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The incomplete blocking of small-sized polysulfides by pore size and the effect on Li+ transport are generally neglected when the size-sieving effect is employed to suppress the shuttling of polysulfides. Herein, ion-selective modified layers with pore sizes equal to, greater than, and less than 0.8 nm, respectively, on the polypropylene separator are fabricated to obtain the preferable pore size for separation of polysulfides and Li+. As a result, the modified layer with a pore size of 0.8 nm can efficiently inhibit the shuttling of polysulfides and simultaneously boost the diffusion of Li+ under the double effect of the size advantage and electrostatic shielding. Consequently, the battery using a separator with a modified layer having a pore size of 0.8 nm possesses a lower capacity attenuation of 0.047% after 1000 cycles at 2.0 C. This work serves as a vital guide for suppressing polysulfide shuttle using ion-selective sieving effects for lithium-sulfur batteries.
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It is undeniable that the dissolution of polysulfides is beneficial in speeding up the conversion rate of sulfur in electrochemical reactions. But it also brings the bothersome "shuttle effect". Therefore, if polysulfides can be retained on the cathode side, the efficient utilization of the polysulfides can be guaranteed to achieve the excellent performance of lithium-sulfur batteries. Based on this idea, considerable methods have been developed to inhibit the shuttling of polysulfides. It is necessary to emphasize that no matter which method is used, the solvation mechanism, and existence forms of polysulfides are essential to analyze. Especially, it is important to clarify the sizes of different forms of polysulfides when using the size effect to inhibit the shuttling of polysulfides. In this review, a comprehensive summary and in-depth discussion of the solvation mechanism, the existing forms of polysulfides, and the influencing factors affecting polysulfides species are presented. Meanwhile, the size of diverse polysulfide species is sorted out for the first time. Depending on the size of polysulfides, tactics of using size effect in cathode, separator, and interlayer parts are elaborated. Finally, a design idea of materials pore size is proposed to satisfy the use of size effect to inhibit polysulfides shuttle.
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Nanomaterials are widely used in many fields for their unique physical and chemical properties and especially demonstrate irreplaceability in energy storage systems. In this paper, a novel composite of copper sulfide with hypha-like core-shell nano-structure is synthesized by in situ phase inversion method, which serves as high stability negative electrode materials of zinc-ion batteries (ZIBs). The unique structure facilitates efficient electron and ion transport, enhances the kinetics of electrochemical reactions, and effectively suppresses the undesired expansion and decomposition of transition metal compounds. As a result, the half battery exhibits high specific capacity (250.2 mAh g-1 at 0.1 A g-1), reliable rate performance, and cycle stability (98.3 mAh g-1 at 1 A g-1 after 500 cycles). Additionally, when assembled with ZnxMnO2 positive to form a full battery, it demonstrates good cycling capacity at an intermediate current density of 2 A g-1, while maintaining excellent structural stability over 5,000 cycles (61% retention).
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Although lithium-sulfur batteries (LSBs) are considered as the promising next rechargeable storage system ascribing to their decent specific capacity of inorganic sulfur, the development is partially impeded by inferior electronic conductivity, severe shuttle effect, and large volume variation. To tackle the issues above, a great deal of effort is made on sulfur-containing polymer (SCP) that shows better electrochemical performance. Nevertheless, sluggish conversion of lithium polysulfides (LiPSs) obstructs battery performance yet. Herein, electrocatalytic LiPSs with full conversion by tailoring the interfacial electric field are discovered based on gold nanoparticles (AuNPs) anchored on sulfurized polyaniline (SPANI). A downhill path of Gibbs free energy from organosulfur polymer to intermediate product means more spontaneously and favorable for full conversion, as the significant enhancement of electron density of state in the vicinity of the HOMO level for the AuNPs increase the electron transition probability rate. This composite delivers satisfactory electrochemical performance, especially increased rate capacity of >300 mAh g-1. Furthermore, catalyst mechanism on molecule level is proposed that AuNPsdominate chemical enhancement and higher electron delocalizablility betweenAuNPs and LiPSs molecules. These results can erect a promising strategy for enhancing lithium polysulfides full conversion.
