High-performance Sodium-ion Batteries Research Articles

Heterostructure of Ta5+-substituted Na3V2(PO4)3–TaN promoting the activation of V4+/V5+ redox couple for high performance sodium-ion batteries

Currently, low capacity with poor kinetics seriously hinders the development of Na3V2(PO4)3 (NVP). Herein, a simultaneous optimized scheme of Ta5+ substitution and carbon nanotubes (CNTs) enwrapping is proposed. The substitution of hypervalent Ta5+ at V3+ site introduces a favorable n-type doping effect to generate extra electrons, increasing electron concentration to accelerate electronic conductivity. Ta5+ behaves as a pillar ion to expand Na + migration channel and stabilize the skeleton. Moreover, a new phase of TaN is produced, which embeds into the Na3V2(PO4)3 phase to generate grain boundary. Benefiting from this heterojunction, Na+ diffusion rate could be effectively promoted. The addition of CNTs further restricts agglomeration growth of particles, making the grains smaller and more uniform. Benefiting from the synergetic improved kinetics, a higher voltage platform at 3.9 V is activated. Due to the investigations of ex-situ X-ray photoelectron spectroscopy, the extra plateau is derived from the V4+/V5+ redox couple. Moreover, Density Functional Theoretical calculation suggests the favorable Ta5+ substitution optimizes the electronic structure of NVP to reduce the band gap. Accordingly, the modified NVPT/C@CNTs0.15 submits 125.5 mA h g−1 at 0.1C, and delivers a high value of 77.5 mA h g−1 at 100 C with retention rate of 81.03% after 12000 cycles.

Ultrafine Mn-rich P2-type Na0.67Fe0.1Mn0.9O2 particles via combustion synthesis as high-performance sodium-ion battery cathode

Layered transition metal oxide is considered as one of the most promising cathode materials for sodium-ion batteries due to the abundant reserves of Na, Fe, and Mn. Moreover, the trivalent Fe substitution weakens the Jahn–Teller effect and enhance the crystal structure during the de/intercalation of Na+. Herein, a series of Mn-rich P2-type Na0.67Fe0.1Mn0.9O2 (NFMO-600, NFMO-700 and NFMO-800) are prepared using combustion synthesis followed by calcinating at 600, 700 and 800 °C, respectively. As confirmed by XRD and SEM, NFMO-700 owns ultrafine high-purity crystal particles with a larger layer spacing and a smaller crystal size. Owing to these unique structures, NFMO-700 exhibits excellent electrochemical performance, delivering an impressive 179 mA h g−1 at 0.2C, with a capacity retention of 84.43 % after 100 cycles at 0.5C.

Preparation of Enriched Closed-Pores Hard Carbon for High-Performance Sodium-Ion Batteries by the Poly(vinyl butyral) Template Method

Preparation of Enriched Closed-Pores Hard Carbon for High-Performance Sodium-Ion Batteries by the Poly(vinyl butyral) Template Method

Hollow Layered Iron-Based Prussian Blue Cathode with Reduced Defects for High-Performance Sodium-Ion Batteries.

Fe-based Prussian blue (Fe-PB) analogues have emerged as promising cathode materials for sodium-ion batteries, owing to their cost-effectiveness, high theoretical capacity, and environmental friendliness. However, their practical application is hindered by [Fe(CN)6] defects, negatively impacting capacity and cycle stability. This work reports a hollow layered Fe-PB composite material using 1,3,5-benzenetricarboxylic acid (BTA) as a chelating and etching agent by the hydrothermal method. Compared to benzoic acid, our approach significantly reduces defects and enhances the yield of Fe-PB. Notably, the hollow layered structure shortens the diffusion path of sodium ions, enhances the activity of low-spin Fe in the Fe-PB lattice, and mitigates volume changes during Na-ion insertion/extraction into/from Fe-PB. As a sodium-ion battery cathode, this hollow layered Fe-PB exhibits an impressive initial capacity of 95.9 mAh g-1 at a high current density of 1 A g-1. Even after 500 cycles, it still maintains a considerable discharge capacity of 73.1 mAh g-1, showing a significantly lower capacity decay rate (0.048%) compared to the control sample (0.089%). Moreover, the full cell with BTA-PB-1.6 as the cathode and HC as the anode provides a considerable energy density of 312.2 Wh kg-1 at a power density of 291.0 W kg-1. This research not only enhances the Na storage performance of Fe-PB but also increases the yield of products obtained by hydrothermal methods, providing some technical reference for the production of PB materials using the low-yield hydrothermal method.

