Anode For SIBs Research Articles

Preparation, enhanced Na+ storage performance and mechanism of Sb/C nanobilayer film as anode for SIBs by magnetron sputtering

Preparation, enhanced Na+ storage performance and mechanism of Sb/C nanobilayer film as anode for SIBs by magnetron sputtering

Investigation of Solid Electrolyte Interphase Regarding Extra Capacity in Fe‐Fe3C as a Superior Sodium‐Ion Anode Material

AbstractSodium‐ion batteries (SIBs) offer promising advantages over lithium‐ion batteries (LIBs) due to sodium's abundance and lower cost. However, challenges like thick solid electrolyte interphase (SEI) layers and the larger radius of sodium (1.02 Å vs. 0.76 Å for lithium) make graphite, the most common LIB anode, unsuitable for SIBs. To realize the maximum potential of carbon anode for SIBs, one of the main strategies is to fabricate carbon materials with tailored microstructures and to enhance redox reactivity by incorporating catalytic metals. In this work, the Fe‐Fe3C nanoparticles embedded in worm‐like graphitic carbon (Fe‐Fe3C@GC) were synthesized by a simple chemical vapor deposition. This hybrid structure promotes the catalytic activity to achieve additional capacities through the reversible SEI layer formation, in detail, by the reversible interconversion of ester and ether derivatives as well as conductivity enhancement. Furthermore, in situ formed Fe2O3 from Fe(0) contributed extra capacity. The Fe‐Fe3C@GC showed a large reversible discharge capacity of 376.2 mAh g−1 with a fading rate of 0.013% per cycle after 1000 cycles at a current density of 50 mA g−1. A full cell coupled with an FeOF cathode delivered a high energy density of 602.8 Wh kg−1.

Bulk Alloy Anodes for Sodium‐Ion Batteries

AbstractSodium‐ion batteries (SIBs) are considered a promising candidate for next‐generation energy storage systems due to the abundance of available sodium resources. The practical application of SIBs critically depends on developing durable electrode materials with high capacity and long lifespan, particularly when it comes to finding suitable anode materials. Alloy‐type anodes are appealing for their high capacities owing to the multiple electron transfer alloying reaction mechanism, making them ideal for high‐energy‐density SIBs. However, the huge volume change during charge/discharge process can cause the active material pulverization to detach from the current collector, leading to poor cycling performance, especially for bulk alloy anodes. Despite this challenge, recent progress in bulk or micro‐sized alloy anodes for SIBs have shown promise. This review highlights the up‐to‐date advancements and research on bulk alloy‐based anode materials for SIBs, including synthetic strategies and electrochemical performance. The crucial role of bulk alloy anodes in advancing SIB technology is discussed, along with a summary of research on bulk alloy‐type anodes and their compounds for sodium storage. Strategies to improve the electrochemical performance of bulk alloy‐based anode materials are also explored. Additionally, the potential of multi‐component alloys and high‐entropy alloys as future research directions for alloy‐based anodes is proposed.

Effect of precursor particle size on the microstructure and Na storage performance of semi-coke derived carbon

The microstructure of carbon-based materials exerts a decisive influence on their Na storage performance. Furthermore, its evolution process may be influenced by the size of precursor particles during the pyrolysis preparation process. In this work, semi-coke has been used as the precursor, and its particle size (median particle sizes of 3, 7, 11, 15, and 19 μm) is investigated for its impact on the microstructure and Na storage performance of the resulting carbon materials (SDC-X, X = 3, 7, 11, 15, or 19). As the size of semi-coke increases from 3 μm to 19 μm, the highly-disordered carbon content of SDC-X decreases from 41.27 % to 30.94 %, while the content of pseudo-graphitic carbon associated with plateau capacity remains nearly constant. When SDC-X are employed as anodes for sodium-ion batteries, the initial coulombic efficiency (ICE) rose from 77.4 % to 82.3 % with the increase of size, primarily due to the increase in the ICE of slope region. However, despite SDC-19 having the highest ICE, its reversible capacity, rate, and cycle performance are inferior compared with the others due to its higher order degree and larger particle size. Therefore, carbon-based materials used as anodes for SIBs require a trade-off between particle size and the electrochemical performance.

