Creating High-entropy Single Atoms on Transition Disulfides through Substrate-induced Redox Dynamics for Efficient Electrocatalytic Hydrogen Evolution.

The controllable anchoring of multiple metal single-atoms (SAs) into a single support exhibits scientific and technological opportunities,while marrying the concentration-complex multimetallic SAs and high-entropy SAs (HESAs) into one SAC system remains a substantial challenge.Here, we present a substrate-mediated SAs formation strategy to successfully fabricate a library of multimetallic SAs and HESAs on MoS2 and MoSe2 supports, which can precisely control the doping location of SAs. Specially, the contents of SAs can continuously increase until the accessible Mo atoms on TMDs carriers are completely replaced by SAs, thus allowing the of much higher metal contents.In-depth mechanistic study shows that the well-controlled synthesis of multimetallic SAs and HESAs is realized by controlling the reversible redox reaction occurred on the TMDs/TM ion interface.As a proof-of-concept application, a variety of SAs-TMDs were applied to hydrogen evolution reaction. The optimized HESAs-TMDs (Pt,Ru,Rh,Pd,Re-MoSe2) delivers a much higher activity and durability than state of-the-art Pt. Thus, our work will broaden the family of single-atom catalysts and provide a new guideline for the rational design of high-performance single-atom catalysts.

Well-dispersed Pt/Nb2O5on zeolitic imidazolate framework derived nitrogen-doped carbon for efficient oxygen reduction reaction.

In this work, an advanced hybrid material was constructed by incorporating niobium pentoxide (Nb2O5) nanocrystals with nitrogen-doped carbon (NC) derived from ZIF-8 dodecahedrons, serving as a support, referred to as Nb2O5/NC. Pt nanocrystals were dispersed onto Nb2O5/NC using a simple impregnation reduction method. The obtained Pt/Nb2O5/NC electrocatalyst showed high oxygen reduction reaction (ORR) activity due to three-phase mutual contacting structure with well-dispersed Pt and Nb2O5NPs. In addition, the conductive NC benefits electron transfer, while the induced Nb2O5can regulate the electronic structure of Pt element and anchor Pt nanocrystals, thereby enhancing the ORR activity and stability. The half-wave potential (E1/2) for Pt/Nb2O5/NC is 0.886 V, which is higher than that of Pt/NC (E1/2= 0.826 V). The stability examinations demonstrated that Pt/Nb2O5/NC exhibited higher electrocatalytic durability than Pt/NC. Our work provides a new direction for synthesis and structural design of precious metal/oxides hybrid electrocatalysts.

Polypyrrole pre-intercalation engineering-induced NH4+ removal in tunnel ammonium vanadate toward high-performance zinc ion batteries.

Ammonium vanadate with stable bi-layered structure and superior mass-specific capacity have emerged as competitive cathode materials for aqueous rechargeable zinc-ion batteries (AZIBs). Nevertheless, fragile NH…O bonds and too strong electrostatic interaction by virtue of excessive NH4+ will lead to sluggish Zn2+ ion mobility, further largely affects the electro-chemical performance of ammonium vanadate in AZIBs. The present work incorporates polypyrrole (PPy) to partially replace NH4+ in NH4V4O10 (NVO), resulting in the significantly enlarged interlayers (from 10.1 to 11.9 Å), remarkable electronic conductivity, increased oxygen vacancies and reinforced layered structure. The partial removal of NH4+ will alleviate the irreversible deammoniation to protect the laminate structures from collapse during ion insertion/extraction. The expanded interlayer spacing and the increased oxygen vacancies by the virtue of the introduction of polypyrrole improve the ionic diffusion, enabling exceptional rate performance of NH4V4O10. As expected, the resulting polypyrrole intercalated ammonium vanadate (NVOY) presents a superior discharge capacity of 431.9 mAh g-1 at 0.5 A g-1 and remarkable cycling stability of 219.1 mAh g-1 at 20 A g-1 with 78 % capacity retention after 1500 cycles. The in-situ electrochemical impedance spectroscopy (EIS), in-situ X-ray diffraction (XRD), ex-situ X-ray photoelectron spectroscopy (XPS) and ex-situ high resolution transmission electron microscopy (HR-TEM) analysis investigate a highly reversible intercalation Zn-storage mechanism, and the enhanced the redox kinetics are related to the combined effect of interlayer regulation, high electronic conductivity and oxygen defect engineering by partial substitution NH4+ of PPy incorporation.

