Anode For Sodium-ion Batteries Research Articles

Heterostructured Mn-Sn Bimetallic Sulfide Nanocubes Confined in N, S-co-Doped Carbon Framework as High-Performance Anodes for Sodium-Ion Batteries.

Benefiting from its high theoretical capacity, tin disulfide (SnS2) draws abundant interest and attention for its promising practical prospect for sodium-ion batteries (SIBs). However, the huge volumetric variation in sodiation/desodiation reactions usually results in the fast decay of rate and cycling properties, which seriously obstructs its future applicable foregrounds. Herein, heterostructured Mn-Sn bimetallic sulfide nanocubes confined in N and S-codoped carbon (MSS@NSC) were rationally designed via a facile coprecipitation followed by a sulfurization strategy. When used as anodes for SIBs, the heterojunctions at the interfaces effectively accelerate the Na+ diffusion rate to promote the sodium-storage reaction kinetics. The N and S-codoped carbon provides a rapid conductive framework for the fast charge transport during the sodium-storage process. Moreover, the beneficial confinement effect of the NSC layer effectively guarantees a superb cycle property for the MSS@NSC anode. The favorable synergistic effects between the highly conductive framework of the NSC and MSS heterostructure endow the MSS@NSC anode with satisfactory electrochemical Na-storage properties.

Ab Initio Prediction of Two-Dimensional GeSiBi2 Monolayer as Potential Anode Materials for Sodium-Ion Batteries.

The conceptualization and deployment of electrode materials for rechargeable sodium-ion batteries are key concerns for next-generation energy storage systems. In this contribution, the configuration stability of single-layer GeSiBi2 is systematically discussed based on first-principles calculations, and its potential as an anode material is further investigated. It is demonstrated that the phonon spectrum confirms the dynamic stability and the adsorption energy identifies a strong interaction between Na atoms and the substrate material. The electronic bands indicative of inherent metallicity contribute to the enhancement of electronic conductivity after Na adsorption. The multilayer adsorption of Na provides a theoretical capacity of 361.7 mAh/g, which is comparable to that of other representative two-dimensional anode materials. Moreover, the low diffusion barriers of 0.19 and 0.15 eV further guarantee the fast diffusion kinetics. These contributions signal that GeSiBi2 can be a compatible candidate for sodium-ion batteries anodes.

Liquid Gallium-Assisted Pyrolysis of MOF Affording CNT Non-Hollow Frameworks in High Yields for High-Performance Sodium-Ion Battery Anode.

Carbon materials have great potential for applications in energy, biology, and environment due to their excellent chemical and physical properties. Their preparation by carbonization methods encounters limitations and the carbon loss during pyrolysis in the form of gaseous molecules results in low yield of carbon materials. Herein a low-energy (600°C) and high-yield (82wt.%) carbonization strategy is developed using liquid gallium-assisted pyrolysis of metal-organic frameworks (MOFs) affording the N-doped carbon nanotube (CNT) non-hollow frameworks encapsulating Co nanoparticles. The liquid gallium layer offers protection against air, promotes heat transfer, and limits the escape of small carbonaceous gaseous molecules, which greatly improve the yields of the pyrolysis reaction. Experimental and theoretical results reveal that the synergistic interaction between CNTs and N/O-containing groups gives a non-hollow framework composed of N/O-enriched and open CNTs (NOCNTF-15, 15 denotes the 15mm thickness of the liquid gallium layer during the pyrolysis) with high specific capacity (185mAhg-1 at 10Ag-1) and ultra-stable cyclability (stable operation at 10Ag-1 and 50°C for 20000 cycles). This study provides a unique approach to carbonization that facilitates the practical application of low-cost CNTs and other MOFs-derived carbon materials in high-performance sodium-ion batteries (SIBs).

Azatriangulenetrione as the Anode Material for Sodium-Ion Batteries: Reversible Redox Chemistry Mediated by Lone Pair Electrons.