Uncovering and preventing polytellurides dissolution enables stable sodium-ion storage: A case study of SnTe

Metal tellurides (MTes) have emerged as promising candidates for high-specific energy sodium-ion batteries owing to their superior volumetric capacity and exceptional intrinsic conductivity. Nevertheless, their practical application faces challenges associated with pronounced capacity degradation associated with unclear decay mechanisms. In this study, we uncover, for the first time, that the dissolution and shuttling of intermediates (NaxTey) are responsible for the rapid capacity decay in alloy- and conversion-type MTe anodes. Based on this discovery, we propose a novel structural engineering strategy that involves confining ultrafine SnTe nanoparticles within a fibrous carbon matrix, facilitating the smooth immobilization and highly reversible conversion of NaxTey. State-of-the-art in-/ex-situ tests and density functional theory calculations elucidate the evolution and shuttling mechanisms of NaxTey, highlighting the van der Waals barrier of the carbon matrix and the remarkable chemisorption of N and S dopant sites towards Na2Te2 and Na2Te intermediates. Significantly, the chemisorption capacity of NaxTey is enhanced through the optimization of doping content and bonding type of N and S, resulting in excellent stability of SnTe embedded in a high-content N and S co-doped carbon fiber matrix (SnTe@SHNC). The elaborate SnTe@SHNC composites demonstrate exceptional performance, enduring over 1000 cycles at 1.0 A g−1 with an ultraslow capacity decay rate of 0.028 % per cycle. This work provides valuable insight into the pivotal role of controlling NaxTey in the design of durable MTe anodes for advanced SIBs.

S-doped MXene@porous carbon nano-fiber composite for improved sodium storage performance

Sodium-ion batteries have attracted considerable interest of many scholars due to their low cost and similar energy storage mechanism to lithium-ion batteries. Considering the poor electrochemical redox reaction kinetics and low structural stability resulting from the larger radius of Na+ (0.102 nm), we have elaborately designed novel sulfur-doped MXene/porous carbon nano-fiber composites (S-MX@CNF) as anodes for SIBs via a synergistic assembly and sulfidation treatment approach. The S-MX@CNF composites have a multi-layered structure, which not only prevents restacking of MXene layers and increases accessible active sites, but also enhances the overall electrode conductivity. The composites exhibit a unique interconnected conductive network frame structure and increased interlayer spacing, which facilitates fast ionic and electronic transport rates. Additionally, the robust composites exhibit high chemical stability, enabling it to tolerate volume changes during the rapid charge/discharge process. As a result of these synergistic effects, the S-MX@CNF displays a high reversible capacity of 304 mAh/g (0.5 A/g) after 1000 cycles and long cycle stability of 170 mAh/g (3 A/g) with only 0.1 % degradation per cycle within 4900 cycles. This work opens up new opportunities for further advances in synergistic assembly and heteroatom doping strategies for composites in energy storage devices.

Recent advances in Sb-based anodes for Li/Na/K-ion batteries and all-solid-state Li-ion batteries

In recent decades, lithium-ion batteries (LIBs) have emerged as a primary focus in the energy-storage field owing to their superior energy and power densities. However, concerns regarding the depletion of non-abundant lithium resources have prompted the exploration and development of emerging energy-storage technologies, such as sodium- (SIBs) and potassium-ion batteries (PIBs). In addition, all-solid-state LIBs (ASSLIBs) have been developed to address the issues of flammability and explosiveness associated with liquid electrolytes. Among the various alloy-based anodes, antimony (Sb) anodes exhibit high energy densities owing to their high theoretical volumetric capacities that are attributable to their high densities. However, Sb anodes exhibit poor cyclabilities owing to excessive volume changes during cycling. To mitigate this issue, researchers have investigated the use of diverse solutions, including solid electrolyte interface control, structural control, and composite/alloy formation. Herein, we review and summarize Sb-based anode materials for LIBs, SIBs, PIBs, and ASSLIBs developed over the past five years (2018-present), focusing on their reaction mechanisms and multiple approaches used to achieve optimal electrochemical performance. We anticipate that this review will provide a comprehensive database of Sb-based anodes for LIBs, SIBs, PIBs, and ASSLIBs, thereby advancing relevant studies in the energy-storage-systems field.

Heterostructure Engineering Enables MoSe2 with Superior Alkali-Ion Storage

Molybdenum diselenide (MoSe2) is a promising anode for alkali-ion storage due to its intrinsic advantages. However, MoSe2 still encounters the issues of structural instability and poor rate performance caused by drastic volume change and sluggish reaction kinetics. Reasonable design of electrode structure is crucial for achieving superior electrochemical performance. Herein, a novel hierarchical structure coupled with 1D/1D subunits is elaborately designed and constructed, in which the MoSe2/CoSe2 heterostructure is the “trunk” and the N-doped carbon nanotubes are the “branches” (MoSe2/CoSe2/NCNTs). Benefiting from the properties endowed by unique configurations, MoSe2/CoSe2/NCNTs electrodes manifest faster reaction kinetics and better structure durability. Evaluated as an anode for LIBs and SIBs, MoSe2/CoSe2/NCNTs deliver high reversible capacity, superior rate capability (452 at 10 A g−1 in LIBs and 296 at 10 A g−1 in SIBs), and prominent cycle life (553 after 2000 cycles at 5 A g−1 in LIBs and 310 after 2000 cycles at 5 A g−1 in SIBs). Such design conception can also provide guidance for the development of other high-performance electrodes.