G-C3N4 confined Sb2Se3 as high-performance anode towards rapid and stable Na-ion storage

Sb2Se3 is considered a promising anode material for sodium-ion batteries (SIBs) due to its abundant reserves, low cost, and high theoretical capacity. Nevertheless, significant volume changes and slow electron transfer kinetics significantly limit its rate capability and cycle stability. In this work, we constructed g-C3N4-coated Sb2Se3 nanorods (Sb2Se3@g-C3N4) through the hydrothermal method and subsequent thermal treatment to enhance kinetics and achieve high cycle stability. The coating enhances the structure stability, insertion/extraction reversibility of Na+, and electrochemical reaction activity. Benefiting from the unique structure and composition, Sb2Se3@g-C3N4 (8 wt%) nanorod exhibits excellent rate properties with high desodiation capacities of 376.7, 345.5, 336.1, 322.7, 301.4, and 275.0 mAh g−1 at 0.1, 0.5, 1, 2, 5, and 10 A g−1, respectively. Even at 5 A g−1, Sb2Se3@g-C3N4 (8 wt%) exhibits high cycle stability with a capacity retention of approximately 86.7% after 600 cycles. Ex-situ XRD and XPS results confirm that the introduction of g-C3N4 on the surface of Sb2Se3 inhibits the volumetric expansion and electrode pulverization of Sb2Se3, thereby improving the structural stability of the composite material, resulting in an excellent electrochemical capability of Sb2Se3@g-C3N4 nanorods. Sb2Se3@g-C3N4 nanorods show massive potential as an anode material for the next-generation high-performance SIBs.

A surface-induced assembly strategy to fabricate flexible carbon nanofiber/coal-based carbon dots films as free-standing anodes for high-performance sodium-ion batteries

Flexible electrodes with superior stability, high performance, and low cost have drawn numerous considerations in energy storage devices. Here, we developed a facile and robust strategy to prepare coal-based carbon dots (i.e., CDs) with high yields derived from lignite by microwave-assisted mild oxidation and further fabricate a carbon nanofiber film decorated with CDs (i.e., CNF@CDs) by electrospinning water-soluble CDs with polyacrylonitrile (i.e., PAN) through thermal treatment and carbonization and applied as flexible electrodes for sodium-ion batteries. The as-prepared CNF@CDs as binder-free anode presents a reversible capacity of 223 mAh g−1 at 20 mA g−1 and obtains a high capacity retention of 96% over 400 cycles. The outstanding electrochemical properties were attributed to the unique structure of CNF@CDs with the optimal ratio of carbon nanofiber and coal-based carbon dots, in which carbon fiber with the 3D framework facilitates the speed of ion diffusion and electron transport as well as the surface-induced assembly of CDs on the surface of the PAN fibers brings in strong structure stability and electrode integrity. The current study supplies a novel and effective approach to constructing flexible electrodes with superior stability and high performances from low-cost materials, which has potential application prospects in flexible energy storage devices.

One-step in-situ synthesis of bimetallic-doped disordered carbons as anode for high-performance sodium-ion batteries

Since sodium-ion batteries are considered to be the promising energy storage devices, carbon materials as the anodes have been intensively studied. They have good cycling stability, but their capacities are generally not high enough to meet the increasing demands. In order to solve this problem, a carbon-bimetallic composite is synthesized in one step using a simple pyrolysis method with low-cost biomass and cobalt ferrate as the precursors. This simple synthesis method allows the in-situ production of bi-alloys embedded into disordered carbon matrix derived from the tapioca starch to form high-performance anode material for sodium-ion batteries. The initial discharge capacity is 712 mA h g−1 at 0.05 A g−1and the initial Coulombic efficiency is 89.2%. Moreover, the introduction of bi-alloys not only facilitates the reaction kinetics, but also effectively mitigates the volume expansion and consequently promotes the cyclability. As a result, the half-cell sodium-ion battery delivers a capacity of more than 419 mA h g−1 at a high current of 10 A g−1, and after 200 cycles at a current density of 1 A g−1, its capacity degradation is only 0.2% per cycle with a Coulombic efficiency of about 100%. This high-performance materials with a low-cost preparation method could be great potential for commercialized applications.