Redox-active organic molecules have potential as electrode materials, but their cycling stability is often limited by the irreversible formation of σ-bonds from the radical intermediates. Herein, we present an effective approach to achieve high reversibility by using lone pair electrons to mediate intramolecular radical-radical coupling. Azatriangulenetrione (1) was examined as the anode in sodium-ion batteries, which displayed a reversible four-step, one-electron redox chemistry. In situ electron spin resonance, ex situ Fourier transform infrared/X-ray photoelectron spectroscopy, and density functional theory calculation revealed that the unstable radical anions can couple with each other through the lone pair electrons of the central nitrogen atom, leading to stabilized radical species. Furthermore, scan-rate-dependent cyclic voltammetry measurements and galvanostatic intermittent titration techniques demonstrated that the redox reaction kinetics for radical formation were much faster than the radical paring process. This study offers deep insights into the design of highly reversible organic electrodes.

Binderless Electrodeposited NiCo2S4-MWCNT as a Potential Anode Material for Sodium-Ion Batteries

Abstract Conversion type ternary NiCo2S4, exhibiting high electrical conductivity (~1.25 × 106 S m-1) and high theoretical capacity (703 mAh g-1), has gained interest as an anode material for sodium-ion batteries (SIBs). Despite its potential, NiCo2S4 (NCS) has extensive volume expansion during cycling. This study introduces the NCS-multi-walled carbon nanotube (MWCNT) onto a carbon fiber (CF) electrode (NCS and NCS-MWCNT@CF), developed through electrodeposition, which addresses these limitations. The unique sheet-like morphology of NCS, featuring abundant pores, ensures good access to the electrolyte. Incorporating a three-dimensional conductive CF framework that acts as a free-standing current collector helps prevent the agglomeration of NCS particles and mitigates volume expansion by providing enough buffer space in the layers of the CF matrix. Our findings reveal that NCS on CF electrodes deliver a second cycle capacity of 620 mA g-1 at 30 mA g-1 and retain 72 % capacity after 200 cycles. At 200 mA g-1, the NCS@CF electrodes deliver 378 mAh g-1 in the second cycle with 68% capacity retention in the 200th cycle, whereas NCS-MWCNT@CF delivers 538 mAh g-1 at 200 mA g-1, maintaining 86 % capacity after 100 cycles, making it a potential anode for SIBs.

Unlocking the potential of a chemically modified blue phosphorene as anode materials for high-performance sodium-ion batteries

Blue phosphorene (Blu-Pn) has recently been identified as a new two-dimensional (2D) form of black phosphorus via the epitaxial growth method and has shown the ability to host a substantial amount of Na while serving as an anode in sodium-ion batteries (NIBs). However, its structural instability is an issue that hinders its further exploitability in NIBs. In this paper, we propose to chemically modify the Blu-Pn network by substituting six phosphorus atoms with a carbon source in the form of a C6 ring, constructing a new and robust CP2 nanosheet. Based on the state-of-the-art non-local van der Waals corrected density functional theory and ab initio molecular dynamic (AIMD) simulations, we systematically explore the feasibility of the designed CP2 as a potential anode material for NIBs. Adding a C6 ring in the Blu-Pn lattice reduces its energy gap from 2 eV to 1.3 eV, which disappears after Na adsorption, indicating a conductive character. Attributed to the synergistic effect, the adsorption energy of Na on CP2 nanosheet (−2.22 eV) is greatly decreased in comparison to the pristine carbon source (e.g., graphene with −0.78 eV) and pristine Blu-Pn (−1.85 eV). The Na diffusivity on CP2 at 300 K is predicted to be 4.90 × 10−11 m2/s by AIMD. The specific capacity is up to 604.1 mAh/g, which exceeds that of the commercialized graphite anode (372 mA h/g). Ultimately, the designed electrode provides a small open circuit potential of 0.66 V that falls within a desirable voltage range. This work paves the way for exploring Blu-Pn 2D anode materials for NIBs technology and provides valuable insights into surface chemical modification towards the long-term stability of Blu-Pn.