Ultra-thin and Mechanically Stable LiCoO2 -Electrolyte Interphase Enabled by Mg2+ Involved Electrolyte.

LiCoO2 (LCO) cathode materials have attracted significant attention for its potential to provide higher energy density in current Lithium-ion batteries (LIBs). However, the structure and performance degradation are exacerbated by increasing voltage due to the catastrophic reaction between the applied electrolyte and delithiated LCO. The present study focuses on the construction of physically and chemically robust Mg-integrated cathode-electrolyte interface (MCEI) to address this issue, by incorporating Magnesium bis(trifluoromethanesulfonyl)imide (Mg[TFSI]2 ) as an electrolyte additive. During formation cycles, the strong MCEI is formed and maintained its 2 nm thickness throughout long-term cycling. Notably, Mg is detected not only in the robust MCEI, but also imbedded in the surface of the LCO lattice. As a result, the parasitic interfacial side reactions, surface phase reconstruction, particle cracking, Co dissolution and shuttling are considerably suppressed, resulting in long-term cycling stability of LCO up to 4.5 V. Therefore, benefit from the double protection of the strong MCEI, the Li||LCO coin cell and the Ah-level Graphite||LCO pouch cell exhibit high capacity retention by using Mg-electrolyte, which are 88.13% after 200 cycles and 90.4% after 300 cycles, respectively. This work provides a novel approach for the rational design of traditional electrolyte additives.

ZnSe/SnSe Heterostructure Incorporated with Selenium/Nitrogen Co-Doped Carbon Nanofiber Skeleton for Sodium-Ion Batteries.

Effective strategies toward building exquisite nanostructures with enhanced structural integrity and improved reaction kinetics will carry forward the practical application of alloy-based materials as anodes in batteries. Herein, a free-standing 3D carbon nanofiber (CNF) skeleton incorporated with heterostructured binary metal selenides (ZnSe/SnSe) nanoboxes is developed for Na-ion storage anodes, which can facilitate Na+ ion migration, improve structure integrity, and enhance the electrochemical reaction kinetics. During the carbonization and selenization process, selenium/nitrogen (Se/N) is co-doped into the 3D CNF skeleton, which can improve the conductivity and wettability of the CNF matrices. More importantly, the ZnSe/SnSe heterostructures and the Se/N co-doping CNFs can have a synergistic interfacial coupling effect and built-in electric field in the heterogeneous interfaces of ZnSe/SnSe hetero-boundaries as well as the interfaces between the CNF matrix and the selenide heterostructures, which can enable fast ion/electron transport and accelerate surface/internal reaction kinetics for Na-ion storage. The ZnSe/SnSe@Se,N-CNFs exhibit superior Na-ion storage performance than the comparative ZnSe/SnSe, ZnSe and SnSe powders, which deliver an excellent rate performance (882.0, 773.6, 695.7, 634.2, and 559.0 mAh g-1 at current rates of 0.1, 0.2, 0.5, 1, and 2 A g-1) and long-life cycling stability of 587.5 mAh g-1 for 3500 cycles at 2 A g-1.

Challenges and approaches of single-crystal Ni-rich layered cathodes in lithium batteries.