Compatibility and effect of capacity ratios between Na3V2(PO4)3 and hard carbon in highly concentrated sodium bis (fluorosulfonyl) imide electrolyte

From the standpoint of preserving the Earth's resources and ensuring the long-term viability of humanity, it is imperative to transition away from lithium-ion batteries. High-performance and safe sodium-ion batteries have recently emerged as promising advanced batteries for application in stationary energy storage, attributed to their low cost and abundance of sodium ion. We demonstrate the compatibility and effect of the negative-positive capacity ratio in full-cell Na3V2(PO4)3 and hard carbon in high-concentration electrolytes. Thanks to the excellent oxidation stability of the electrolyte, during 100 cycles, the full cell with a negative-positive capacity ratio of 1.1 demonstrated a consistent capacity of around 100 mAh g-1 with a capacity retention of 90.7%, whereas the full cell with a ratio of 1.0 showed a steady discharge capacity of roughly 90 mAh g-1 with a capacity retention of approaching 100% at a current density of C/5.

Boosting sodium-ion battery performance using Na3(VO)2(PO4)2F microrods self-embedded in a 3D conductive interpenetrated framework

Na3(VO)2(PO4)2F (NVPOF) is considered as a promising cathode candidate for sodium-ion batteries (SIBs) owing to the high theoretical capacity and operating voltage. However, the challenges of its rate capability and cyclability limit its widespread application. Herein, the reduced graphene oxide decorated NVPOF microrods (NVPOF@G) are successfully synthesized by a facile hydrothermal-induced self-assembly procedure. It is found that the graphene oxides added act as a crystal nucleation growth regulator and provide rapid Na+ and electron transport in the electrodes. The prepared NVPOF@G microrods exhibit a superior rate capability of 82.2 mAh g−1 at 50 C (fast discharge in 72 s) as well as considerable long-term cycle stability with a capacity retention of 87.6% over 1000 cycles at 0.5 C. Even at 50 °C, the NVPOF@G still achieves a high reversible capacity of 109.4 mAh g−1 with a capacity retention of 87.7% after 1000 cycles. This microrod structure shows superior structural stability, even at high temperatures (50 °C). Such a cathode incorporates the benefits of batteries and supercapacitors. This work gives a way to fabricate microrod-structure phosphate-based materials for commercial applications in high-performance SIBs.

Coaxial Electrospinning of CoS1.097@C Core–Shell Fibers Anode Material for High-Performance Sodium-Ion Batteries

As an important component that affects the storage performance of sodium-ion batteries (SIBs), novel anode materials still need to be well explored. Herein, CoS1.097@C core–shell fibers as anode material were designed via coaxial electrospinning, stabilization, and carbonization. Specially, CoS1.097 powders are distributed in the inner shell of carbon fibers, and sufficient pore spaces are present among themselves. The unique encapsulation structure, porous characteristics, and one-dimensional conductive carbon shell can enable the CoS1.097@C core–shell fibers’ high initial specific capacity, excellent rate capability, and long cycle life. The initial charge and discharge capacities of the electrode at 50 mA g−1 are 386.0 and 830.9 mAh g−1, respectively. After 2000 cycles at 500 mA g−1, the discharge capacity is 216.3 mAh g−1. Even at 3000 mA g−1, the rate capacity can be maintained at 83.3 mAh g−1.

Theoretical prediction of two-dimensional CrSi2N4 as a potential anode material for Na-ion batteries

Efficient anode materials are critical for high-performance rechargeable lithium-ion batteries (LIBs) and sodium-ion batteries. This paper systematically investigates the potential of the CrSi2N4 monolayer as anode material for LIBs and sodium-ion batteries by first-principles density functional theory calculations. It was found that CrSi2N4 exhibits outstanding performance in sodium-ion batteries, with a low diffusion energy barrier of 0.10 eV and a high theoretical specific capacity of 490 mAh g−1. Meanwhile, the average open circuit voltage is 0.47 V, comparable to the typical anode materials. In addition, a small lattice constant change of 0.3%–3.1% ensures the cycling stability of CrSi2N4 in sodium-ion batteries. This work suggests a promising candidate anode material for sodium-ion batteries.