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Carbon-based hole transport layer-free perovskite solar cells (PSCs) based on methylammonium lead triiodide (MAPbI3 ) have become one of the research focus due to low cost, easy preparation, and good optoelectronic properties. However, instability of perovskite under vacancy defects and stress-strain makes it difficult to achieve high-efficiency and stable power output. Here, a soft-structured long-chain 2D pentanamine iodide (abbreviated as "PI") is used to improve perovskite quality and interfacial mechanical compatibility. PI containing CH3 (CH2 )4 NH3 + and I- ions not only passivate defects at grain boundaries, but also effectively alleviate residual stress during high temperature annealing via decreasing Young's modulus of perovskite film. Most importantly, PI effectively increases matching degree of Young's modulus between MAPbI3 (47.1 GPa) and carbon (6.7 GPa), and strengthens adhesive fracture energy (Gc ) between perovskite and carbon, which is helpful for outward release of nascent interfacial stress generated under service conditions. Consequently, photoelectric conversion efficiency (PCE) of optimal device is enhanced from 10.85% to 13.76% and operational stability is also significantly improved. 83.1% output is maintained after aging for 720 h at room temperature and 25-60% relative humidity (RH). This strategy of regulation from chemistry and physics provides a strategy for efficient and stable carbon-based PSCs.
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Chromium is a multivalent metal with great development in the energy storage field because it can effectively improve the electrochemical performance of the material. However, chromium(VI) is soluble in water and toxic, which causes serious metal pollution in the environment. In addition, nanoplastics are difficult to degrade and easy to accumulate, which is an urgent environmental problem to be solved. Therefore, we choose Zea mays to absorb chromium ions, nanopolystyrene, nanocarboxylic polystyrene, and their complexes, which can coordinate and decompose with various polymers in Z. mays, and produce coordination, conjugation, mixed valence, and adjacent group effects. Due to the above effects, the UV-vis spectrum of the material is blueshifted; the X-ray photoelectron spectroscopy peaks of Cr 2p have a chemical shift; the pore structure is optimized; the graphitization degree is improved; the content of N, O, and Cr in the material increases; and the elements are evenly distributed. The series of optimization processes makes the electrodes exhibit excellent electrochemical performance in both supercapacitors and lithium-ion batteries. At 0.5 A·g-1, the specific capacitance of the electrode reaches 490 F·g-1. After 10,000 cycles, its specific capacitance remains at 429.3 F·g-1, and the Coulombic efficiency is 89.9%. In lithium-ion batteries, the initial discharging capacity of the electrode is 1071.7 mAh·g-1 at 0.05 A·g-1. After 5000 cycles, its specific capacity can still reach 242 mAh·g-1 at 0.2 A·g-1, and the Coulombic efficiency is above 95%.
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With the development of flexible and wearable electronic devices, it is a new challenge for polymer hydrogel electrolytes to combine high mechanical flexibility and electrochemical performance into one membrane. In general, the high content of water in hydrogel electrolyte membranes always leads to poor mechanical strength, and limits their applications in flexible energy storage devices. In this work, based on the "salting out" phenomenon in Hofmeister effect, a kind of gelatin-based hydrogel electrolyte membrane is fabricated with high mechanical strength and ionic conductivity by soaking pre-gelated gelatin hydrogel in 2 m ZnSO4 aqueous. Among various gelatin-based electrolyte membranes, the gelatin-ZnSO4 electrolyte membrane delivers the "salting out" property of Hofmeister effect, which improves both the mechanical strength and electrochemical performance of gelatin-based electrolyte membranes. The breaking strength reaches 1.5 MPa. When applied to supercapacitors and zinc-ion batteries, it can sustain over 7500 and 9300 cycles for repeated charging and discharging processes. This study provides a very simple and universal method to prepare polymer hydrogel electrolytes with high strength, toughness, and stability, and its applications in flexible energy storage devices provide a new idea for the construction of secure and stable flexible and wearable electronic devices.
