Electrochemical Energy Storage with a Reversible Nonaqueous Room‐Temperature Aluminum–Sulfur Chemistry

A reversible room‐temperature aluminum–sulfur (Al‐S) battery is demonstrated with a strategically designed cathode structure and an ionic liquid electrolyte. Discharge–charge mechanism of the Al‐S battery is proposed based on a sequence of electrochemical, microscopic, and spectroscopic analyses. The electrochemical process of the Al‐S battery involves the formation of a series of polysulfides and sulfide. The high‐order polysulfides (S_x^2?, x ≥ 6) are soluble in the ionic liquid electrolyte. Electrochemical transitions between S₆^2? and the insoluble low‐order polysulfides or sulfide (S_x ^2?, 1 ≤ x < 6) are reversible. A single‐wall carbon nanotube coating applied to the battery separator helps alleviate the diffusion of the polysulfide species and reduces the polarization behavior of the Al‐S batteries.     

Molecular‐Level Design of Pyrrhotite Electrocatalyst Decorated Hierarchical Porous Carbon Spheres as Nanoreactors for Lithium–Sulfur Batteries

Lithium–sulfur batteries (LSBs) are a class of new‐generation rechargeable high‐energy‐density batteries. However, the persisting issue of lithium polysulfides (LiPs) dissolution and the shuttling effect that impedes the efficiency of LSBs are challenging to resolve. Herein a general synthesis of highly dispersed pyrrhotite Fe_1?xS nanoparticles embedded in hierarchically porous nitrogen‐doped carbon spheres (Fe_1?xS‐NC) is proposed. Fe_1?xS‐NC has a high specific surface area (627 m² g^?1), large pore volume (0.41 cm³ g^?1), and enhanced adsorption and electrocatalytic transition toward LiPs. Furthermore, in situ generated large mesoporous pores within carbon spheres can accommodate high sulfur loading of up to 75%, and sustain volume variations during charge/discharge cycles as well as improve ionic/mass transfer. The exceptional adsorption properties of Fe_1?xS‐NC for LiPs are predicted theoretically and confirmed experimentally. Subsequently, the electrocatalytic activity of Fe_1?xS‐NC is thoroughly verified. The results confirm Fe_1?xS‐NC is a highly efficient nanoreactor for sulfur loading. Consequently, the Fe_1?xS‐NC nanoreactor performs extremely well as a cathodic material for LSBs, exhibiting a high initial capacity of 1070 mAh g^?1 with nearly no capacity loss after 200 cycles at 0.5 C. Furthermore, the resulting LSBs display remarkably enhanced rate capability and cyclability even at a high sulfur loading of 8.14 mg cm^?2.     

Covalent Encapsulation of Sulfur in a MOF‐Derived S,N‐Doped Porous Carbon Host Realized via the Vapor‐Infiltration Method Results in Enhanced Sodium–Sulfur Battery Performance

Practical applications of room temperature sodium–sulfur batteries are still inhibited by the poor conductivity and slow reaction kinetics of sulfur, and dissolution of intermediate polysulfides in the commonly used electrolytes. To address these issues, starting from a novel 3D Zn‐based metal–organic framework with 2,5‐thiophenedicarboxylic acid and 1,4‐bis(pyrid‐4‐yl) benzene as ligands, a S, N‐doped porous carbon host with 3D tubular holes for sulfur storage is fabricated. In contrast to the commonly used melt‐diffusion method to confine sulfur physically, a vapor‐infiltration method is utilized to achieve sulfur/carbon composite with covalent bonds, which can join electrochemical reaction without low voltage activation. A polydopamine derived N‐doped carbon layer is further coated on the composite to confine the high‐temperature‐induced gas‐phase sulfur inside the host. S and N dopants increase the polarity of the carbon host to restrict diffusion of sulfur, and its 3D porous structure provides a large storage area for sulfur. As a result, the obtained composite shows outstanding electrochemical performance with 467 mAh g^?1 (1262 mAh g^?1_(sulfur)) at 0.1 A g^?1, 270 mAh g^?1 (730 mAh g^?1_(sulfur)) after 1000 cycles at 1 A g^?1 and 201 mAh g^?1 (543 mAh g^?1_(sulfur)) at 5.0 A g^?1.     