Regulating nitrogen/sulfur terminals on 3D porous Ti3C2 MXene with enhanced reaction kinetics toward high-performance alkali metal ion storage

In this paper, we have developed a simple and efficient sulfur-amine chemistry strategy to prepare a three-dimensional (3D) porous Ti3C2Tx composite with large amounts of N and S terminal groups. The well-designed 3D macroporous architecture presents enlarged interlayer spacing, large specific surface area, and unique porous structure, which successfully solves the re-stacking issue of MXene during storage and electrode fabrication. It is the amount of concentrated hydrochloric acid added to the S-EDA (ethylenediamine)/MXene colloidal suspension that is critical to the formation of 3D morphology. In addition, N and S terminals on MXene could improve the adsorption ability of K+. Owing to the synergistic effect of the structure design and terminal modification, the N, S codoped three-dimensional porous Ti3C2Tx (3D-NSPM) material shows a high surface capacitive contribution and rapid diffusion kinetics for K+ and Na+. As a result, the as-prepared 3D-NSPM delivers high reversible capacity (237 and 273 mAh g−1 at 0.1 A g−1 for PIBs and SIBs, respectively), superb cycling stability (84.9% capacity retention after 10,000 cycles at 1 A g−1 in PIBs and 74.0% capacity retention after 2200 cycles at 1 A g−1 in SIBs), and excellent rate capability (111 and 196 mAh g−1 at 5 A g−1 for PIBs and SIBs, respectively), which are superior to other MXene-based anodes for PIBs and SIBs. Moreover, the described strategy provides a new insight for constructing the 3D porous structure from 2D building blocks beyond MXene.

Non-graphitic carbon as sodium-ion battery anode materials with improved ratio of plateau to sloping capacities prepared from lignite-based organic maceral

Herein, huminite concentrate is obtained from lignite with high yield of 68.9 % by density gradient separation, subsequently converted to non-graphitic carbon (HM-H) by carbonization at 1400 °C for 2 h. Huminite concentrate possesses relatively high oxygen content and considerable amount of aromatic component, with modest yield of volatile matter during pyrolysis, resulting in optimized carbon phase distribution and enhanced electrical conductivity of HM-H. Compared with HM prepared by direct carbonization of lignite, HM-H has slightly higher contents of pseudo-graphitic and graphite-like carbons, and lower content of highly disordered one. Notably, HM-H exhibits remarkably improved electrical conductivity (1773 S m−1) than HM (1406 S m−1). Compared with HM anode for SIBs, HM-H one delivers higher plateau capacity (170.1 mAh g−1) meanwhile lower sloping capacity (91.8 mAh g−1), with significantly improved rate and cycling performances. Full cell assorted with NaFe1/3Ni1/3Mn1/3O2 cathode and HM-H anode demonstrates higher energy density of 210.5 Wh kg−1 than its counterpart (193.8 Wh kg−1) at 20 mA g−1, with superior rate performance (208.6 mAh g−1 at 200 mA g−1) and a capacity retention ratio of 89.7 % after 100 cycles. This work provides a facile and effective strategy for preparing non-graphitic carbon as high-performance anode materials for SIBs.

Topochemically synthesized Nb3VS6 as a stable anode for sodium-ion batteries.

Ternary metal sulfides having layered morphology are considered as potential active materials for various applications. Herein, Nb3VS6 is synthesized topochemically for the first time using a Nb-V-HDA complex having a lamellar structure by employing H2S gas as the sulfidation agent. Nb3VS6, as an anode for SIBs, exhibited a specific capacity of 101.15 mA h g-1 at 0.5 A g-1, along with excellent cycling stability with 100% capacity retention after 2500 cycles.

Chromium tetraphosphide (CrP4) as a high-performance anode for Li ion and Na ion batteries

The CrP4 nanoparticles and CrP4/C nanocomposite were synthesized via high-energy mechanical milling and applied as anodes for LIBs and SIBs.

