Robust Lithium Research Articles

Cobalt(II)‐Centered Fluorinated Phthalocyanine‐Sulfur SNAr Chemistry for Robust Lithium–Sulfur Batteries with Superior Conversion Kinetics

AbstractDue to the exceptional theoretical energy density and low cost of elemental sulfur, lithium–sulfur (Li–S) batteries are spotlighted as promising post‐lithium‐ion batteries. Despite these advantages, the performance of Li–S batteries would need to be improved further for their wide dissemination in practical applications. Here, cobalt(II)‐centered fluorinated phthalocyanine, namely, F‐Co(II)Pc, is reported as a multi‐functional component for sulfur cathodes with the following benefits: 1) enhanced conversion kinetics as a result of the catalytic effect of the cobalt(II) center, 2) efficient sulfur linkage via the fluorine functionality, which undergoes a nucleophilic aromatic substitution (SNAr) reaction, 3) suppression of the shuttling issue by the nitrogen atoms because of their strong affinity with polysulfides, and 4) the necessary aromaticity to engage in π–π interaction with reduced graphene oxide for electrical conductivity. The resulting electrode has promising electrochemical properties, such as sustainable cycling for 700 cycles and robust operation with a sulfur loading of 12 mgsulfur cm−2, unveiling the promising nature of phthalocyanine and its related molecular families for advanced Li–S batteries.

Solid Solution of Bi and Sb for Robust Lithium Storage Enabled by Consecutive Alloying Reaction.

Materials with alloying reactions have significant potential as electrodes for lithium-ion batteries (LIBs) due to its high theoretical capacity and appropriate lithiation potentials. Nonetheless, their cycling performance is inferior due to violent volume expansion and severe pulverization of active materials. Herein, solid solution of Bi0.5 Sb0.5 encapsulated with carbon is discovered to enable consecutive alloying reactions with manageable volume change, suitable for developing LIBs with high capacity and robust cyclability. A Sb-rich shell and Bi-rich core structure is formed in cycling since the alloying reaction between Sb and Li occurs first, followed by the alloying reaction between Bi and Li. Such a consecutive alloying reaction obeying the thermodynamic path is experimentally realized by the carbon capsulation, which acts as a protecting solid layer to avoid polarized reactions occurred when exposed directly to liquid electrolyte. The LIBs using Bi0.5 Sb0.5 @carbon run on the consecutive alloying reactions exhibits high capacity, prolonged lifespan (489.4 mAh g-1 after 2000 cycles at 1 A g-1 ) and fast kinetic, while those using bare Bi0.5 Sb0.5 suffer from worsened kinetic and thus a poor cycling performance owning to the polarized reactions. The work paves a way of developing alloy electrodes for alkaline-ion rechargeable batteries with potential industry applications.

Tubular CoFeP@CN as a Mott–Schottky Catalyst with Multiple Adsorption Sites for Robust Lithium−Sulfur Batteries

AbstractThe shuttle effect and the sluggish reaction kinetics of lithium polysulfide (LiPS) seriously compromise the performance of lithium–sulfur batteries (LSBs). To overcome these limitations and enable the fabrication of robust LSBs, here the use of a Mott–Schottky catalyst based on bimetallic phosphide CoFeP nanocrystals supported on carbon nitride tubular nanostructures as sulfur hosts is proposed. Theoretical calculations and experimental data confirm that CoFeP@CN composites are characterized by a suitable electronic structure and charge rearrangement that allows them to act as a Mott–Schottky catalyst to accelerate LiPS conversion. In addition, the tubular geometry of CoFeP@CN composites facilitates the diffusion of Li ions, accommodates volume change during the reaction, and offers abundant lithiophilic/sulfiphilic sites to effectively trap soluble LiPS. Therefore, S@CoFeP@CN electrodes deliver a superior rate performance of 630 mAh g−1 at 5 C, and remarkable cycling stability with 90.44% capacity retention over 700 cycles. Coin cells with high sulfur loading, 4.1 mg cm−2, and pouch cells with 0.1 Ah capacities are further produced to validate their superior cycling stability. In addition, it is demonstrated here that CoFeP@CN hosts greatly alleviate the often overlooked issues of low energy efficiency and serious self‐discharging in LSBs.