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The attapulgite@carbon/NiCo layered double hydroxide nanocomposites based on waste adsorbents are manufactured via simple and eco-friendly calcination and hydrothermal methods, by which they would be considerable electrode materials for advanced supercapacitors. To achieve sustainable development, the spent tetracycline-loaded attapulgite can act as a cost-effective available carbon source as well as a matrix material for carbon species and NiCo layered double hydroxide simultaneously. A controlled amount of attapulgite@carbon could be used to regulate the electrochemical properties of nanocomposites. The generated electrodes possess superior electrochemical properties with a specific capacitance of 2013.8 F g-1 at 0.5 A g-1, a retention rate of 87.7% at 5 A g-1, and a cyclic stability of 64.9% for 4000 cycles at 5 A g-1. Thus, the asymmetric supercapacitor device assembled with attapulgite@carbon/NiCo layered double hydroxide nanocomposites||active carbon shows a maximum capacitance of 231.3 F g-1 at 0.5 A g-1, with a preeminent energy density of 82.2 Wh kg-1 when its power density is 4318 W kg-1. This approach would contribute to the development of supercapacitors in an efficient and effective manner, as well as provide a feasible strategy for solving tetracycline pollution and recycling waste adsorbents to achieve sustainable development.
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Herein, we synthesized a CdSe quantum dots (QDs)-decorated ternary metal oxide nanocomposite of ZnO/TiO2/CuO through a simple hydrothermal method. The prepared nanocomposite exhibited monoclinic, hexagonal, and cubic phase structures in XRD (X-ray diffraction) analysis. UV-vis absorbance spectra showed the broad absorption spectrum. SEM (scanning electron microscopy) clearly showed the presence of nanoparticles and confirmed the elements through elemental mapping. TEM (transmission electron microscopy) confirmed the nanostructure of metal oxides decorated with QDs. The average particle size was 45 nm for metal oxides and 7 nm for QDs. XPS (X-ray photoelectron spectroscopy) also confirmed the surface elemental composition. The prepared nanocomposites were introduced as photoanodes in DSSCs (dye-sensitized solar cells) and as photocatalysts for industrial dye solution. Among these samples, CdSe@CuO/TiO2/ZnO showed an improved performance of PCE (photon conversion efficiency) of 3.68% in DSSC and 96% photocatalytic degradation efficiency. It showed a recycling efficiency of â¼92% after 4 cycles against methylene blue (MB) organic dye under visible light irradiation.
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Well-defined thermoswitchable Janus gold nanoparticles with stimuli-responsive hydrophilic polymer brushes were fabricated by combining ligand exchange reactions and the Langmuir technique. Stimuli-responsive polydi(ethylene glycol) methyl ether methacrylate was prepared by addition-fragmentation chain-transfer polymerization. The polymer brushes were then anchored onto the nanoparticle surface by interfacial ligand exchange reactions with hexanethiolate-protected gold nanoparticles, leading to the formation of a hydrophilic (polymer) hemisphere and a hydrophobic (hexanethiolate) one. The resulting Janus nanoparticles showed temperature-switchable wettability, hydrophobicity at high temperatures, and hydrophilicity at low temperatures, due to thermally induced conformational transition of the polymer ligands. The results further highlight the importance of interfacial engineering in the deliberate functionalization of nanoparticle materials.