High energy density and high safety are incompatible with each other in a lithium battery, which challenges today's energy storage and power applications. Ni-rich layered transition metal oxides (NMCs) have been identified as the primary cathode candidate for powering next-generation electric vehicles and have been extensively studied in the last two decades, leading to the fast growth of their market share, including both polycrystalline and single-crystal NMC cathodes. Single-crystal NMCs appear to be superior to polycrystalline NMCs, especially at low Ni content (≤60%). However, Ni-rich single-crystal NMC cathodes experience even faster capacity decay than polycrystalline NMC cathodes, rendering them unsuitable for practical application. Accordingly, this work will systematically review the attenuation mechanism of single-crystal NMCs and generate fresh insights into valuable research pathways. This perspective will provide a direction for the development of Ni-rich single-crystal NMC cathodes.

Biomimetic Nanozyme-Decorated Hydrogels with H2O2-Activated Oxygenation for Modulating Immune Microenvironment in Diabetic Wound.

Diabetic foot ulcers (DFUs) remain a devastating threat to human health. While hydrogels are promising systems for DFU-based wound management, their effectiveness is often hindered by the immune response and hostile wound microenvironment associated with the uncontrollable accumulation of reactive oxygen species and hypoxia. Here, we develop a therapeutic wound dressing using a biomimetic hydrogel system with the decoration of catalase-mimic nanozyme, namely, MnCoO@PDA/CPH. The hydrogel can be designed to match the mechanical and electrical cues of skins simultaneously with H2O2-activated oxygenation ability. As a proof of concept, DFU-based rat models are created to validate the therapeutic efficacy of the MnCoO@PDA/CPH hydrogel in vivo. The results indicate that the developed hydrogel can promote DFU healing and improve the quality of the healed wound as featured by alleviated proinflammatory, increased re-epithelialization, highly ordered collagen deposition, and functional blood vessel growth.

Building Atomic Scale and Dense Fe─N4 Edge Sites of Highly Efficient Fe─N─C Oxygen Reduction Catalysts Using a Sacrificial Bimetallic Pyrolysis Strategy.

Replacing high-cost and scarce platinum (Pt) with transition metal and nitrogen co-doped carbon (M/N/C, M = Fe, Co, Mn, and so on) catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells has largely been impeded by the unsatisfactory ORR activity of M/N/C due to the low site utilization and inferior intrinsic activity of the M─N4 active center. Here, these limits are overcome by using a sacrificial bimetallic pyrolysis strategy to synthesize Fe─N─C catalyst by implanting the Cd ions in the backbone of ZIF-8, leading to exposure of inaccessible FeN4 edge sites (that is, increasing active site density (SD)) and high fast mass transport at the catalyst layer of cathode. As a result, the final obtained Fe(Cd)─N─C catalyst has an active site density of 33.01 µmol g-1 (with 33.01% site utilization) over 5.8 times higher than that of Fe─N─C catalyst. Specially, the optimal catalyst delivers a high ORR performance with a half-wave potential of 0.837 (vs RHE) in a 0.1 m HClO4 electrolyte, which surpasses most of Fe-based catalysts.

Revealing the role of hydrogen bond coupling structure for enhanced performance of the solid-state electrolyte.

Achieving practical applications of PEO-based composite solid electrolyte (CPE) batteries requires the precise design of filler structures at the molecular level to form stable composite interfacial phases, which in turn improve the conductivity of Li+ and inhibit the nucleation growth of lithium dendrites. Some functional fillers suffer from severe agglomeration due to poor compatibility with the polymer base or grain boundary migration, resulting in limited improvement in cell performance. In this paper, ILs@KAP1 is reported as a filler to enhance the performance of PEO-based batteries. Thereinto, the hypercrosslinked phosphorus ligand polymer-containing KAP1, designed at the molecular level, has an abundant porous structure, hydrogen bonding network, and a rigid skeleton structure of benzene rings. These can be used both to improve the flammability with PEO-based and to reduce the crystallinity of the polymer electrolyte. Ionic liquids (ILs) are encapsulated in the nanochannels of KAP1, and thus a 3D Li+ conducting framework could be formed. In this case, it could not only facilitate the wettability of the contact interface with the electrode, significantly promoting its compatibility and providing a fast Li+ transport path, but also facilitate the formation of LiF, Li3N and Li2O rich SEI components, further fostering the uniform deposition/exfoliation of lithium. The LFP||CPE||Li battery assembled with ILs@KAP1-PEO-CPE has a high initial discharge specific capacity about 156 mAh/g at 1C and a remaining capacity about 121.8 mAh/g after 300 cycles (capacity retention of 78.07%).