Stable interfaces constructed by concentrated ether electrolytes to render robust lithium metal batteries

Lithium metal batteries (LMBs) are highly considered as promising candidates for next-generation energy storage systems. However, routine electrolytes cannot tolerate the high potential at cathodes and low potential at anodes simultaneously, leading to severe interfacial reactions. Herein, a highly concentrated electrolyte (HCE) region trapped in porous carbon coating layer is adopted to form a stable and highly conductive solid electrolyte interphase (SEI) on Li metal surface. The protected Li metal anode can potentially match the high-voltage cathode in ester electrolytes. Synergistically, this ingenious design promises high-voltage-resistant interfaces at cathodes and stable SEI with abundance of inorganic components at anodes simultaneously in high-voltage LMBs. The feasibility of this interface-regulation strategy is demonstrated in Li | LiFePO4 batteries, realizing a lifespan twice as long as the routine cells, with a huge capacity retention enhancement from 46.4% to 88.7% after 100 cycles. This contribution proof-of-concepts the emerging principles on the formation and regulation of stable electrode/electrolyte interfaces in the cathode and anode simultaneously towards the next-generation high-energy–density batteries.

Hierarchical Nanoreactor with Multiple Adsorption and Catalytic Sites for Robust Lithium-Sulfur Batteries.

Developing high-performance cathode host materials is fundamental to solve the low utilization of sulfur, the sluggish redox kinetics, and the lithium polysulfide (LiPS) shuttle effect in lithium-sulfur batteries (LSBs). Here, a multifunctional Ag/VN@Co/NCNT nanocomposite with multiple adsorption and catalytic sites within hierarchical nanoreactors is reported as a robust sulfur host for LSB cathodes. In this hierarchical nanoreactor, heterostructured Ag/VN nanorods serve as a highly conductive backbone structure and provide internal catalytic and adsorption sites for LiPS conversion. Interconnected nitrogen-doped carbon nanotubes (NCNTs), in situ grown from the Ag/VN surface, greatly improve the overall specific surface area for sulfur dispersion and accommodate volume changes in the reaction process. Owing to their high LiPS adsorption ability, outer Co nanoparticles at the top of the NCNTs catch escaped LiPS, thus effectively suppressing the shuttle effect and enhancing kinetics. Benefiting from the multiple adsorption and catalytic sites of the developed hierarchical nanoreactors, Ag/VN@Co/NCNTs@S cathodes display outstanding electrochemical performances, including a superior rate performance of 609.7 mAh g-1 at 4 C and a good stability with a capacity decay of 0.018% per cycle after 2000 cycles at 2 C. These properties demonstrate the exceptional potential of Ag/VN@Co/NCNTs@S nanocomposites and approach LSBs closer to their real-world application.

Robust lithium storage of block copolymer-templated mesoporous TiNb2O7 and TiNb2O7@C anodes evaluated in half-cell and full-battery configurations

We report a facile Pluronic F127-mediated evaporation-induced self-assembly (EISA) process for the scalable preparation of mesoporous TiNb2O7 (m-TNO) with an uniform grain size of ~12 nm. The elaborated m-TNO are demonstrated as an excellent anode material for lithium-ion batteries (LIBs) able to deliver a high discharge specific capacity of 235.7 mAh/g at 1 C and 109.2 mAh/g even at 20 C, with high capacity retention rate up to 94.6% after 100 cycles at 1 C in half cell. In addition, the m-TNO electrode delivers a specific capacity of 257.1 mAh/g at a current density of 0.5 C in the m-TNO/LiFePO4 full cell, and a high discharge capacity of 185.1 mAh/g can be achieved with a capacity retention rate of 78.7% even at 1 C after 800 cycles. To further improve the electrochemical performances, carbon-coated m-TNO (m-TNO@C) is also synthesized by calcining the mixture of m-TNO and glucose. The initial discharge specific capacity of m-TNO@C is 248.4 mAh/g, and the capacity retention after 100 cycles at 1 C is 90.1%. The conductive carbon layer on m-TNO significantly improves the electronic conductivity of m-TNO. Cyclic voltammetry (CV) and electrical impedance spectroscopy (EIS) analyses show that coating the carbon layer by grinding will reduce the Li+ ion diffusion rate and lower its rate performance under the high current density, compared with the uncoated counterpart. Both of m-TNO and m-TNO@C deliver long-term cyclic stability with the large capacity of ~160 mAh/g even at 5 C after 800 cycle, accompanied by the capacity retention rate of ~70%, exhibiting excellent electrochemical performances in LIBs.

Intralayered Ostwald Ripening-Induced Self-Catalyzed Growth of CNTs on MXene for Robust Lithium-Sulfur Batteries.