Sulfur‐Embedded Activated Multichannel Carbon Nanofiber Composites for Long‐Life,High‐Rate Lithium–Sulfur Batteries

Despite the 3–5 fold higher energy density than the conventional Li‐ion cells at a lower cost, commercialization of Li–S batteries is hindered by the insulating nature of sulfur and the dissolution of intermediate polysulfides (Li₂S _X , 4 < X ≤ 8) into the electrolyte. The authors demonstrate here multichannel carbon nanofibers that are composed of parallel mesoporous channels connected with micropores as sulfur containment. In addition, hydroxyl functional groups are formed on the carbon surface through a chemical activation to enhance the interaction between sulfur and carbon. In the sulfur embedded composite, the mesoporous multichannel enhances the active material utilization and sulfur loading, while the micropores act as a reaction chamber for sulfur component and trap site for polysulfide with the assistance of the functional groups. This sulfur–carbon composite electrode with 2.2 mg cm^?2 sulfur displays excellent performance with high rate capability (initial capacity of 1351 mA h g^?1 at C/5 rate and 847 mA h g^?1 at 5C rate), maintaining 920 mA h g^?1 even after 300 cycles (a decay of 0.07% per cycle). Furthermore, a stable reversible capacity of as high as ≈1100 mA h g^?1 is realized with a higher sulfur loading of 4.6 mg cm^?2.     

Highly Dispersed Cobalt Clusters in Nitrogen‐Doped Porous Carbon Enable Multiple Effects for High‐Performance Li–S Battery

The lithium–sulfur (Li–S) battery is considered a promising candidate for the next generation of energy storage system due to its high specific energy density and low cost of raw materials. However, the practical application of Li–S batteries is severely limited by several weaknesses such as the shuttle effect of polysulfides and the insulation of the electrochemical products of sulfur and Li₂S/Li₂S₂. Here, by doping nitrogen and integrating highly dispersed cobalt catalysts, a porous carbon nanocage derived from glucose adsorbed metal–organic framework is developed as the host for a sulfur cathode. This host structure combines the reported positive effects, including high conductivity, high sulfur loading, effective stress release, fast lithium‐ion kinetics, fast interface charge transport, fast redox of Li₂S_n, and strong physical/chemical absorption, achieving a long cycle life (86% of capacity retention at 1C within 500 cycles) and high rate performance (600 mAh g^?1 at 5C) for a Li–S battery. By combining experiments and density functional theoretical calculations, it is demonstrated that the well‐dispersed cobalt clusters play an important role in greatly improving the diffusion dynamics of lithium, and enhance the absorption and conversion capability of polysulfides in the host structure.     

Polysulfide‐Shuttle Control in Lithium‐Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON‐Type Solid Electrolyte

A NaSICON‐type Li⁺‐ion conductive membrane with a formula of Li_{1+ x} Y _x Zr_{2? x} (PO₄)₃ (LYZP) (x = 0–0.15) has been explored as a solid‐electrolyte/separator to suppress polysulfide‐crossover in lithium‐sulfur (Li‐S) batteries. The LYZP membrane with a reasonable Li⁺‐ion conductivity shows both favorable chemical compatibility with the lithium polysulfide species and exhibits good electrochemical stability under the operating conditions of the Li‐S batteries. Through an integration of the LYZP solid electrolyte with the liquid electrolyte, the hybrid Li‐S batteries show greatly enhanced cyclability in contrast to the conventional Li‐S batteries with the porous polymer (e.g., Celgard) separator. At a rate of C/5, the hybrid Li ||LYZP|| Li₂S₆ batteries developed in this study (with a Li‐metal anode, a liquid/LYZP hybrid electrolyte, and a dissolved lithium polysulfide cathode) delivers an initial discharge capacity of ≈1000 mA h g^?1 (based on the active sulfur material) and retains ≈90% of the initial capacity after 150 cycles with a low capacity fade‐rate of <0.07% per cycle.     

Rechargeable Iron–Sulfur Battery without Polysulfide Shuttling

Sulfur represents one of the most promising cathode materials for next‐generation batteries; however, the widely observed polysulfide dissolution/shuttling phenomenon in metal–sulfur redox chemistries has severely restricted their applications. Here it is demonstrated that when pairing the sulfur electrode with the iron metal anode, the inherent insolubility of iron sulfides renders the shuttling‐free nature of the Fe–S electrochemical reactions. Consequently, the sulfur electrode exhibits promising performance for Fe²⁺ storage, where a high capacity of ≈1050 mAh g^?1, low polarization of ≈0.16 V as well as stable cycling of 150 cycles are realized. The Fe–S redox mechanism is further revealed as an intriguing stepwise conversion of S₈ ? FeS₂ ? Fe₃S₄ ? FeS, where a low volume expansion of ≈32.6% and all‐solid‐state phase transitions facilitate the reaction reversibility. This study suggests an alternative direction to exploit sulfur electrodes in rechargeable transition metal–sulfur batteries.     