Enantioselective construction of triaryl-substituted all-carbon quaternary stereocenters via organocatalytic arylation of oxindoles with azonaphthalenes.

Azonaphthalenes have been verified as a class of effective arylation reagents in a variety of asymmetric transformations. Here a highly efficient approach to construct triaryl-substituted all-carbon quaternary stereocenters through chiral phosphoric acid-catalyzed enantioselective arylation of 3-aryl-2-oxindoles with azonaphthalenes is disclosed. This chemistry is scalable and displays excellent functional group tolerance, furnishing a series of 3,3-disubstituted 2-oxindole derivatives in good yields with excellent enantiocontrol. Preliminary mechanistic data suggest that the initially formed direct addition intermediate undergoes intramolecular annulation under acidic reaction conditions.

Enhanced electrocatalytic performance for oxygen evolution reaction via active interfaces of Co3O4arrays@FeOx/Carbon cloth heterostructure by plasma-enhanced atomic layer deposition.

Oxygen evolution reaction (OER) is a necessary procedure in various devices including water splitting and rechargeable metal-air batteries but required a higher potential to improve oxygen evolution efficiency due to its slow reaction kinetics. In order to solve this problem, a heterostructured electrocatalyst (Co3O4@FeOx/CC) is synthesized by deposition of iron oxides (FeOx) on carbon cloth (CC) via plasma-enhanced atomic layer deposition, then growth of the cobalt oxide (Co3O4) nanosheet arrays. The deposition cycle of FeOxon the CC strongly influences thein situgrowth and distribution of Co3O4nanosheets and electronic conductivity of the electrocatalyst. Owing to the high accessible and electroactive areas and improved electrical conductivity, the free-standing electrode of Co3O4@FeOx/CC with 100 deposition cycles of FeOxexhibits excellent electrocatalytic performance for OER with a low overpotential of 314.0 mV at 10 mA cm-2and a small Tafel slope of 29.2 mV dec-1in alkaline solution, which is much better than that of Co3O4/CC (448 mV), and even commercial RuO2(380 mV). This design and optimization strategy shows a promising way to synthesize ideally designed catalytic architectures for application in energy storage and conversion.

Mutual Self-Regulation of d-Electrons of Single Atoms and Adjacent Nanoparticles for Bifunctional Oxygen Electrocatalysis and Rechargeable Zinc-Air Batteries.