The distinguishable physicochemical properties of MXenes render them attractive in electrochemical energy storage. However, the strong tendency to self-restack owing to the van der Waals interactions between the MXene layers incurs a massive decrease in surface area and blocking of ions transfer and electrolytes penetration. Here, in situ generated Ti3 C2 Tx MXene-carbon nanotubes (Ti3 C2 Tx -CNTs) hybrids are reported via low-temperature self-catalyzing growth of CNTs on Ti3 C2 Tx nanosheets without the addition of any catalyst precursors. With combined spectroscopic studies and theoretical calculation results, it is certified that the intralayered Ostwald ripening-induced Ti3 C2 Tx nanomesh structure contributes to the uniform precipitation of ultrafine metal Ti catalysts on Ti3 C2 Tx , thus giving rise to the in situ CNTs formation on the surface of Ti3 C2 Tx with high integrity. Taking advantages of intimate electrolyte penetration, unobstructed 3D Li+ /e transport, and rich electroactive sites, the Ti3 C2 Tx -CNTs hybrids are confirmed to be ideal 3D scaffolds for accommodating sulfur and regulating the polysulfides conversion for high-loaded lithium-sulfur batteries.

Electroless Formation of a Fluorinated Li/Na Hybrid Interphase for Robust Lithium Anodes

Engineering a stable solid electrolyte interphase (SEI) is one of the critical maneuvers in improving the performance of a lithium anode for high-energy-density rechargeable lithium batteries. Herein, we build a fluorinated lithium/sodium hybrid interphase via a facile electroless electrolyte-soaking approach to stabilize the repeated plating/stripping of lithium metal. Jointed experimental and computational characterizations reveal that the fluorinated hybrid SEI mainly consisting of NaF, LiF, LixPOyFz, and organic components features a mosaic polycrystalline structure with enriched grain boundaries and superior interfacial properties toward Li. This LiF/NaF hybrid SEI exhibits improved ionic conductivity and mechanical strength in comparison to the SEI without NaF. Remarkably, the fluorinated hybrid SEI enables an extended dendrite-free cycling of metallic Li over 1300 h at a high areal capacity of 10 mAh cm-2 in symmetrical cells. Furthermore, full cells based on the LiFePO4 cathode and hybrid SEI-protected Li anode sustain long-term stability and good capacity retention (96.70% after 200 cycles) at 0.5 C. This work could provide a new avenue for designing robust multifunctional SEI to upgrade the metallic lithium anode.

In Situ Curing Technology for Dual Ceramic Composed by Organic–Inorganic Functional Polymer Gel Electrolyte for Dendritic‐Free and Robust Lithium–Metal Batteries

AbstractLithium–metal batteries (LiMBs) are promising energy storage devices due to the high capacity and minimum negative electrochemical potential. Nevertheless, their concrete applications remain disturbed by unbalanced electrolyte–electrode interfaces, limited electrochemical window, and high risk. Herein, a novel strategy to obtain dual ceramic‐based electrolytes that possesses a great potential in energy storages and higher level of energy densities in LiMBs. Dual‐ceramic (lithium aluminum titanium phosphate ‐lithium lanthanum titanium oxide (LATP‐LLTO)) gel polymer electrolyte (DCGPE) film developed via the curable system aims to prepare flexible Li+ interpenetrating network film to integrate the two ceramic structures with polyethylene oxide (PEO) to yield the free‐standing electrolytes film for better battery safety and desired interfacial stability. The DCGPEs films present a satisfactory electrochemical performance, including good ionic conductivity, large transference number, and wide electrochemical stability window at room temperature. Most importantly, the fundamental function of LATP and LLTO is to support building a stable solid‐electrolyte‐interphase and limits the growth of dendrites. Thus, prepared dual ceramic‐based electrolytes effectively render to inhibit lithium dendrite growth in a symmetrical cell Li//PEO + 10% LATP + 15% LLTO//Li test during charge/discharge at a current density of 2 and 0.25 mA cm−2 above 2400 h without short‐circuiting occurrence at room temperature. Besides, the battery assembled of LiFePO4/PEO + 10% LATP + 20% LLTO/Li exhibits superior cyclic stability with high Coulombic efficiency. This study recommends that the binary network structures of Li‐ion conductor help to design a prime solution of promising electrolyte for high‐performance LiMBs applications.