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Carbon/metal composites derived from metal-organic frameworks (MOFs) have attracted widespread attention due to their excellent electronic conductivity, adjustable porosity, and outstanding stability. However, traditional synthesis methods are limited by the dense stereo geometry and large crystal grain size of MOFs, resulting in many metals active sites are buried in the carbon matrix. While the common strategy involves incorporating additional dispersed media into material, this leads to a decrease in practical metal content. In this study, nanosized copper-metal-organic frameworks (Cu-MOFs) are in-situ grown on surface of carbon spheres by pre-anchoring copper ions, and the hybrid composite of porous carbon/copper oxide with high copper atom utilization rate is prepared through activation and pyrolysis methods. This strategy effectively addresses the issue of insufficient exposure of metal sites, and the obtained composite material exhibits high effective copper atom utilization rate, large specific surface area (2052.3 m2·g-1), diverse pore structure, outstanding specific capacity (1076.5F·g-1 at 0.5 A·g-1), and excellent cycle stability. Furthermore, this highly atom-economical universal method has positive significance in application fields of catalysis, energy storage, and adsorption.
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"Fast-charging" lithium-ion batteries have gained a multitude of attention in recent years since they could be applied to energy storage areas like electric vehicles, grids, and subsea operations. Unfortunately, the excellent energy density could fail to sustain optimally while lithium-ion batteries are exposed to fast-charging conditions. In actuality, the crystal structure of electrode materials represents the critical factor for influencing the electrode performance. Accordingly, employing anode materials with low diffusion barrier could improve the "fast-charging" performance of the lithium-ion battery. In this Review, first, the "fast-charging" principle of lithium-ion battery and ion diffusion path in the crystal are briefly outlined. Next, the application prospects of "fast-charging" anode materials with various crystal structures are evaluated to search "fast-charging" anode materials with stable, safe, and long lifespan, solving the remaining challenges associated with high power and high safety. Finally, summarizing recent research advances for typical "fast-charging" anode materials, including preparation methods for advanced morphologies and the latest techniques for ameliorating performance. Furthermore, an outlook is given on the ongoing breakthroughs for "fast-charging" anode materials of lithium-ion batteries. Intercalated materials (niobium-based, carbon-based, titanium-based, vanadium-based) with favorable cycling stability are predominantly limited by undesired electronic conductivity and theoretical specific capacity. Accordingly, addressing the electrical conductivity of these materials constitutes an effective trend for realizing fast-charging. The conversion-type transition metal oxide and phosphorus-based materials with high theoretical specific capacity typically undergoes significant volume variation during charging and discharging. Consequently, alleviating the volume expansion could significantly fulfill the application of these materials in fast-charging batteries.
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In order to achieve high-performance and stable sodium-ion batteries, numerous attempts have been made to construct continuous ion transport pathways, in which a separator is one of the key components that affects the battery performance. In this study, a novel low-tortuosity woven fabric separator is fabricated by combining a weaving technique with a cellulose-solution method, followed by an infusion of a TEMPO-oxidized bacterial cellulose slurry into woven fabric substrates. The macropores in the fabric combine with the micropores in the oxidized bacterial cellulose to form a separator with a suitable pore structure and low tortuosity, forming a continuous sodium ion transport channel within the sodium-ion battery and effectively enhancing ion transport dynamics. The results show that, compared with a commercial polypropylene separator, the TEMPO-oxidized bacterial cellulose-woven fabric separator has a special weaving structure and lower tortuosity (0.77), as well as significant advantages in tensile strength (3.07 MPa), ionic conductivity (1.15 mS c), ionic transfer number (0.75), thermal stability, and electrochemical stability. This novel and simple preparation method provides new possibilities for achieving high-performance separators of sodium-ion batteries through rational structural design by textile technology.
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Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries; however, its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries. The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials, explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials, and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials. This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials, with particular focuses on their molecular, crystalline, and aggregation structures. Furthermore, the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses. Finally, future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.