High‐Performance All‐Solid‐State Lithium–Sulfur Batteries Enabled by Amorphous Sulfur‐Coated Reduced Graphene Oxide Cathodes

Safety and the polysulfide shuttle reaction are two major challenges for liquid electrolyte lithium–sulfur (Li–S) batteries. Although use of solid‐state electrolytes can overcome these two challenges, it also brings new challenges by increasing the interface resistance and stress/strain. In this work, the interface resistance and stress/strain of sulfur cathodes are significantly reduced by conformal coating ≈2 nm sulfur (S) onto reduced graphene oxide (rGO). An Li–S full cell consisting of an rGO@S‐Li₁₀GeP₂S₁₂‐acetylene black (AB) composite cathode is evaluated. At 60 °C, the all‐solid‐state Li–S cell demonstrates a similar electrochemical performance as in liquid organic electrolyte, with high rate capacities of 1525.6, 1384.5, 1336.3, 903.2, 502.6, and 204.7 mA h g^?1 at 0.05, 0.1, 0.5, 1.0, 2.0, and 5.0 C, respectively. It can maintain a high and reversible capacity of 830 mA h g^?1 at 1.0 C for 750 cycles. The uniform distribution of the rGO@S nanocomposite in the Li₁₀GeP₂S₁₂‐AB matrix generates uniform volume changes during lithiation/delithiation, significantly reducing the stress/strain, thus extending the cycle life. Minimization of the stress/strain of solid cells is the key for a long cycle life of all‐solid‐state Li–S batteries.     

Sodium Sulfide Cathodes Superseding Hard Carbon Pre‐sodiation for the Production and Operation of Sodium–Sulfur Batteries at Room Temperature

This study demonstrates for the first time a room temperature sodium–sulfur (RT Na–S) full cell assembled based on a pristine hard carbon (HC) anode combined with a nanostructured Na₂S/C cathode. The development of cells without the demanding, time‐consuming and costly pre‐sodiation of the HC anode is essential for the realization of practically relevant RT Na–S prototype batteries. New approaches for Na₂S/C cathode fabrication employing carbothermal reduction of Na₂SO₄ at varying temperatures (660 to 1060 °C) are presented. Initial evaluation of the resulting cathodes in a dedicated cell setup reveals 36 stable cycles and a capacity of 740 mAh g_S^?1, which correlates to ≈85% of the maximum value known from literature on Na₂S‐based cells. The Na₂S/C cathode with the highest capacity utilization is implemented into a full cell concept applying a pristine HC anode. Various full cell electrolyte compositions with fluoroethylene carbonate (FEC) additive have been combined with a special charging procedure during the first cycle supporting in situ solid electrolyte interphase (SEI) formation on the HC anode to obtain increased cycling stability and cathode utilization. The best performing cell setup has delivered a total of 350 mAh g_S^?1, representing the first functional full cell based on a Na₂S/C cathode and a pristine HC anode today.     

Tailored Reaction Route by Micropore Confinement for Li–S Batteries Operating under Lean Electrolyte Conditions

Lithium‐sulfur (Li–S) batteries are one of the most promising alternative energy storage systems beyond Li‐ion batteries. However, the sluggish kinetics of the nucleation and growth of the solid discharge product of Li₂S/Li₂S₂ in the lower discharge plateau has been recently identified as a critical hurdle for attaining high specific capacity in Li–S batteries with high sulfur loadings under lean electrolyte conditions. Herein, a new strategy of breaking the charge‐transport bottleneck by successful generation of experimentally verified stable Li₂S₂ and a reservoir of quasi‐solid lithium polysulfides within the micropores of activated carbon fiber cloth as a high‐sulfur‐loading host is proposed. The developed Li–S cell is capable of delivering a highly sustainable areal capacity of 6.0 mAh cm^?2 under lower electrolyte to sulfur ratios (<3.0 mL_E g_S^?1). Micropore confinement leads to generation of solid Li₂S₂ that enables high utilization of the entire electroactive area by its inherent self‐healing capacity. This strategy opens a new avenue for rational material designs for Li–S batteries under lean electrolyte condition.     