Amorphous MoS3 decoration on 2D functionalized MXene as a bifunctional electrode for stable and robust lithium storage

The development of electrode materials with the synergistic effects of good chemical stability and high electrical conductivity has improved the sluggish ion kinetics and severe capacity degradation of rechargeable lithium batteries. Herein, a multifunctional heterostructure material (MoS3-Ti3C2Tx) comprising a functionalized MXene (Ti3C2Tx) and amorphous MoS3 is prepared by a scalable electrostatic self-assembly method. Remarkably, as lithium-ion battery anodes, the resultant MoS3-Ti3C2Tx not only exhibits increased electrochemical activity, accelerated lithium-ion diffusion and fast charge transfer kinetics but also shows high specific capacity, excellent rate performance and long-term cycling stability. By virtue of these merits, MoS3-Ti3C2Tx offers an excellent reversible capacity of 1043 mAh g−1 at 200 mA g−1 and exhibited a capacity of 568 mAh g−1 at a current density of 2 A g−1 after 1000 cycles. When acting as the cathode for lithium-sulfur batteries, the amorphous MoS3 anchored on MXene demonstrates high capture and catalytic activity towards polysulfide conversion. Accordingly, the optimized electrode exhibits a capacity of 836 mAh g−1 at 0.2C after 100 cycles and a satisfactory rate performance of 463 mAh g−1 at 2C after 400 cycles. Moreover, the associated conversion mechanism is studied by ex situ XPS. These results demonstrate that heterostructure composites constructed by an amorphous sulfide and surface functionalized MXene are feasible electrode materials for both lithium-sulfur batteries and lithium-ion batteries.

Restructured rimous copper foam as robust lithium host

Uncontrollable growth of lithium (Li) dendrites and infinite volume change during cycling limit the practical implementation of Li metal anode in batteries. Three-dimensional (3D) porous materials with interconnected conductive skeleton are expected as ideal hosts to boost uniform Li deposition by reducing the local current density and Li nucleation barrier. However, surface modifications for the 3D conductive frameworks are complicated and costly, and most of these host materials can only afford shallow cycling at smaller current densities. Herein, a new strategy is proposed to fabricate rimous Cu foam (RCF) with ant-nest-like porous skeleton via a novel polysulfide-assisted reconstruction approach. The interconnected conducting Cu network with a larger and lithiophilic surface enables uniform and deep Li deposition into the interior space of RCF. The unique ant-nest-like interior channel not only endows a high intake capacity for Li, but also abstains volume fluctuation of Li anode during cycling. Therefore, the RCF-modified Li anode delivers excellent cycling stability with high Coulombic efficiency of 99% after 660 cycles at 1 ​mA ​cm−2 and small overpotential of 30 ​mV over 200 ​h under a high plating/stripping rate of 3 ​mA ​cm−2. More importantly, full cells paired with practical-level LiFePO4 cathode exhibit exceptional performance under high current densities.

PVDF-supported graphene foam as a robust current collector for lithium metal anodes.

Lithium metal batteries have drawn much attention due to their ultrahigh energy density. However, the safety hazards and limited lifetime caused by severe lithium dendrite growth during cycling hinder their real application. To address this issue and improve the electrochemical performance of current lithium batteries, a current collector beyond the traditional copper foil for lithium anodes is highly needed. We proposed and prepared a PVDF-supported graphene foam (PSGF) structure as an effective current collector for lithium metal anodes. Because of its structural stability, large surface area, and lithiophilic surface chemistry, the corresponding lithium metal anode (PSGF@Li) shows an extended cycling life (∼1000 h), a decreased voltage hysteresis (∼80 mV) and an improved coulombic efficiency (∼99%). Furthermore, the practical application of the PSGF@Li anode in a full cell system was also demonstrated.

Ultrahigh Rate Performance of a Robust Lithium Nickel Manganese Cobalt Oxide Cathode with Preferentially Orientated Li-Diffusing Channels.

