with well-controlled compositions and reveal significant layered-like cation ordering in the DRXs. A scheme is proposed to describe how the layered-like anisotropy could exist in rock salt structures with an overall cubic diffraction pattern. Furthermore, we raise a model of Li-ion transport based on the proposed scheme, which complements the theory of Li percolation in DRXs. The electrochemical behavior of the DRX cathodes used in the study supports the scheme and clearly demonstrates the role of layered anisotropy in the battery performance of DRXs.

A Nonstoichiometric Niobium Oxide/Graphite Composite for Fast-Charge Lithium-Ion Batteries.

Electrification of transportation has spurred the development of fast-charge energy storage devices. High-power lithium-ion batteries require electrode materials that can store lithium quickly and reversibly. Herein, the design and construction of a Nb2 O5-δ /graphite composite electrode that demonstrates remarkable rate capability and durability are reported. The presence of graphite enables the formation of a dominant Nb12 O29 phase and a minor T-Nb2 O5 phase. The high rate capability is attributed to the enhanced electronic conductivity and lower energy barriers for fast lithium diffusion in both Nb12 O29 and T-Nb2 O5 , as unraveled by density functional theory calculations. The excellent durability or long cycling life is originated from the coherent redox behavior of Nb ions and high reversibility of lithium intercalation/deintercalation, as revealed by operando X-ray absorption spectroscopy analysis. When tested in a half-cell at high cycling rates, the composite electrode delivers a specific capability of 120 mAh g-1 at 80 C and retains over 150 mAh g-1 after 2000 cycles at 30 C, implying that it is a highly promising anode material for fast-charging lithium-ion batteries.

Enhanced Magnetic Order and Reversed Magnetization Induced by Strong Antiferromagnetic Coupling at Hybrid Ferromagnetic-Organic Heterojunctions.

Organic-molecular magnets based on a metal-organic framework with chemically tuned electronic and magnetic properties have been attracting tremendous attention due to their promising applications in molecular magnetic sensors, magnetic particle medicines, molecular spintronics, etc. Here, we investigated the magnetic behavior of a heterojunction comprising a ferromagnetic nickel (Ni) film and an organic semiconductor (OSC) 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) layer. Through the magneto-optical Kerr effect (MOKE), a photoemission electron microscopy (PEEM), X-ray magnetic circular dichroism (XMCD), and X-ray photoelectron spectroscopy (XPS), we found that the adsorption of F4-TCNQ on Cu(100)/Ni not only reverses the in-plane magnetization direction originally exhibited by the Ni layer but also results in enhanced magnetic ordering. Furthermore, the cyano group (CN) in adsorbed F4-TCNQ was found spin-polarized along with conspicuous charge transfer with Ni. The density functional theory (DFT) calculations suggest that the experimentally found spin polarization originates from hybridization between the CN group's π orbitals and Ni's d band. These findings signify that the hybrid states at the organic-ferromagnet interface play a key role in tailoring the magnetic behavior of interfaces. For the case of the F4-TCNQ and Ni heterojunction reported here, interface coupling is an antiferromagnetic one.

Stable Pd-Cu Hydride Catalyst for Efficient Hydrogen Evolution.

Pd has been regarded as one of the alternatives to Pt as a promising hydrogen evolution reaction (HER) catalyst. Strategies including Pd-metal alloys (Pd-M) and Pd hydrides (PdHx) have been proposed to boost HER performances. However, the stability issues, e.g., the dissolution in Pd-M and the hydrogen releasing in PdHx, restrict the industrial application of Pd-based HER catalysts. We here design and synthesize a stable Pd-Cu hydride (PdCu0.2H0.43) catalyst, combining the advantages of both Pd-M and PdHx structures and improving the HER durability simultaneously. The hydrogen intercalation is realized under atmospheric pressure (1.0 atm) following our synthetic approach that imparts high stability to the Pd-Cu hydride structure. The obtained PdCu0.2H0.43 catalyst exhibits a small overpotential of 28 mV at 10 mA/cm2, a low Tafel slope of 23 mV/dec, and excellent HER durability due to its appropriate hydrogen adsorption free energy and alleviated metal dissolution rate.