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Poly(3, 4-ethylenedioxythiophene) (PEDOT) as a new generation of intelligent conductive polymers, is attracting much attention in the field of tissue engineering. However, its water dispersibility, conductivity, and biocompatibility are incompatible, which limit its further development. In this work, biocompatible electrode material of PEDOT doped with sodium sulfonated alginate (SS) which contains two functional groups of sulfonic acid and carboxylic acid per repeat unit of the macromolecule. The as dual-site doping strategy simultaneously boosts anticoagulant and electrochemical performances, for example, good hydrophilicity (water contact angle of 59.40°), well dispersibility (dispersion solution unstratified in 30 days), high conductivity (4.45 S m-1), and enhanced anticoagulant property (extended activated partial thrombin time value of 59.0 s), forming an adjustable PEDOT: biomacromolecule interface; this fills the technical gap of implantable bioelectronics in terms of coagulation and thrombosis risk. At the same time, the assembled all-in-one supercapacitor with anticoagulant properties is prepared by PEDOT: sodium sulfonated alginate as electrode material and sodium alginate hydrogel as electrolyte layer. The dual-site doping strategy provides a new opinion for the design and optimization of functional conductive polymers and its applications in implantable energy storage fields.
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The power conversion efficiency of metal halide perovskite solar cells (PSCs) has increased dramatically in recent years, but there are still major bottlenecks in the commercial application of such materials, including intrinsic instability caused by external stimuli such as water, oxygen, and radiation, as well as local stress generated inside the perovskite and external stress caused by poor interlayer contact. However, some crucial sources of instability cannot be overcome by conventional encapsulation engineering. Among them, the tensile strain can weaken the chemical bonds in the perovskite lattice, thereby reducing the defects formation energy and activation energy of ion migration and accelerating the degradation rate of the perovskite crystal. This review expounds the latest in-depth understanding of microstrain in perovskite film from the thermodynamic sources and influences on the perovskite physicochemical structure and photoelectric performance. Furthermore, it also summarizes the effective strategies for strain regulation and interlayer contact performance improvement, which are conducive to the improvement of photovoltaic performance and internal stability of PSCs. Finally, we present a prospective outlook on how to achieve more stable and higher efficiency PSCs through strain engineering.
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The electrochemical interfacial interaction of electrode materials with liquid electrolytes in electrochemical energy storage systems including supercapacitors, metal ion batteries, and metal-based batteries have become a research hotspot and play a decisive role in electrochemical energy storage in terms of charging and discharging reaction principles of the electrode materials. However, there is still a long way from maturity due to the challenges related to the unsatisfactory electrolyte-philicity of electrode materials. In the last 20 years, several studies have been directed at discovering strategies to improve the electrolyte-philicity of electrode materials, optimizing the electrochemical interfacial interaction of the electrode materials with liquid electrolytes and exploring the relationship between electrolyte-philicity and electrochemical energy storage performance in the charging and discharging processes of the electrode materials. Unfortunately, the systematic and in-depth understanding of electrolyte-philicity of electrode materials has not been grasped in electrochemical energy storage systems. In this review, we highlight the fundamental scientific understanding of electrolyte-philicity of electrode materials and the relationship among electrolyte-philicity and electrochemical energy storage performance of electrode materials. The definition of electrolyte-philicity of electrode materials is first proposed based on the interaction between the electrode material and electrolyte ions as the essence of electrochemical energy storage of the electrode materials. More important, how the electrolyte-philicity of electrode materials optimizes the electrochemical energy storage performance of the electrode materials has been expounded from the rapid and effective contact of the electrode materials with electrolyte ions under uncharged state to electrochemical interfacial interaction between the electrode materials and electrolytes under the charged state. Then, the fundamental physical and chemical interactions so that the electrode materials may be electrolyte-philic are summarized, and the mechanisms of improving the electrolyte-philicity of electrode materials by surface modification are illustrated based on those interactions. Finally, the future perspectives for important areas of electrolyte-philicity of electrode materials are presented.