Ultrafine Co3Se4 Nanoparticles in Nitrogen‐Doped 3D Carbon Matrix for High‐Stable and Long‐Cycle‐Life Lithium Sulfur Batteries

Lithium–sulfur batteries are a promising high energy output solution for substitution of traditional lithium ion batteries. In recent times research in this field has stepped into the exploration of practical applications. However, their applications are impeded by cycling stability and short life‐span mainly due to the notorious polysulfide shuttle effect. In this work, a multifunctional sulfur host fabricated by grafting highly conductive Co₃Se₄ nanoparticles onto the surface of an N‐doped 3D carbon matrix to inhibit the polysulfide shuttle and improve the sulfur utilization is proposed. By regulating the carbon matrix and the Co₃Se₄ distribution, N‐CN‐750@Co₃Se₄‐0.1 m with abundant polar sites is experimentally and theoretically shown to be a good LiPSs absorbent and a sulfur conversion accelerator. The S/N‐CN‐750@Co₃Se₄‐0.1 m cathode shows excellent sulfur utilization, rate performance, and cyclic durability. A prolonged cycling test of the as‐fabricated S/N‐CN‐750@Co₃Se₄‐0.1 m cathode is carried out at 0.2 C for more than 5 months which delivers a high initial capacity of 1150.3 mAh g^?1 and retains 531.0 mAh g^?1 after 800 cycles with an ultralow capacity reduction of 0.067% per cycle, maintaining Coulombic efficiency of more than 99.3%. The reaction details are characterized and analyzed by ex situ measurements. This work highly emphasizes the potential capabilities of transition‐metal selenides in lithium–sulfur batteries.     

Fabrication of N‐doped Graphene–Carbon Nanotube Hybrids from Prussian Blue for Lithium–Sulfur Batteries

Hybrid nanostructures containing 1D carbon nanotubes and 2D graphene sheets have many promising applications due to their unique physical and chemical properties. In this study, the authors find Prussian blue (dehydrated sodium ferrocyanide) can be converted to N‐doped graphene–carbon nanotube hybrid materials through a simple one‐step pyrolysis process. Through field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, Raman spectra, atomic force microscopy, and isothermal analyses, the authors identify that 2D graphene and 1D carbon nanotubes are bonded seamlessly during the growth stage. When used as the sulfur scaffold for lithium–sulfur batteries, it demonstrates outstanding electrochemical performance, including a high reversible capacity (1221 mA h g^?1 at 0.2 C rate), excellent rate capability (458 and 220 mA h g^?1 at 5 and 10 C rates, respectively), and excellent cycling stability (321 and 164 mA h g^?1 at 5 and 10 C (1 C = 1673 mA g^?1) after 1000 cycles). The enhancement of electrochemical performance can be attributed to the 3D architecture of the hybrid material, in which, additionally, the nitrogen doping generates defects and active sites for improved interfacial adsorption. Furthermore, the nitrogen doping enables the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much‐improved cycling performance. Therefore, the hybrid material functions as a redox shuttle to catenate and bind polysulfides, and convert them to insoluble lithium sulfide during reduction. The strategy reported in this paper could open a new avenue for low cost synthesis of N‐doped graphene–carbon nanotube hybrid materials for high performance lithium–sulfur batteries.     

Simultaneous Cobalt and Phosphorous Doping of MoS2 for Improved Catalytic Performance on Polysulfide Conversion in Lithium–Sulfur Batteries

The lithium–sulfur batteries are susceptible to the loss of sulfur as dissolved polysulfides in the electrolyte and their ensuing redox shutting effect. The acceleration of the conversion kinetics of dissolved polysulfides into the insoluble sulfur and lithium sulfide via electrocatalysis has the appeal of being a root‐cause solution. MoS₂ is the most common electrocatalyst used for this purpose. It is demonstrated that how the effectiveness can be improved by simultaneous cobalt and phosphorus doping of MoS₂ nanotubes (P‐Mo_0.9Co_0.1S₂‐2, containing 1.81 at% of P). Cobalt doping induces the transformation of MoS₂ from 2H phase to metallic 1T phase, which improves the electrical conductivity of the MoS₂. The Co–P coordinated sites on the catalyst surface are highly active for the polysulfide conversion reactions. Consequently, a sulfur cathode with P‐Mo_0.9Co_0.1S₂‐2 can decrease the capacity fade rate from 0.28% per cycle before modification (over 150 cycles at 0.5C rate) to 0.046% per cycle after modification (over 600 cycles at 1C rate). P‐Mo_0.9Co_0.1S₂‐2 also enhances the high rate performance from a capacity of 338 to 931 mAh g^?1 at 6C rate. The results of this study provide the first direct evidence of the beneficial effects of heteroatom codoping of polysulfide conversion catalysts.     