Enhanced CO2 Electrochemical Reduction Performance over Cu@AuCu Catalysts at High Noble Metal Utilization Efficiency.

The electrochemical CO2 reduction reaction (CO2RR) represents a viable alternative to help close the anthropogenic carbon cycle and convert intermittent electricity from renewable energy sources to chemical energy in the form of value-added chemicals. The development of economic catalysts possessing high faradaic efficiency (FE) and mass activity (MA) toward CO2RR is critical in accelerating CO2 utilization technology. Herein, an elaborate Au-Cu catalyst where an alloyed AuCu shell caps on a Cu core (Cu@AuCu) is developed and evaluated for CO2-to-CO electrochemical conversion. Specific roles of Cu and Au for CO2RR are revealed in the alloyed core-shell structure, respectively, and a compositional-dependent volcano-plot is disclosed for the Cu@AuCu catalysts toward selective CO production. As a result, the Au2-Cu8 alloyed core-shell catalyst (only 17% Au content) achieves an FECO value as high as 94% and an MACO of 439 mA/mgAu at -0.8 V (vs RHE), superior to the values for pure Au, reflecting its high noble metal utilization efficiency.

Dissociation of water on atomic oxygen-covered Rh nanoclusters supported on graphene/Ru(0001).

We studied the dissociation of water (H2O*, with * denoting adspecies) on atomic oxygen (O*)-covered Rh nanoclusters (RhO* ) supported on a graphene film grown on a Ru(0001) surface [G/Ru(0001)] under ultrahigh-vacuum conditions and with varied surface-probe techniques and calculations based on density-functional theory. The graphene had a single rotational domain; its lattice expanded by about 5.7% to match the Ru substrate structurally better. The Rh clusters were grown by depositing Rh vapors onto G/Ru(0001); they had an fcc phase and grew in (111) orientation. Water adsorbed on the Rh clusters was dissociated exclusively in the presence of O*, like that on a Rh(111) single-crystal surface. Contrary to the case on Rh(111)O* , excess O* (even at a saturation level) on small RhO* clusters (diameter of 30-34 Å) continued to promote, instead of inhibiting, the dissociation of water; the produced hydroxyl (OH*) increased generally with the concentration of O* on the clusters. The difference results from more reactive O* on the RhO* clusters. O* on RhO* clusters activated the dissociation via both the formation of hydrogen bonds with H2O* and abstraction of H directly from H2O*, whereas O* on Rh(111)O* assisted the dissociation largely via the formation of hydrogen bonds, which was readily obstructed with an increased O* coverage. As the disproportionation (2 OH* → H2O* + O*) is endothermic on the RhO* clusters but exothermic on Rh(111)O* , OH* produced on RhO* clusters showed a thermal stability superior to that on the Rh(111)O* surface-thermally stable up to 400 K.

Dependence on Size of Supported Rh Nanoclusters in the Dehydrogenation of Methanol-d4 Obstructed by CO.

The size effect on the activity of a catalyst has been a focal issue since ideal catalysts were pursued, whereas that on the degradation of a catalyst, by reaction intermediates such as CO, is little discussed. We demonstrate that the dehydrogenation of methanol-d4 on supported Rh nanoclusters precovered with CO (Rh-CO clusters) was obstructed, indicated by a decreased production of CO and D2; the obstructive effect exhibits a remarkable dependence on the cluster size, with a minimum at a cluster diameter near 1.4 nm. The decreased production arose from a decreased reaction probability controlled by the increased activation energy for each dehydrogenation step (including formation of methoxy-d3), adsorption energies of CO, and repulsion from the CO array on the Rh-CO surface. The effects of these factors in deactivating the clusters varied separately with the cluster size. Consequently, the size effect on the CO poisoning should be taken into account in engineering the cluster size to optimize the catalytic performance.