Cobalt selenide confined in nitrogen-doped carbon skeleton as high-rated capability anode for sodium-ion batteries

Cobalt selenide confined in nitrogen-doped carbon skeleton as high-rated capability anode for sodium-ion batteries

"Lasagna"-Structured SnS-TaS2 Misfit Layered Sulfide for Capacitive and Robust Sodium-Ion Storage.

Stannous sulfide (SnS), a conversion-alloying type anode for sodium-ion batteries, is strong Na+ storage activity, a low voltage platform, and high theoretical capacity. However, grain pulverization induced by intolerable volume change and phase aggregation causes quick capacity degradation and unsatisfactory rate capability. Herein, a novel "lasagna" strategy is developed by embedding a SnS layer into the interlayer of an electrochemically robust and electron-active TaS2 to form a misfit layered (SnS)1.15TaS2 superlattice. For Na+ storage, the rationally designed (SnS)1.15TaS2 anode exhibits high specific capacity, excellent rate capability, and robust cycling stability (729 mAh cm-3 at 15 C after 2000 cycles). Moreover, the as-assembled (SnS)1.15TaS2 || Na3V2(PO4)3 full cells achieve robust and fast Na+ storage performance with ≈100% capacity retention after 650 cycles at 15 C, which also demonstrates good low-temperature performance at -20°C with a capacity retention of 75% and 2 C high-rate charge/discharge ability.

"Lasagna"-Structured SnS-TaS2 Misfit Layered Sulfide for Capacitive and Robust Sodium-Ion Storage.

Stannous sulfide (SnS), a conversion-alloying type anode for sodium-ion batteries, is strong Na+ storage activity, a low voltage platform, and high theoretical capacity. However, grain pulverization induced by intolerable volume change and phase aggregation causes quick capacity degradation and unsatisfactory rate capability. Herein, a novel "lasagna" strategy is developed by embedding a SnS layer into the interlayer of an electrochemically robust and electron-active TaS2 to form a misfit layered (SnS)1.15TaS2 superlattice. For Na+ storage, the rationally designed (SnS)1.15TaS2 anode exhibits high specific capacity, excellent rate capability, and robust cycling stability (729 mAh cm-3 at 15 C after 2000 cycles). Moreover, the as-assembled (SnS)1.15TaS2 || Na3V2(PO4)3 full cells achieve robust and fast Na+ storage performance with ≈100% capacity retention after 650 cycles at 15 C, which also demonstrates good low-temperature performance at -20°C with a capacity retention of 75% and 2 C high-rate charge/discharge ability.

Understanding and Mitigating Lattice Collapse Degradation in Layered Oxide Materials for Sodium-Ion Battery Anode.

Na2Ti3O7 has attracted significant attention due to its ecofriendliness and cost-effectiveness for sodium-ion batteries. However, their limited cycling stability hampers their practical applications. Herein, we elucidate a mechanism of structural degradation caused by the heterogeneous phase transition in the Na2Ti3O7 anode using aberration-corrected (scanning) transmission electron microscopy (S)TEM and in situ TEM. It is found that the unevenly distributed phase transition results in the accumulation of strain, which promotes the growth of microcracks and eventually leads to structural decomposition and electrochemical failure. Motivated by this degradation mechanism, nanowires were proposed, and the structural stability is thus improved with the lattice strain effectively released. These findings deepen our understanding of ion transport and degradation mechanisms in intercalated layered electrode materials while emphasizing the significance of the material structure engineered for improving electrode performance.

Vacancies-Induced Delocalized States Cobalt Phosphide for Binder-Free Anode Toward Stable and High-Rate Sodium-Ion Batteries.