Lithium nickel manganese cobalt oxide (NMC) materials, with low cost and high energy density, are considered to be among the most promising cathode materials for Li-ion batteries (LIBs). However, several issues have hindered their further deployment, particularly for high-powered applications, including limited rate capability, capacity loss during cycling (especially at high temperatures and high voltages), and difficulty in reproducibly preparing the desired particle morphology. In this work, we have developed a robust LiNi0.33Mn0.33Co0.33O2 cathode material (NMC-111) capable of high-rate performance for LIBs. Our high power NMC-111 (HP-NMC) cathode materials showed significantly enhanced electrochemical performance, relative to a commercial NMC-111 (c-NMC), with discharge capacities of 138 and 131 mAh/g at high current rates of 20 and 30 C, respectively. The material also exhibited enhanced cycling stability under both room temperature and at 50 °C. We ascribe the high performance of our material to a unique crystalline microstructure observed by electron microscopy characterization, which showed preferential orientation of the Li-diffusing channels radially outward. This HP-NMC material achieved one of the highest performance metrics among NMC materials reported to date, especially for high-powered electric vehicles.

Robust Lithium Metal Anodes Realized by Lithiophilic 3D Porous Current Collectors for Constructing High-Energy Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are attractive candidates for next-generation rechargeable batteries. With the steady development of sulfur cathodes, the recent revival of research on dendrite-free Li metal anodes offers opportunities to improve the stabilities and safety of Li-S batteries. However, the low capacities and low Li utilizations of current Li anodes hinder the improvement of the energy densities of Li-S batteries. Here, we present a facile approach to fabricate lithiophilic three-dimensional porous current collectors by modifying commercial metal foams with yolk-shell structured N-doped porous carbon nanosheets. Benefiting from the structure-based rational design, this current collector is able to generate dendrite-free Li anodes with improved Coulombic efficiencies and life spans, enabling carbon/sulfur cathodes to exhibit significantly enhanced stabilities (e.g., 78.1% of capacity retention after 1400 cycles). More importantly, we successfully constructed a high-areal-capacity Li-S full cell (9.84 mAh cm-2) with 82% Li utilization. This work provides a promising route toward high-energy-density Li-S batteries.

Blocking Polysulfide with Co2B@CNT via "Synergetic Adsorptive Effect" toward Ultrahigh-Rate Capability and Robust Lithium-Sulfur Battery.

Li-S batteries have attracted great interest as the next-generation secondary batteries due to their high energy density, being environmentally friendly, and low price. However, the road to commercialization of lithium-sulfur batteries remains limited owing to the "shuttle effect" of soluble polysulfides, which results in the inferior cycle stability. Herein, a potent functional separator is developed to restrain the "shuttle effect" by coating Co2B@carbon nanotube layer on the commercialized polypropylene separator. In merits of the coadsorption of Co sites and B sites, such Co2B shows highly efficient polysulfides block (11.67 mg/m2 for Li2S6). Besides, the composite also exhibits obviously catalysis from Li2S8 to Li2S. By combining the fast electron transportation along the carbon nanotube, a superior rate performance is achieved with the modified separator and common carbon-sulfur cathode. Typically, the cell with Co2B@CNT shows prominent cycling life with a capacity degradation of 0.0072% per cycle (3000 cycles) and ultrahigh-rate capability at 5 C current (1172.8 mAh/g), which outstands the previously reported polysulfides barrier layer. The cell with Co2B@CNT can exhibit electrochemical performance at areal capacity of 5.5 mAh/cm2 (0.5 C) when the sulfur loading increased to 5.8 mg/cm2. This work defines an efficacious strategy to restrain the "shuttle effect" of polysulfides and shed light on the great potential of borides in Li-S battery.

Efficient and robust lithium metal electrodes enabled by synergistic surface activation–passivation of copper frameworks

The synergistic surface tailoring of three-dimensional Cu frameworks achieved via Ag-induced activation and Al2O3-induced passivation leads to a significant improvement in the Li plating–stripping efficiency and cycling performance.

Nitrogen, sulfur-codoped micro-mesoporous carbon derived from boat-fruited sterculia seed for robust lithium-sulfur batteries.

The diverse textures and tunable surface properties of abundant bioresources offer great opportunities to utilize biochar materials as sulfur hosts for naturally boosting the electrochemical performances of Li–S batteries. Herein, a N, S-codoped micro–mesoporous carbon was synthesized from boat-fruited sterculia seed, and used as a sulfur host matrix for Li–S batteries. After sulfur infiltration (≈62% sulfur) and cell assembly, the obtained S/NSBC cathode shows outstanding discharge–charge performance, good rate capability, and especially long cycling stability. A high initial discharge capacity of 1478 mA h g−1 was achieved at 0.1C, and the reversible discharge capacity was still retained at 649 mA h g−1 after 500 cycles at 0.5C with ultralow decay rate of 0.08% per cycle, and especially zero-capacity-decay after 300 cycles. Such superior electrochemical performance of S/NSBC cathode is attributed to the synergy of the unique 3D conductive micro–mesoporous frameworks and huge N, S-codoped polar surface within the carbon matrix, which can physically confine the dissolved polysulfides within the pore structures, and chemically anchor the polysulfides through chemical interaction between lithium polysulfides and N and S sites, thus enabling the favorable reaction kinetics, efficient utilization of sulfur, and effective mitigation of polysulfide diffusion and shuttling within the cathode. This work well manifests the great feasibility and superiority of utilizing bioresources for high performance Li–S batteries.