Rechargeable zinc-air batteries (ZABs) are a promising energy conversion device, which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction (ORR) and oxygen evolution reactions (OER). Herein, we fabricate a range of bifunctional M-N-C (metal-nitrogen-carbon) catalysts containing M-Nx coordination sites and M/MxC nanoparticles (M = Co, Fe, and Cu) using a new class of γ-cyclodextrin (CD) based metal-organic framework as the precursor. With the two types of active sites interacting with each other in the catalysts, the obtained Fe@C-FeNC and Co@C-CoNC display superior alkaline ORR activity in terms of low half-wave (E1/2) potential (~ 0.917 and 0.906 V, respectively), which are higher than Cu@C-CuNC (~ 0.829 V) and the commercial Pt/C (~ 0.861 V). As a bifunctional electrocatalyst, the Co@C-CoNC exhibits the best performance, showing a bifunctional ORR/OER overpotential (ΔE) of ~ 0.732 V, which is much lower than that of Fe@C-FeNC (~ 0.831 V) and Cu@C-CuNC (~ 1.411 V), as well as most of the robust bifunctional electrocatalysts reported to date. Synchrotron X-ray absorption spectroscopy and density functional theory simulations reveal that the strong electronic correlation between metallic Co nanoparticles and the atomic Co-N4 sites in the Co@C-CoNC catalyst can increase the d-electron density near the Fermi level and thus effectively optimize the adsorption/desorption of intermediates in ORR/OER, resulting in an enhanced bifunctional electrocatalytic performance. The Co@C-CoNC-based rechargeable ZAB exhibited a maximum power density of 162.80 mW cm-2 at 270.30 mA cm-2, higher than the combination of commercial Pt/C + RuO2 (~ 158.90 mW cm-2 at 265.80 mA cm-2) catalysts. During the galvanostatic discharge at 10 mA cm-2, the ZAB delivered an almost stable discharge voltage of 1.2 V for ~ 140 h, signifying the virtue of excellent bifunctional ORR/OER electrocatalytic activity.

Correction: Long cyclic stability of acidic aqueous zinc-ion batteries achieved by atomic layer deposition: the effect of the induced orientation growth of the Zn anode.

Correction for 'Long cyclic stability of acidic aqueous zinc-ion batteries achieved by atomic layer deposition: the effect of the induced orientation growth of the Zn anode' by Zhisen Zeng et al., Nanoscale, 2021, 13, 12223-12232, https://doi.org/10.1039/d1nr02620h.

Engineering Energy Level of FeN4 Sites via Dual-Atom Site Construction Toward Efficient Oxygen Reduction.

Single-atom catalysts based on metal-N4 moieties and embedded in a graphite matrix (defined as MNC) are promising for oxygen reduction reaction (ORR). However, the performance of MNC catalysts is still far from satisfactory due to their imperfect adsorption energy to oxygen species. Herein, single-atom FeNC is leveraged as a model system and report an adjacent Ru-N4 moiety modulation effect to optimize the catalyst's electronic configuration and ORR performance. Theoretical simulations and physical characterizations reveal that the incorporation of Ru-N4 sites as the modulator can alter the d-band electronic energy of Fe center to weaken the FeO binding affinity, thus resulting in the lower adsorption energy of ORR intermediates at Fe sites. Thanks to the synergetic effects of neighboring Fe and Ru single-atom pairs, the FeN4 /RuN4 catalyst exhibits a half-wave potential of 0.958 V and negligible activity degradation after 10 000 cycles in 0.1 m KOH. Metal-air batteries using this catalyst in the cathode side exhibit a high power density of 219.5 mW cm-2 and excellent cycling stability for over 2370 h, outperforming the state-of-the-art catalysts.

A Shuttle-Free Solid-State Cu-Li Battery Based on a Sandwich-Structured Electrolyte.

Cu-Li batteries leveraging the two-electron redox property of Cu can offer high energy density and low cost. However, Cu-Li batteries are plagued by limited solubility and a shuttle effect of Cu ions in traditional electrolytes, which leads to low energy density and poor cycling stability. In this work, we rationally design a solid-state sandwich electrolyte for solid-state Cu-Li batteries, in which a deep-eutectic-solvent gel with high Cu-ion solubility is devised as a Cu-ion reservoir while a ceramic Li1.4 Al0.4 Ti1.6 (PO4 )3 interlayer is used to block Cu-ion crossover. Because of the high ionic conductivity (0.55 mS cm-1 at 25 °C), wide electrochemical window (>4.5 V vs. Li+ /Li), and high Cu ion solubility of solid-state sandwich electrolyte, a solid-state Cu-Li battery demonstrates a high energy density of 1 485 Wh kgCu -1 and long-term cyclability with 97 % capacity retention over 120 cycles. The present study lays the groundwork for future research into low-cost solid-state Cu-Li batteries.