Imidazole-Linked Fully Conjugated Covalent Organic Framework for High-Performance Sodium-Ion Battery

Imidazole-Linked Fully Conjugated Covalent Organic Framework for High-Performance Sodium-Ion Battery

Solid-phase construction of high-performance sodium-ion battery cathode materials with three-dimensional porous structure: Na4MnCr(PO4)3/C

Na4MnCr(PO4)3 is a promising cathode material with high redox potential and high energy density, but the intrinsic poor electronic conductivity and substandard structural stability restrict its practical application. Herein, porous Na4MnCr(PO4)3/C with conductive networks and improved electrochemical properties is synthesized by a facile modified solid-state process using citric acid as a multifunctional additive. The results reveal that citric acid can be used as a grinding aid to make the raw materials mix more evenly and speed up the efficiency of ball milling. Besides, 3D conductive network and porous structure originated from polycondensation and carbonization of citric acid can promote the electrochemical properties of Na4MnCr(PO4)3/C by enhancing the electronic/ionic conductivity and (de)intercalation reaction kinetics. As expected, the optimal Na4MnCr(PO4)3/C delivers a high reversible capacity of 130.5 mAh g−1 at 0.1C rate, and exhibits a capacity retention of 82.62% at 10C rate after 500 cycles. In addition, the reversible biphasic reaction of the cathode is confirmed by the constant galvanostatic intermittent titration technique and ex-situ XRD, which shows great potential of the synthesized Na4MnCr(PO4)3/C for practical applications.

Dual-complexing agent dominated synthesis of carbon coated Na3V2(PO4)3 cathodes for high-performance sodium ion batteries

The currently prevailing single complexing agent-dominated sol-gel technologies for Na3V2(PO4)3 (NVP) cathodes in sodium-ion batteries (SIBs) always result in limited modification effects, especially in regards to the particle size of NVP and the quality of carbon coatings. Herein, we report a citric acid and glycine co-complexed strategy for fabricating carbon-coated NVP. It creates a favorable synergy for optimizing the microstructure and electrochemical performance of the NVP cathode. The introduction of glycine in citric acid not only decreases the solution viscosity for facilitated metal-ion diffusion, but also induces the self-construction of a 3D network through heteromolecular hydrogen bonds. The optimized carbon-coated NVP by co-complexing of citric acid and glycine (named as NVP/CG-5.0) presents distinctly decreased particle size, improved dispersity and moderate carbon coating thickness of ∼2 nm. It also features a large specific surface area of 44.4 m2 g−1 with rich mesopores. Impressively, the NVP/CG-5.0 electrode exhibits substantially improved electrochemical performance, such as the elevated specific capacity of 108.3 mAh g−1 with high initial Coulombic efficiency (95.2%), high capacity retention of 81.3% after 2000 cycles at 2 C and excellent rate performance (88.2 mAh g−1 at 20.0 C). Furthermore, the assembled NVP/CG-5.0║hard carbon full battery also exhibits superior electrochemical performance, suggesting the great potential of the co-complexed strategy for developing high-performance NVP cathodes in SIBs.

Self-assembly of N,S-MXene/3DPC heterostructure with multiple charge transfer channels for high-performance supercapacitors and sodium-ion batteries

Individual MXene (Ti3C3Tx) films tend to re-accumulate, seriously reducing the electrochemical properties. Herein, a viable hydrothermal method is being adopted to achieve the self-assembly of N and S co-doped three-dimensional porous carbon (3DPC) with conductive networks and MXene. For SCs, the N,S-MXene/3DPC electrode displays 412.7 F g−1 at 1 A g−1. When all-solid-state asymmetric SCs (ASCs) are manufactured with active carbon, the N,S-MXene/3DPC//AC ASCs present 210.5 F g−1 at 1 A g−1 and retain 97.5% of initial cycle through 5000 rotations. The energy density reaches its maximum of 94.7 Wh kg−1 at 900 W kg−1. In addition, the N,S-MXene/3DPC anode of SIBs demonstrates a reversible capability of 465.5 mAh g−1 at 0.2 A g−1. It also sustains a remarkable 72.9% preservation of capacity over 1000 rotations at 2.0 A g−1. The excellent electrochemical performance is attributed to following points: 3DPC with conductive networks can provide multiple transfer paths for ions and charges and support MXene. The co-doping of N and S for 3DPC can provide numerous active sites for electrochemical reactions, while the addition of MXene improves conductivity and mechanical stability. The N,S-MXene/3DPC material and its preparation method exhibit great potential for application in the field of electrochemical energy storage.