Metal phosphides with easy synthesis, controllable morphology, and high capacity are considered as potential anodes for sodium-ion batteries (SIBs). However, the inherent shortcomings of metal phosphating materials, such as conductivity, kinetics, volume strain, etc are not satisfactory, which hinders their large-scale application. Here, a CoP@carbon nanofibers-composite containing rich Co─N─C heterointerface and phosphorus vacancies grown on carbon cloth (CoP1-x@MEC) is synthesized as SIB anode to accomplish extraordinary capacity and ultra-long cycle life. The hybrid composite nanoreactor effectively impregnates defective CoP as active reaction center while offering Co─N─C layer to buffer the volume expansion during charge-discharge process. These vast active interfaces, favored electrolyte infiltration, and a well-structured ion-electron transport network synergistically improve Na+ storage and electrode kinetics. By virtue of these superiorities, CoP1-x@MEC binder-free anode delivers superb SIBs performance including a high areal capacity (2.47 mAh cm-2@0.2mA cm-2), high rate capability (0.443 mAh cm-2@6mA cm-2), and long cycling stability (300 cycles without decay), thus holding great promise for inexpensive binder-free anode-based SIBs for practical applications.

ZIF-derived "cocoon"-like in-situ Zn/N-doped carbon as high-capacity anodes for Li/Na-ion batteries

Owing to the unique structure and physicochemical properties, including high specific surface area, self-doped N atoms, open pore structure and good chemical stability, zeolitic imidazolate frameworks (ZIFs) and their derivatives have been widely used in the field of energy storage. Here, a new type of "cocoon"-like Zn/N doped ZIF-derived porous carbon (Zn@N-C-800) is synthesized as an anode for lithium-ion batteries (LIBs) and sodium ion batteries (SIBs) through a one-step carbonization process using a novel Zn-ZIF as the precursor. In Zn@N-C-800, the "cocoon"-like disordered carbon skeleton is conducive to electrolyte infiltration, while the Zn/N doping can provide additional active sites for ion storage. Benefiting from these unique structural characteristics, Zn@N-C-800 achieves excellent electrochemical performances as anode for both LIBs and SIBs: an ultrahigh rate capability of 352 mAh g−1 can be delivered at 12.8 A g−1 for LIBs; an outstanding long-term cycling stability (312 mAh g−1 at 1 A g−1 after 2000 cycles) can be achieved for SIBs. This paper provides new ideas for the design and preparation of high-performance anodes for LIBs and SIBs.

Steric Hindrance Engineering to Modulate the Closed Pores Formation of Polymer-Derived Hard Carbon for High-Performance Sodium-Ion Batteries.

The closed pores play a critical role in improving the sodium storage capacity of hard carbon (HC) anode, however, their formation mechanism as well as the efficient modulation strategy at molecular level in the polymer-derived HCs is still lacking. In this work, the steric hindrance effect has been proposed to create closed pores in the polymer-derived HCs for the first time through grafting the aromatic rings within and between the main chains in the precursor. The experimental data and theoretical calculation demonstrate that steric-hindrance effect from the aromatic ring side group can increase backbone rigidity and the internal free volumes in the polymer precursor, which can prevent the over graphitization and facilitate the formation of closed pores during the carbonization process. As a result, the as-prepared HC anode exhibits a remarkably enhanced discharge capacity of 340.3 mAh/g at 0.1 C, improved rate performance (210.7 mAh/g at 5 C) as well as boosted cycling stability (86.4% over 1000 cycles at 2C). This work provides a new insight into the formation mechanisms of closed pores via steric hindrance engineering, which can shed light on the development of high-performance polymer-derived HC anode for sodium-ion batteries.