Boosting Polysulfide Redox Kinetics by Graphene‐Supported Ni Nanoparticles with Carbon Coating

Lithium–sulfur batteries have attracted extensive attention because of their high energy density. However, their application is still impeded by the inherent sluggish kinetics and solubility of intermediate products (i.e., polysulfides) of the sulfur cathode. Herein, graphene‐supported Ni nanoparticles with a carbon coating are fabricated by directly carbonizing a metal–organic framework/graphene oxide composite, which is then dispersed on a commercial glass fiber membrane to form a separator with electrocatalytic activity. In situ analysis and electrochemical investigation demonstrate that this modified separator can effectively suppress the shuttle effect and regulate the catalytic conversion of intercepted polysulfides, which is also confirmed by density functional theory calculations. It is found that Ni–C sites can chemically interact with polysulfides and stabilize the radical S₃^?? through Ni? S bonds to enable fast dynamic equilibrium with S₆^2?, while Ni nanoparticles reduce the oxidation barrier of Li₂S and accelerate ion/electron transport. As a result, the corresponding lithium–sulfur battery shows a high cycle stability (88% capacity retention over 100 cycles) even with a high sulfur mass loading of 8 mg cm^?2 and lean electrolyte (6.25 µ L mg^?1). Surprisingly, benefitting from the improved kinetics, the battery can work well at ?50 °C, which is rarely achieved by conventional Li–S batteries.     

Tungsten Disulfide Catalysts Supported on a Carbon Cloth Interlayer for High Performance Li–S Battery

The capacity limitations of insertion‐compound cathodes has motivated interest in a sulfur cathode for a rechargeable battery cell with a metallic‐lithium anode; but irreversible capacity loss owing to solubility of intermediate Li₂S_x (x = 2–8) polysulfides in the organic‐liquid electrolytes used has prevented practical application. A dual‐function cathode structure consisting of layered tungsten disulfide (WS₂) supported both on the cathode current collector and on a carbon cloth interlayer (CCl) gives excellent performance in a lithium half‐cell by providing strong adsorption of the soluble Li₂S_x on the WS₂ with fast access to electrons from the current collector via a blocking carbon cloth interlayer.     

Improved Cycling Performance of Li‐Excess Cation‐Disordered Cathode Materials upon Fluorine Substitution

The recent discovery of Li‐excess cation‐disordered rock salt cathodes has greatly enlarged the design space of Li‐ion cathode materials. Evidence of facile lattice fluorine substitution for oxygen has further provided an important strategy to enhance the cycling performance of this class of materials. Here, a group of Mn³⁺–Nb⁵⁺‐based cation‐disordered oxyfluorides, Li_1.2Mn³⁺_0.6+0.5xNb⁵⁺_0.2?0.5xO_2?xF_x (x = 0, 0.05, 0.1, 0.15, 0.2) is investigated and it is found that fluorination improves capacity retention in a very significant way. Combining spectroscopic methods and ab initio calculations, it is demonstrated that the increased transition‐metal redox (Mn³⁺/Mn⁴⁺) capacity that can be accommodated upon fluorination reduces reliance on oxygen redox and leads to less oxygen loss, as evidenced by differential electrochemical mass spectroscopy measurements. Furthermore, it is found that fluorine substitution also decreases the Mn³⁺‐induced Jahn–Teller distortion, leading to an orbital rearrangement that further increases the contribution of Mn‐redox capacity to the overall capacity.     

High‐Energy,High‐Rate,Lithium–Sulfur Batteries: Synergetic Effect of Hollow TiO2‐Webbed Carbon Nanotubes and a Dual Functional Carbon‐Paper Interlayer

A novel nanocomposite cathode consisting of sulfur and hollow‐mesoporous titania (HMT) embedded within carbon nanotubes (CNT), which is designated as S‐HMT@CNT, has been obtained by encapsulating elemental sulfur into the pores of hollow‐mesoporous, spherical TiO₂ particles that are connected via CNT. A carbon‐paper interlayer, referred to as dual functional porous carbon wall (DF‐PCW), has been obtained by filling the voids in TiO₂ spheres with carbon and then etching the TiO₂ template with a chemical process. The DF‐PCW interlayer provides a medium for scavenging the lithium polysulfides and suppressing them from diffusing to the anode side when it is inserted between the sulfur cathode and the separator. Lithium–sulfur cells fabricated with the thus prepared S‐HMT@CNT cathode and the DF‐PCW interlayer exhibit superior performance due to the containment of sulfur in TiO₂ and improved lithium–ion and electron transports. The Li–S cells display high capacity with excellent capacity retention at rates as high as 1C, 2C, and 5C rates.     