Progress and Prospect of Bimetallic Oxides for Sodium-Ion Batteries: Synthesis, Mechanism, and Optimization Strategy.

Sodium-ion batteries (SIBs) are considered as an alternative to and even replacement of lithium-ion batteries in the near future in order to address the energy crisis and scarcity of lithium resources due to the wide distribution and abundance of sodium resources on the earth. The exploration and development of high-performance anode materials are critical to the practical applications of advanced SIBs. Among various anode materials, bimetallic oxides (BMOs) have attracted special research attention because of their abundance, easy access, rich redox reactions, enhanced capacity and satisfactory cycling stability. Although many BMO anode materials have been reported as anode materials in SIBs, very limited studies summarized the progress and prospect of BMOs in practical applications of SIBs. In this review, recent progress and challenges of BMO anode materials for SIBs have been comprehensively summarized and discussed. First, the preparation methods and sodium storage mechanisms of BMOs are discussed. Then, the challenges, optimization strategies, and sodium storage performance of BMO anode materials have been reviewed and summarized. Finally, the prospects and future research directions of BMOs in SIBs have been proposed. This review aims to provide insight into the efficient design and optimization of BMO anode materials for high-performance SIBs.

Strongly coupled C@MoSe2@OMWCNT heterostructure as an anode for sodium-ion batteries

MoSe2, with its extraordinary theoretical capacity, has emerged as a profoundly auspicious anode material for Sodium-ion Batteries (SIBs). However, the actual realization of SIBs encounters hurdles arising from insufficient electron and ion transportation capabilities, along with the irreversible transformation of Mo/Na2Se into MoSe2, eventually substituted by Mo/Se. In this investigation, By employing Mo-based complexes, we have achieved a triumphant synthesis of C@MoSe2@OMWCNT (oxidized multiwall carbon nanotubes) materials, wherein OMWCNTs serve as the fundamental substrate. Theoretical analysis has revealed that the utilization of OMWCNTs not only enhances the structural stability of the anode materials but also improves the electrical conductivity and Na+ ion mobility (the Na+ diffusion barrier: (MoSe2) 0.91 eV vs (C@MoSe2@OMWCNT) 0.41 eV) of the C@MoSe2@OMWCNT. These properties make C@MoSe2@OMWCNT a promising candidate for the development of high-performance SIBs. Furthermore, the Ex-situ Transmission Electron Microscopy (TEM) examination, unveils the emergence of Se and MoSe2 within the C@MoSe2@OMWCNT. The findings indicate that the outer carbon coating layer efficiently prevents contact between Se and the electrolyte, thereby impeding the formation of polyselenides. When C@MoSe2@OMWCNT is employed as the anode for the SIB, it exhibits exceptional cycle stability, with a capacity of 303 mA h g−1 and 189 mA h g−1 after 500 and 3000 cycles, respectively, under a current density of 5 A g−1. Overall, this investigation provides valuable insights into the design and synthesis of advanced anode materials for SIBs, which could have significant implications for the development of next-generation energy storage devices.