Properties of Ti2CO2 and Ti2CO2/G heterostructures as anodes of sodium-ion batteries by first-principles study

Properties of Ti2CO2 and Ti2CO2/G heterostructures as anodes of sodium-ion batteries by first-principles study

Low cobalt single atoms loading on N-doped carbon for high Na storage performance

Cobalt single atoms on nitrogen-doped carbon (CoSAs/N-C) were successfully synthesized through the pyrolysis of metal-organic supramolecular self-template. Only 0.12 wt% metal-doped CoSAs/N-C anodes bring a rate capacity enhancement of 195 mAh g−1 compared to the blank group of nitrogen-doped carbon electrodes at 0.1 A g−1. In addition, the CoSAs/N-C anodes exhibit remarkable sodium-ion storage capacities of 285 mAh g−1 after 2000 cycles at 1.0 A g−1 and 133 mAh g−1 with an exceptional cycling stability for 10,000 cycles at an ultra-high current density of 20 A g−1, thereby showcasing excellent Na ion storage performance. Ex-situ X-ray photoelectron spectroscopic study demonstrates that some N atoms in CoSAs/N-C can reversibly store and release Na ions during discharge and charge cycles. The full cell assembled with CoSAs/N-C anode and Na3V2(PO4)3 cathode displays Coulombic efficiency of >99.7 % after 200 cycles at 0.5 A g−1. Density functional theory (DFT) calculations further reveal that the presence of single-atom Co results in a decrease in the Na binding energy surrounding pyrrolic-N and pyridinic-N structures. This moderate binding energy may be beneficial for Na ion adsorption and desorption. This study opens up new possibilities of fabricating advanced metal single atom anodes for high-performance sodium-ion batteries.

Upscaling Brønsted acid intercalation and exfoliation of graphite into graphene by polyoxometalate clusters for sodium-ion battery application

Non-oxidative intercalation of graphite avoids damage to graphene lattices and is a suitable method to produce high-quality graphene. However, the yield of exfoliated graphene is low in this process due to the poor delamination efficiency of guest species. In this study, a Brønsted acid intercalation protocol is developed involving polyoxometalate (POM) clusters (H6P2W18O62) as guests and intercalation of graphite is realized at the sub-nanometer scale. Theoretical simulation based on DFT elucidates the stepwise intercalation mechanism of Brønsted acid molecules and clusters. Unlike common molecules/ionic guests, intercalation of POM clusters induces large expansion and extensive donor–acceptor interactions among graphite interlayers. This significantly weakens the van der Waals forces and promotes exfoliation efficiency of graphene layers. The exfoliated graphene possesses outstanding features of large lateral size, thin thickness, and high purity, and shows excellent performance as the anode for high power sodium-ion batteries. This work proffers a new pathway toward non-oxidative intercalation of graphite for large-scale production of graphene.

Sub-minute carbonization of polymer/carbon nanotube films by microwave induction heating for ultrafast preparation of hard carbon anodes for sodium-ion batteries

Hard carbons (HCs) are excellent anode materials for sodium-ion batteries (SIBs). However, the carbonization and granulation of HC powders involve complex processes and require considerable energy. Here, we developed a facile method for manufacturing HC anodes for SIBs via a novel microwave induction heating (MIH) process for polymer/single-walled carbon nanotube (SWCNT) films. Numerical simulations solving electromagnetic field and heat transfer problems revealed the MIH mechanism; the electric current induced by the applied microwave enables direct Joule heating of the SWCNT networks in the composite film. Consequently, the composite films could be heated to the target temperatures (800–1400 °C) and free-standing HC/SWCNT anodes could be prepared by applying MIH for only 30 s. Comparative analyses confirmed that ultrafast MIH is a reliable technique for producing HC anodes and can replace conventional carbonization processes which require a high-temperature furnace. Moreover, the HC/SWCNT anodes prepared by the ultrafast MIH were successfully applied to the SIB full cells. Finally, the feasibility of MIH for scalable roll-to-roll production of HC anodes was verified through local heating tests using a circular sheet larger than a resonator.