Promoted activity of annealed Rh nanoclusters on thin films of Al2O3/NiAl(100) in the dehydrogenation of Methanol-d4.

Annealed Rh nanoclusters on an ordered thin film of Al2O3/NiAl(100) were shown to exhibit a promoted reactivity toward the decomposition of methanol-d4, under both ultrahigh vacuum and near-ambient-pressure conditions. The Rh clusters were grown with vapor deposition onto the Al2O3/NiAl(100) surface at 300 K and annealed to 700 K. The decomposition of methanol-d4 proceeded only through dehydrogenation, with CO and deuterium as products, on Rh clusters both as prepared and annealed. Nevertheless, the catalytic reactivity of the annealed clusters, measured with the production of either CO or deuterium per surface Rh site from the reaction, became at least 2-3 times that of the as-prepared ones. The promoted reactivity results from an altered support effect associated with an annealing-induced mass transport at the surface. Our results demonstrate a possibility to practically prepare reactive Rh clusters, regardless of the cluster size, that can tolerate an elevated reaction temperature, with no decreased reactivity.

Optimization of Pt-Oxygen-Containing Species Anodes for Ethanol Oxidation Reaction: High Performance of Pt-AuSnOx Electrocatalyst.

Pt-oxygen-containing species (Pt-OCS) catalysts, in which OCS (e.g., metal-oxides) are decorated on a Pt surface, possess enhanced ethanol oxidation reaction (EOR) activity and stability compared with pure Pt and are promising in practical applications of direct ethanol fuel cells. We investigate the promotion roles of Pt-OCS electrocatalysts toward the EOR via a combination of density functional theory (DFT) calculations and experiments, providing a rational design strategy for Pt-OCS catalysts. It is revealed that Pt-AuO and Pt-SnO excel in EOR activity and stability, respectively, among the DFT screening of various Pt-OCS systems, and this is confirmed by the following experiments. Moreover, an optimized Pt-AuSnO catalyst is proposed by DFT calculations, taking advantage of both Pt-AuO and Pt-SnO. The as-prepared Pt-AuSnO catalyst delivers an EOR activity that is 9.7 times higher than that of Pt and shows desired stability. These findings are expected to elucidate the mechanistic insights into Pt-OCS materials and lead to advanced EOR electrocatalysts.

Dependence on co-adsorbed water in the reforming reaction of ethanol on a Rh(111) surface.

We have studied the reforming reaction of ethanol co-adsorbed with atomic oxygen (O*, * denotes adspecies) and deuterated water (D2O*) on a Rh(111) surface, with varied surface probe techniques under UHV conditions and with density-functional-theory calculations. Adsorbed ethanol molecules were found to penetrate readily through pre-adsorbed water, even up to eight overlayers, to react at the Rh surface; they decomposed at a probability promoted by the water overlayers. The production probabilities of H2, CO, CH2CH2 and CH4 continued to increase with co-adsorbed D2O*, up to two D2O overlayers, despite separate increasing rates; above two D2O overlayers, those of H2, CO and CH2CH2 were approximately saturated while that of CH4 decreased. The increased (or saturated) production probabilities are rationalized with an increased (saturated) concentration of surface hydroxyl (OD*, formed by O* abstracting D from D2O*), whose intermolecular hydrogen bonding with adsorbed ethanol facilitates proton transfer from ethanol to OD* and thus enhances the reaction probability. The decreasing behavior of CH4 could also involve the competition for H* with the formation of H2 and HDO.

Distinct dependence on size of Pt and Rh nanoclusters on graphene/Pt(111) in the decomposition of methanol-d4.