Nickel-iron layered double hydroxides and reduced graphene oxide composite with robust lithium ion adsorption ability for high-capacity energy storage systems

Rationally designed electrode materials with high capacity, excellent stability, and good rate capability are essential for high-performance energy storage systems. This study reported the design of nickel-iron layered double hydroxides nanosheets and reduced graphene oxide composites (NiFe-LDHs/rGO composites) for high-capacity LIB electrode. The NiFe-LDHs/rGO composites were prepared by adsorption of Ni2+ and Fe3+ ions onto the graphene oxide (GO) surface, co-deposition of NiFe-LDHs nanosheets from the adsorbed ions in alkaline solution, and reduction of GO into rGO. In the composites, a large interlayer spacing of 7.55 Å and proper adsorption energy for Li+ ion (−4.36 eV) in NiFe-LDHs nanosheets greatly facilitate the reversible transport and storage of abundant Li+ ions. Meanwhile, the outer rGO wrappings offer a highly conductive matrix as efficient electron pathways. With these advantages, the NiFe-LDHs/rGO composites demonstrated a good cyclic stability with 602.8 mAh g−1 capacity remained over 80 charge/discharge cycles at a current density of 500 mA g−1. Thus, our studies offer a low-cost NiFe-LDHs/rGO material for high-performance LIBs.

Mesoporous TiO2/TiC@C Composite Membranes with Stable TiO2-C Interface for Robust Lithium Storage

SummaryTransition metal oxides/carbon (TMOs/C) composites are important for high-performance lithium-ion batteries (LIBs), but the development of interface-stable TMOs/C composite anodes for robust lithium storage is still a challenge. Herein, mesoporous TiO2/TiC@C composite membranes were synthesized by an in situ carbothermic reduction method. TiC nanodots with high conductivity and electrochemical inactivity at the TiO2-C interface can significantly enhance the electrical conductivity and structural stability of the membranes. Finite element simulations demonstrate that the TiO2/TiC@C membranes can effectively alleviate tensile and compression stress effects upon lithiation, which is beneficial for robust lithium storage. When used as additives and binder-free electrodes, the TiO2/TiC@C membranes show excellent cycling capability and rate performance. Moreover, a flexible full battery can be assembled by employing the TiO2/TiC@C membranes and shows good performance, highlighting the potential of these membranes in flexible electronics. This work opens an avenue to constructing interface-stable composite structures for the next-generation high-performance LIBs.

C@MoS2@PPy sandwich-like nanotube arrays as an ultrastable and high-rate flexible anode for Li/Na-ion batteries

Flexible electrode with robust mechanical and electrochemical property is crucial for thin film battery technology, especially in deformable electronics. In present work, a self-supported C@MoS2@PPy sandwich-like nanotube arrays (SNTAs) have been engineered and synthesized on steel substrate through a simple template-based approach and further employed as freestanding anode for Li/Na-ion batteries. For the C@MoS2@PPy SNTAs, ultra-thin MoS2 nanosheets are uniformly covered with conductive polypyrrole (PPy) and synchronically deposited on the carbon submicron tube arrays (CSTAs) which is vertically grown on the substrate. The conductive tubular array-type CSTAs skeleton and outer PPy coating not only endow the SNTAs with superior e-/ion conduction, but also preserve the framework stability when complete volumetric swelling occur in MoS2. As a result, such SNTAs electrode show a robust lithium storage (1050 mA h g−1 at 200 μA cm-2/805 mA g-1 over 600 cycles and a rate property of 630 mA h g-1 at 1000 μA cm-2/4027 mA g-1) and also impressive sodium storage (615 mA h g−1 at 50 μA cm-2/201 mA g-1 over 200 cycles and a rate property of 405 mA h g-1 at 250 μA cm-2/1007 mA g-1). These freestanding SNTAs electrode exhibit its promising future in deformable energy storage technologies.