Lattice-confined localized alloying of Bi0.67TaS2 anode enabling ultrafast and stable sodium storage up to 150 C

Bismuth is considered to be a promising anode for sodium-ion batteries due to its low voltage plateau and high volumetric capacity. However, the large volume variation during alloying/dealloying leads to electrode pulverization and performance degradation, especially under high current densities. Herein we propose a lattice-confined localized alloying reaction mechanism to solve the above issues. By chemically embedding Bi atoms in a rigid layered ▪ host framework, the alloying reaction of Bi is spatially and kinetically confined within the ▪ interlayer, allowing for complete recovery of the Bi0.67TaS2 crystal structure after desodiation. The as-prepared Bi0.67TaS2 anode exhibits superior rate performance, achieving capacities of 256 mAh g ▪ at 1 C and 186 mAh g ▪ at 150 C, along with remarkable long-term cycling stability for maintaining 153 mAh g ▪ after 20000 cycles at 150 C. This work demonstrates that the localized alloying mechanism enabled by lattice confinement significantly contributes to both rate and cycling performance, which is expected to provide insights into electrode design for future fast-charging batteries.

In situ synthesis of SnPS3/Ti3C2Tx hybrid anode via molten salt etching method for superior sodium-ion batteries

Recently, SnPS3 has gained attention as an impressive sodium-ion battery anode material because of its significant theoretical specific capacity derived from the conversion-alloying reaction mechanism. Nevertheless, its practical applicability is restricted by insufficient rate ability, and severe capacity loss due to inadequate electrical conductivity and dramatic volume expansion. Inspired by the electrochemical enhancement effect of MXene substrates and the innovative Lewis acidic etching for MXene preparation, SnPS3/Ti3C2Tx MXene (T = –Cl and –O) is constructed by synchronously phospho-sulfurizing Sn/Ti3C2Tx precursor. Benefiting from the boosted Na+ diffusion and electron transfer rates, as well as the mitigated stress expansion, the synthesized SnPS3/Ti3C2Tx composite demonstrates enhanced rate capability (647 mA h g−1 at 10 A g−1) alongside satisfactory long-term cycling stability (capacity retention of 94.6% after 2000 cycles at 5 A g−1). Importantly, the assembled sodium-ion full cell delivers an impressive capacity retention of 97.7% after undergoing 1500 cycles at 2 A g−1. Moreover, the sodium storage mechanism of the SnPS3/Ti3C2Tx electrode is elucidated through in-situ and ex-situ characterizations. This work proposes a novel approach to ameliorate the energy storage performance of thiophosphites by facile in-situ construction of composites with MXene.

Study on the Performance of Aniline Electrodeposited on MnO2 Nanowire as an Anode for Sodium-Ion Batteries.

Manganese dioxide is an ideal anode for sodium-ion batteries due to its rich crystal shapes. However, its low conductivity, low reversible discharge capacity, slow diffusion kinetics, and poor cyclic stability limit its potential for industrial application. The design of manganese dioxide (MnO2) with various morphologies, such as nanowires, nanorods, and nanoflowers, has proven effective in enhancing its electrochemical performance. Stacking nanowire structures is of interest as they increase the open space by forming an interconnected network, thus facilitating favorable diffusion pathways for sodium ions. Concurrently, the substantial increase in the electrolyte contact area efficiently mitigates the strain induced by the volume expansion associated with the repetitive migration and insertion of sodium ions. Based on previous research, this work presents the structural design of flexible MnO2/polyaniline (MnO2/PANI) nanowires assembled on carbon cloth (CC), an innovation in MnO2 modification. Compared to conventional MnO2 nanowires, the MnO2/PANI nanowires exhibit enhanced structural stability and improved dynamic performance, thereby marking a significant advancement in their material properties. This MnO2/PANI composite exhibits a rate capacity of approximately 200 mA h g-1 after 60 cycles at a current density of 0.1 A g-1, and maintains a rate capacity of 182 mA h g-1 even after 200 cycles under the same current density. This study not only provides new insights into the underlying mechanisms governing energy storage in MnO2/PANI nanowires but also paves the way for their further development and optimization as anodes for sodium-ion batteries, thereby opening up fresh avenues for research and application.