Field-assisted conductive substrate sparks the redox kinetics of Co9S8 in Li- and Na-ion batteries

As a promising candidate electrode material in both Li- and Na-ion batteries (L/SIBs), the application of Co9S8 is being hindered by its unsatisfactory electrochemical performance caused by the sluggish ion diffusion kinetics and drastic volume expansion. Herein, a hybrid material composed of Co9S8−x, N-doped carbon foam that seeded with Co nanoparticles (Co9S8−x@Co-NC) is constructed. Particularly, theoretical and experimental results imply that a built-in electric field at the interface of Co and NC is observed due to the variation of Fermi levels, forming rich Mott-Schottky-like heterointerfaces, which can significantly enhance the charge transfer capability between the active materials of Co9S8 and conductive NC skeleton. Moreover, the sulfur defects in Co9S8−x can not only effectively lower the energy barrier of the ion diffusion and charge transfer processes, but also endow the target sample with more storage/adsorption/active sites for Li+/Na+ ions, thus improving the rate performance of the Co9S8−x@Co-NC composite. As a result, the Co9S8−x@Co-NC exhibits fast surface-controlled redox kinetics and robust cycling stability. For instance, the Co9S8−x@Co-NC displays impressive Li-storage properties in both half and full cells with a high reversible capacity of 1007.4 mA h g−1 at 0.1 A g−1 after 100 cycles and superior rate capability up to 5 A g−1. Moreover, based on these comprehensive merits, the Co9S8−x@Co-NC composite shows decent electrochemical performance (472.2 and 311.1 mA h g−1 at 0.1 and 10 A g−1, respectively) as an anode for SIBs. This work presents an effective strategy for the construction of Mott-Schottky-like heterointerfaces in Co9S8 based materials and provides specific inspiration for future works designing high-performance electrodes via interfacial engineering.

Preparation of disodium terephthalate/multi-walled carbon nanotube composite as an anode material for sodium-ion batteries: Performance and mechanism

Compared with the scarce resources of lithium-ion batteries (LIBs), sodium-ion batteries have been attracting research attentions as an ideal carrier for large-scale energy storage systems due to their abundant raw material resources. Organic materials are gaining importance as SIB anodes due to their advantages of simple preparation method, recyclability, and multi-electron reactions. In this work, disodium terephthalate/multi-walled carbon nanotube (Na2TP/MWCNT) organic composite was prepared as SIB anode material by an anti-solvent method. Experimental results indicated that the optimum sodium storage can be achieved with 10 wt% MWCNT dosage, where reversible capacities reached 229.9 and 93.2 mA h/g at current densities 0.1 and 2C, respectively. The capacity remained 124.9 mA h/g after 50 cycles at 1C current density, which suggested that the composite could act as a candidate for sodium ion battery anodes.

In-situ growth of nitrogen-doped carbon nanotubes on MXene nanosheets for efficient sodium/potassium-ion storage

For game changing for future of large-scale energy storage technologies, sodium-ion and potassium-ion batteries provide a substitute to lithium-ion batteries. As an excellent candidate anode, MXene still suffers from the blockage of active sites caused by restacking of sheets. Herein, an in-situ decoration of MXene nanosheets with nitrogen-doped carbon nanotubes (CNTs) is introduced, to yield MXene@CNTs. The modification of nitrogen-doped CNTs not only prevents the restacking of MXene and increases ion accessibility but also improves the electrode’s overall conductivity, thereby enhancing electron conduction and ion diffusion kinetics significantly. Therefore, MXene@CNTs exhibits superior sodium/potassium-ion storage performance than pure MXene nanosheets. At 0.05 A g-1, it can deliver reversible capacities of 286 mAh g-1 for SIBs and 250 mAh g-1 for PIBs. This research illustrates the significance of the electrode architecture for electrochemical performances, and the in-situ growth strategy could provide some insight on searching for high-performance MXene-based anodes for SIBs and PIBs.

Facile Synthesis of Nickel Phosphide @ N-Doped Carbon Nanorods with Exceptional Cycling Stability as Li-Ion and Na-Ion Battery Anode Material