Nanozyme-reinforced hydrogel as a H2O2-driven oxygenerator for enhancing prosthetic interface osseointegration in rheumatoid arthritis therapy.

Stem cell-based therapy has drawn attention for enhancing the osseointegration efficiency after joint replacement in the rheumatoid arthritis (RA). However, therapeutic efficacy of this approach is threatened by the accumulated reactive oxygen species (ROS) and poor oxygen supply. Herein, we develop a nanozyme-reinforced hydrogel for reshaping the hostile RA microenvironment and improving prosthetic interface osseointegration. The engineered hydrogel not only scavenges endogenously over-expressed ROS, but also synergistically produces dissolved oxygen. Such performance enables the hydrogel to be utilized as an injectable delivery vehicle of bone marrow-derived mesenchymal stem cells (BMSCs) to protect implanted cells from ROS and hypoxia-mediated death and osteogenic limitation. This nanozyme-reinforced hydrogel encapsulated with BMSCs can alleviate the symptoms of RA, including suppression of local inflammatory cytokines and improvement of osseointegration. This work provides a strategy for solving the long-lasting challenge of stem cell transplantation and revolutionizes conventional intervention methods for improving prosthetic interface osseointegration in RA.

Locally Fluorinated Electrolyte Medium Layer for High-Performance Anode-Free Li-Metal Batteries.

Low cycling Coulombic efficiency (CE) and messy Li dendrite growth problems have greatly hindered the development of anode-free Li-metal batteries (AFLBs). Thus, functional electrolytes for uniform lithium deposition and lithium/electrolyte side reaction suppression are desired. Here, we report a locally fluorinated electrolyte (LFE) medium layer surrounding Cu foils to tailor the chemical compositions of the solid-electrolyte interphase (SEI) in AFLBs for inhibiting the immoderate Li dendrite growth and to suppress the interfacial reaction. This LFE consists of highly concentrated LiTFSI dissolved in a fluoroethylene carbonate and/or succinonitrile plastic mixture. The CE of Cu||LiNi0.8Co0.1Mn0.1O2 (NCM811) AFLB increased to a high level of 99% as envisaged, and the cycling ability was also highly improved. These improvements are facilitated by the formation of a uniform, dense, and LiF-rich SEI. LiF possesses high interfacial energy at the LiF/Li interface, resulting in a more uniform Li deposition process as proved by density functional theory (DFT) calculation results. This work provides a simple yet utility tech for the enhancement of future high-energy-density AFLBs.

A Nanozyme-Immobilized Hydrogel with Endogenous ROS-Scavenging and Oxygen Generation Abilities for Significantly Promoting Oxidative Diabetic Wound Healing.

Non-healing wound is a common complication of diabetic patients associated with high morbidity and mortality. Engineered therapeutic hydrogels have enviable advantages in tissue regeneration, however, they are suboptimal for the healing of diabetic wounds characterized by reactive oxygen species (ROS) accumulation and chronic hypoxia. Here, a unique biological metabolism-inspired hydrogel, for ameliorating this hostile diabetic microenvironment, is presented. Consisting of natural polymers (hydrazide modified hyaluronic acid and aldehyde modified hyaluronic acid) and a metal-organic frameworks derived catalase-mimic nanozyme (ε-polylysine coated mesoporous manganese cobalt oxide), the engineered nanozyme-reinforced hydrogels can not only capture the endogenous elevated ROS in diabetic wounds, but also synergistically produce oxygen through the ROS-driven oxygen production ability. These fascinating properties of hydrogels protect skin cells (e.g., keratinocytes, fibroblasts, and vascular endothelial cells) from ROS and hypoxia-mediated death and proliferation inhibition. Diabetic wounds treated with the nanozyme-reinforced hydrogels highlight the potential of inducing the macrophages polarization from pro-inflammatory phenotype (M1) to anti-inflammatory subtype (M2). The hydrogel dressings demonstrate a prominently accelerated healing rate as shown by alleviating the excessive inflammatory, inducing efficiently proliferation, re-epithelialization, collagen deposition, and neovascularization. This work provides an effective strategy based on nanozyme-reinforced hydrogel as a ROS-driven oxygenerator for enhancing diabetic wound healing.