Capture and Catalytic Conversion of Polysulfides by In Situ Built TiO2‐MXene Heterostructures for Lithium–Sulfur Batteries

The detrimental shuttle effect in lithium–sulfur batteries mainly results from the mobility of soluble polysulfide intermediates and their sluggish conversion kinetics. Herein, presented is a multifunctional catalyst with the merits of strong polysulfides adsorption ability, superior polysulfides conversion activity, high specific surface area, and electron conductivity by in situ crafting of the TiO₂‐MXene (Ti₃C₂T_x) heterostructures. The uniformly distributed TiO₂ on MXene sheets act as capturing centers to immobilize polysulfides, the hetero‐interface ensures rapid diffusion of anchored polysulfides from TiO₂ to MXene, and the oxygen‐terminated MXene surface is endowed with high catalytic activity toward polysulfide conversion. The improved lithium–sulfur batteries deliver 800 mAh g^?1 at 2 C and an ultralow capacity decay of 0.028% per cycle over 1000 cycles at 2 C. Even with a high sulfur loading of 5.1 mg cm^?2, the capacity retention of 93% after 200 cycles is still maintained. This work sheds new insights into the design of high‐performance catalysts with manipulated chemical components and tailored surface chemistry to regulate polysulfides in Li–S batteries.     

NiCo2O4 Nanofibers as Carbon‐Free Sulfur Immobilizer to Fabricate Sulfur‐Based Composite with High Volumetric Capacity for Lithium–Sulfur Battery

Both the energy density and cycle stability are still challenges for lithium–sulfur (Li–S) batteries in future practical applications. Usually, light‐weight and nonpolar carbon materials are used as the hosts of sulfur, however they struggle on the cycle stability and undermine the volumetric energy density of Li–S batteries. Here, heavy NiCo₂O₄ nanofibers as carbon‐free sulfur immobilizers are introduced to fabricate sulfur‐based composites. NiCo₂O₄ can accelerate the catalytic conversion kinetics of soluble intermediate polysulfides by strong chemical interaction, leading to a good cycle stability of sulfur cathodes. Specifically, the S/NiCo₂O₄ composite presents a high gravimetric capacity of 1125 mAh g^?1 at 0.1 C rate with the composite as active material, and a low fading rate of 0.039% per cycle over 1500 cycles at 1 C rate. In particular, the S/NiCo₂O₄ composite with the high tap density of 1.66 g cm^?3 delivers large volumetric capacity of 1867 mAh cm^?3, almost twice that of the conventional S/carbon composites.     

Hierarchical NiCo2S4@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O2 Batteries

The critical challenges of Li‐O₂ batteries lie in sluggish oxygen redox kinetics and undesirable parasitic reactions during the oxygen reduction reaction and oxygen evolution reaction processes, inducing large overpotential and inferior cycle stability. Herein, an elaborately designed 3D hierarchical heterostructure comprising NiCo₂S₄@NiO core–shell arrays on conductive carbon paper is first reported as a freestanding cathode for Li‐O₂ batteries. The unique hierarchical array structures can build up multidimensional channels for oxygen diffusion and electrolyte impregnation. A built‐in interfacial potential between NiCo₂S₄ and NiO can drastically enhance interfacial charge transfer kinetics. According to density functional theory calculations, intrinsic LiO₂‐affinity characteristics of NiCo₂S₄ and NiO play an importantly synergistic role in promoting the formation of large peasecod‐like Li₂O₂, conducive to construct a low‐impedance Li₂O₂/cathode contact interface. As expected, Li‐O₂ cells based on NiCo₂S₄@NiO electrode exhibit an improved overpotential of 0.88 V, a high discharge capacity of 10 050 mAh g^?1 at 200 mA g^?1, an excellent rate capability of 6150 mAh g^?1 at 1.0 A g^?1, and a long‐term cycle stability under a restricted capacity of 1000 mAh g^?1 at 200 mA g^?1. Notably, the reported strategy about heterostructure accouplement may pave a new avenue for the effective electrocatalyst design for Li‐O₂ batteries.