Pt and Rh nanoclusters, grown on deposition of Pt and Rh vapors onto graphene/Pt(111), show separate reactivity toward the decomposition of methanol-d4. The Pt (Rh) clusters had a mean diameter 2.0-3.5 nm (2.1-4.0 nm) and height 0.45-0.94 nm (0.41-0.9 nm) evolving with the coverage; they were structurally ordered, having an fcc phase and growing in (111) orientation, and had lattice constants similar to their bulk values. Methanol-d4 on the Pt clusters did not decompose but desorbed mostly, disparate from that on Pt(111) surface; the disparity arose as the adsorption energies of methanol-d4 on most surface sites of the Pt clusters became smaller than their single crystal counterpart. This size effect, nevertheless, did not apply on the Rh clusters, despite their similar atomic stacking; the Rh clusters showed a reactivity similar to that of the Rh(111) surface because the adsorption energies of methanol-d4 on both Rh clusters and Rh(111) are comparable. The distinct size dependence was rationalized through their electronic structures and charge distribution of Fukui function mapping. Our results suggest that reactive transition metals do not necessarily become more reactive while they are scaled down to nanoscale; their reactivity evolves with their size in a manner largely dependent on their electronic nature.

Operando Investigation into Dynamic Evolution of Cathode-Electrolyte Interfaces in a Li-Ion Battery.

While Li-ion battery cathode-electrolyte interfaces (CEIs) have been extensively investigated in recent decades, accurately identifying the chemical nature and tracking the dynamics of the CEIs during electrochemical cycling still remain a grand challenge. Here we report our findings in the investigation into the dynamic evolution of the interface between a LiNi0.33Co0.33Mn0.33O2 (LNMC) cathode and an ethylene carbonate/dimethyl carbonate (EC/DMC)-based electrolyte using surface-enhanced Raman spectroscopy (SERS) performed on a model cell under typical battery operating conditions. In particular, the strong SERS activity provided by a monolayer of Au nanocubes deposited on a model LNMC electrode (additive-free) enables quasi-quantitative assessment of the CEI evolution during cycling, proving information vital to revealing the dynamics of the species adsorbed on the LNMC surface as a function of cell potential. Furthermore, our theoretical calculation, which is based on the interaction between a model interface-bound molecule and a model LNMC surface, agrees with our experimental observation. The carefully designed operando SERS platform has demonstrated high sensitivity, good surface specificity, and excellent compatibility with extensive electrochemical measurements; it is also applicable to fundamental studies of dynamic interfaces in other electrochemical energy storage and conversion systems.

Fabrication of SnS2/Mn2SnS4/Carbon Heterostructures for Sodium-Ion Batteries with High Initial Coulombic Efficiency and Cycling Stability.

SnS2 has been extensive studied as an anode material for sodium storage owing to its high theoretical specific capacity, whereas the unsatisfied initial Coulombic efficiency (ICE) caused by the partial irreversible conversion reaction during the charge/discharge process is one of the critical issues that hamper its practical applications. Hence, heterostructured SnS2/Mn2SnS4/carbon nanoboxes (SMS/C NBs) have been developed by a facial wet-chemical method and utilized as the anode material of sodium ion batteries. SMS/C NBs can deliver an initial capacity of 841.2 mAh g-1 with high ICE of 90.8%, excellent rate capability (752.3, 604.7, 570.1, 546.9, 519.7, and 488.7 mAh g-1 at the current rate of 0.1, 0.5, 1.0, 2.0, 5.0, and 10.0 A g-1, respectively), and long cycling stability (522.5 mAh g-1 at 5.0 A g-1 after 500 cycles). The existence of SnS2/Mn2SnS4 heterojunctions can effectively stabilize the reaction products Sn and Na2S, greatly prevent the coarsening of nanosized Sn0, and enhance reversible conversion--alloying reaction, which play a key role in improving the ICE and extending the cycling performance. Moreover, the heterostructured SMS coupled with the interacting carbon network provides efficient channels for electrons and Na+ diffusion, resulting in an excellent rate performance.