Localizing bismuth single atoms around tin nanoparticles for efficient CO2 reduction and fabrication of high-performance sodium-ion batteries

The utilization of Bi/Sn alloy-based materials has garnered significant interest as a promising avenue for the development of sodium-ion batteries and the achievement of electrocatalytic CO2 reduction. This is due to their notable attributes of high theoretical specific capacity and low working potential, as well as their abundance and high catalytic activity. Nevertheless, the practical application potential of these alloys is restrained by their inadequate electrical conductivity without incorporating conductive carbon networks to improve the electrical conductivity of the composite material and consequential volumetric fluctuations, which ultimately lead to unsatisfactory cycle life and the depletion of active components. A single-atom Bi-coated Sn nanoparticle was synthesized utilizing metal-organic framework (MOF) compounds as precursors. The resulting composite exhibits the ability to mitigate volume changes that arise during charge and discharge processes, while also enhancing the catalytic activity of the system for CO2 reduction through synergistic effects. Upon pyrolysis of the MOFs at elevated temperatures, a carbon matrix "protective layer" is formed to prevent the loss of active substances under conditions of electrode pulverization. This leads to improved cycle stability and coulomb efficiency of the battery. The ion permeation and gas diffusion are facilitated by the three-dimensional porous structures of composites. The conductive networks further improve the conductivity of materials, prevent the shedding of electrode material from electrodes, and facilitate electron transport. Consequently, the electrode demonstrates exceptional electrochemical performance, as evidenced by a high capacity of 510 mAh g−1 after 1000 cycles and a reversible capacity of 497 mAh g−1 after 500 cycles. Furthermore, the composite material demonstrates a notable degree of selectivity towards CO2 reduction, as evidenced by a coulombic efficiency of 95.7% for HCOOH at a potential of −1.1 V but only a coulombic efficiency of 2.3% for H2. Furthermore, the composite material exhibits commendable stability. The findings presented in this study offer valuable technical insights towards the attainment of carbon neutrality and carbon peaking.

Ball‐Milling Synthesis of Richly Oxygenated Graphene‐Like Nanoplatelets from used Lithium Ion Batteries and Its Application for High Performance Sodium Ion Battery Anode

AbstractThe exploration of waste graphite from used lithium ion batteries (LIBs) and its derivatives for versatile applications is an efficient route to promote the environmental and eco‐friendly recycling of used LIBs. Sodium ion batteries (SIBs) are alternative candidates to LIBs mainly due to similar electrochemical mechanism of SIBs to LIBs and rich natural resource of Na. Herein, a holey waste graphite (hGw) with well‐defined porous structure is produced by the annealing of lithiated waste graphite (Li/Gw) from used LIBs under a flow gas of H2O and subsequent lithium leaching in DI water. Benefiting from the holey structure of hGw, holey graphene nanoplatelets (hGnw) with ultrahigh‐level edge‐grafted oxygen groups (≈37.8 at%) are synthesized by mechanical balling of hGw. As anode for SIBs, the hGnw present outstanding sodium ion storage properties with high initial Coulombic efficiency of 82.4%, high reversible capacity (e.g., 416.1 mAh g−1 at 0.03 A g−1), excellent rate capability (e.g., 153.3 mAh g−1 at 2 A g−1), and long‐term cycling stability (e.g., 152.7 mAh g−1 after 400 cycles at 1.5 A g−1).

Interface engineering of metal sulfides-based composites enables high-performance anode materials for sodium-ion batteries

Metal sulfides (MSs) have attracted much attention as anode materials for sodium-ion batteries (SIBs) due to their high sodium storage capacity. However, the unsatisfactory electrochemical performance induced by the huge volume change and sluggish kinetics hampered the practical application of SIBs. Herein, guided by the heterostructure interface engineering, novel multicomponent metal sulfide-based anodes, including SnS, FeS, and Fe3N embedded in N-doped carbon nanosheets (SnS/FeS/Fe3N/NC NSs), have been synthesized for high-performance SIBs. The as-prepared SnS/FeS/Fe3N/NC NSs with abundant heterointerfaces and high conductivity of N-doped carbon nanosheet matrix can shorten the Na+ diffusion path and promote reaction kinetics during the sodiation/desodiation process. Moreover, the presence of Fe3N can promote the reversible conversion of SnS and FeS during the cycling process. As a consequence, when evaluated as anode materials for SIBs, the SnS/FeS/Fe3N/NC NSs can maintain a high sodium storage capacity of 473.6 mAh g-1 after 600 cycles at 2.0 A g-1 and can still provide a high reversible capacity of 537.4 mAh g-1 even at 5.0 A g-1 This discovery offers a novel strategy for constructing metal sulfide-based anode materials for high-performance SIBs.