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At present, the design and fabrication of polymer membranes with high permeability and good retention ability are still huge challenges. In this study, the commercial Poloxamer 407 (Pluronic F127) is selected as a multifunctional additive, and polyvinylpyrrolidone is used as a pore-forming agent to modify the poly(ether sulfone) membrane by liquid-liquid phase conversion technology to prepare an ultrafiltration membrane with excellent performance. The hydrophobic poly(propylene oxide) segment in Poloxamer 407 guarantees that this copolymer can be firmly anchored to the poly(ether sulfone) matrix, and the hydrophilic poly(ethylene oxide) segments in Poloxamer 407 impart a stronger hydrophilic nature to the modified membrane surface. Therefore, the permeability and hydrophilicity of the modified membrane are significantly improved and the modified membrane also has good stability. When the amount of Poloxamer 407 added to the casting solution reached 0.6 g, the water flux of the modified membrane was as high as 368 L m-2 h-1, and the rejection rate of bovine serum albumin was close to 98%. In the test to isolate organic small molecule dyes, the retention rate of the modified membrane to Congo red is 94.27%. In addition, the modified membrane shows an excellent water flux recovery rate and antifouling ability. It performs well in subsequent cycle tests and long-term membrane life tests and can be used repeatedly. Our work has resulted in poly(ether sulfone) membranes with good performance, which show great potential in the treatment of biomedical wastewater and the removal of industrial organic dye wastewater, it provides ideas for the development and application of amphiphilic polymer materials.
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The electrolyte-wettability of electrode materials in liquid electrolytes plays a crucial role in electrochemical energy storage, conversion systems, and beyond relied on interface electrochemical process. However, most electrode materials do not have satisfactory electrolyte-wettability for possibly electrochemical reaction. In the last 30 years, there are a lot of literature have directed at exploiting methods to improve electrolyte-wettability of electrodes, understanding basic electrolyte-wettability mechanisms of electrode materials, exploring the effect of electrolyte-wettability on its electrochemical energy storage, conversion, and beyond performance. This review systematically and comprehensively evaluates the effect of electrolyte-wettability on electrochemical energy storage performance of the electrode materials used in supercapacitors, metal ion batteries, and metal-based batteries, electrochemical energy conversion performance of the electrode materials used in fuel cells and electrochemical water splitting systems, as well as capacitive deionization performance of the electrode materials used in capacitive deionization systems. Finally, the challenges in approaches for improving electrolyte-wettability of electrode materials, characterization techniques of electrolyte-wettability, as well as electrolyte-wettability of electrode materials applied in special environment and other electrochemical systems with electrodes and liquid electrolytes, which gives future possible directions for constructing interesting electrolyte-wettability to meet the demand of high electrochemical performance, are also discussed.
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An advanced nanostructure with rational micro/mesoporous distribution plays an important role in achieving high electrochemical performance in sodium ion batteries (SIBs), especially the energy storage efficiency in the low-potential region during the charging/discharging processes. Here we propose a method of polymer-blended bacterial cellulose (BC) matrix to tune the micro/mesopores of polymer-BC derived carbon under a mild carbonization temperature. The targeted pore structure and electrochemical performance are optimized by controlling the amount of methyl methacrylate monomers via free-radical polymerization, and carbonized temperature via pyrolysis treatment. The constructed carbon materials display a stable 3D fibrous network with a large specific area and abundant micro/mesopores formed during the pyrolysis of the polymer poly(methyl methacrylate) (PMMA). Taking advantage of the constructed pore structure, the optimized carbon anodes derived from BC/PMMA composites show an enhanced Na+ diffusion rate with a high capacity of 380.66 mA h g-1 at 0.03 A g-1. It is interesting that it possesses superior low-potential capacity, and retains 42% of the total capacity even at a high scan rate of 1 mV s-1. The proposed method of polymer-blended on cellulose matrix provides an energy-efficient way to achieve high low-potential capacity under facile processing conditions for fast sodium ion transport in SIBs.