Constructing robust polymer/two-dimensional Ti3C2TX solid-state electrolyte interphase via in-situ polymerization for high-capacity long-life and dendrite-free lithium metal anodes.

We constructed an artificial polymer/two-dimensional Ti3C2TX (MXene) solid electrolyte interphase (SEI) on a Li metal surface via an in-situ polymerization strategy. The polymer layer provides excellent interface contact and outstanding adaptability for the volume expansion of Li metal, decreasing interface impedance. On the other hand, the two-dimensional MXene with a low Li nucleation energy barrier is beneficial for uniform Li deposition and restraint of interfacial side reactions. In this work, a dense and durable MXene-integrated SEI between the Li metal anode and solid-state electrolyte (SSE) interface is constructed to render the Li/SSE/Li cell to maintain a stable polarization voltage of approximately 50 mV at a capacity of 0.50 mAh cm-2 for over 1000 h. It enables the Li/SSE/LiFePO4 cell to deliver a capacity of 130.1 mAh g-1 at 1C with a capacity retention of 91.4% after 900 cycles. Therefore, we believe that this facile in-situ polymerization method for constructing a layer of polymer/MXene SEI at the interface between Li metal anodes and SSE can promote the practical applications of Li metal batteries.

Double-Enhanced Core-Shell-Shell Sb2S3/Sb@TiO2@C Nanorod Composites for Lithium- and Sodium-Ion Batteries.

For most alloying- and conversion-type anode materials, a huge volume expansion and structure degradation of the electrodes always hinder their applications. In this work, a novel core-shell-shell Sb2S3/Sb@TiO2@C nanorod composite has been designed layer by layer, which includes an inner Sb2S3/Sb heterostructure core protected by an oxygen-deficient TiO2 shell and a conductive carbon shell. It is interesting to observe that, during the carbothermic reduction process, the previous Sb2S3 nanorod cores are partially reduced into a metallic Sb phase and the reduced TiO2 also creates many oxygen vacancies, which can greatly enhance the conductivity of the semiconductor Sb2S3. Thanks to the double effects of the TiO2 middle shell and carbon outer shell, the unique double-shelled structure design creates an enhanced dual protection, which can better accommodate the volume-expansive deformation and preserve the structural integrity of the active Sb2S3/Sb core. Especially, the TiO2 middle layer is self-assembled by numerous nanoparticles acting as a nanopillar backbone, which supports between the nanorod core and outer carbon shell to better buffer the volume changes. As a result, the core-shell-shell Sb2S3/Sb@TiO2@C anode shows lithium and sodium storage performances superior to those of the pristine Sb2S3 and core-shell Sb2S3@TiO2 electrodes. For lithium-ion batteries, the Sb2S3/Sb@TiO2@C nanorod composite achieves an initial discharge/recharge capacity of 1244.9/1005.1 mAh g-1 with an initial Coulombic efficiency of about 80.7%, an enhanced rate capability with a capacity of 593.2 mA h g-1 at 5.0 A g-1, and prolonged cycling life for 500 cycles with a reversible capacity of 495.8 mAh g-1 at 0.5 A g-1. For sodium-ion batteries, the nanorodalso exhibits an improved performance with an initial discharge/recharge capacity of 781.4/574.0 mAh g-1 (initial Coulombic efficiency of about 73.46%) and cycling for 400 cycles with a reversible capacity of 422.6 mAh g-1 at 0.8 A g-1. This research sheds light upon double-shell structure designs with an effective middle shell to enhance the energy storage performance of electrode materials.