Nickel phosphide (Ni2P), as an anode material for both lithium- and sodium-ion batteries, offers high theoretical specific and volumetric capacities. However, considerable challenges include its limited rate capability and low cycle stability arising from its volume change and degradation during cycling. To solve these issues, appropriate composite micro/nanoparticle designs can improve conductivity and provide confinement. Herein, we report a simple pyrolysis method to synthesize nitrogen-doped carbon-coated Ni2P nanorod arrays (Ni2P@NC) from nickel foam and an ionic resin as a source of carbon, nitrogen and phosphorus. The N-doped open-ended carbon shells provide Ni2P containment, good electrical conductivity, efficient electrolyte access and the buffering of bulk strain during cycling. Consequently, as a LIB anode material, Ni2P@NC has impressive specific capacity in long-term cycling (630 mAh g−1 for 150 cycles at 0.1 A g−1) and a high rate capability of 170 mAh g−1 for 6000 cycles at 5 A g−1. Similarly, as a SIB anode, Ni2P@NC retains a sizable 288 mAh g−1 over 300 cycles at 0.1 A g−1, and 150 mAh g−1 over 2000 cycles at 2 A g−1. Furthermore, due to a sizable portion of its capacity coinciding with adequately low voltage, the material shows promise for high volumetric energy storage in full-cell format. Lastly, the simple synthesis method has the potential to produce other carbon-coated metal phosphides for electrochemical applications.

Point-cavity-like carbon layer coated SnS nanotubes with improved energy storage capacity for lithium/sodium ion batteries

Tin monosulfide (SnS) is known as a prospective anode material for lithium/sodium ion batteries due to its high capacity, low cost, and easy preparation. Carbon coating is a powerful strategy to improve poor electronic conductivity and alleviate the large volume expansion of the SnS, thus achieving high electrochemical performances. However, the commonly used carbon coatings strategies usually generate interstices between the SnS and carbonaceous material, interrupting electron and ion transfer and unsatisfied accommodation of volume expansion. Herein, point-cavity-like carbon coated SnS nanotubes (CN/SnS) were synthesized by a close-knit mechanism using polyvinylpyrrolidone (PVP) and carbon nitride (g-C3N4) as carbon sources. The carbonyl group in PVP can form hexahydroxylated stannyl compound with Sn2+, and the amine group can generate CN bond with the g-C3N4 template in an aqueous solution, respectively. The unique construction of CN/SnS can successfully reinforce the electron and ion transfer capability and accommodate volume expansion. The reformative effectivity dramatically improves the energy storage properties of SnS electrode for LIBs/SIBs. The CN/SnS electrode can deliver high specific capacities of 547.7 mAh g−1 at 1.0 A g−1 after 300 cycles for lithium-ion batteries and 298.2 mAh g−1 at 0.1 A g−1 after 200 cycles for sodium-ion batteries, respectively. The structure design is practical and feasible, which could be used to develop high-performance transition metal sulfide/carbon composite anodes for LIBs and SIBs.

ZnS-rGO/CNF Free-Standing Anodes for SIBs: Improved Electrochemical Performance at High C-Rate.

ZnS-graphene composites (ZnSGO) were synthesized by a hydrothermal process and loaded onto carbon nanofibers (CNFs) by electrospinning (ZnS-GO/CNF), to obtain self-standing anodes for SIBs. The characterization techniques (XRPD, SEM, TEM, EDS, TGA, and Raman spectroscopy) confirm that the ZnS nanocrystals (10 nm) with sphalerite structure covered by the graphene sheets were successfully synthesized. In the ZnS-GO/CNF anodes, the active material is homogeneously dispersed in the CNFs' matrix and the ordered carbon source mainly resides in the graphene component. Two self-standing ZnS-GO/CNF anodes (active material amount: 11.3 and 24.9 wt%) were electrochemically tested and compared to a tape-casted ZnS-GO example prepared by conventional methods (active material amount: 70 wt%). The results demonstrate improved specific capacity at high C-rate for the free-standing anodes compared to the tape-casted example (69.93 and 92.59 mAh g-1 at 5 C for 11.3 and 24.9 wt% free-standing anodes, respectively, vs. 50 mAh g-1 for tape-casted). The 24.9 wt% ZnS-GO/CNF anode gives the best cycling performances: we obtained capacities of 255-400 mAh g-1 for 200 cycles and coulombic efficiencies ≥ 99% at 0.5 C, and of 80-90 mAh g-1 for additional 50 cycles at 5 C. The results suggest that self-standing electrodes with improved electrochemical performances at high C-rates can be prepared by a feasible and simple strategy: ex situ synthesis of the active material and addition to the carbon precursor for electrospinning.

Amorphous Germanium Nanomaterials as High‐Performance Anode for Lithium and Sodium‐Ion Batteries

AbstractAmorphous germanium (a‐Ge) is a promising anode material for lithium and sodium‐ion batteries (LIBs and SIBs) due to its higher capacity than traditional graphite materials. Herein, a method to prepare the a‐Ge nano‐materials with a particle size ≈10 nm is proposed by decomposing the CaGe Zintl phase at room temperature. For LIBs, a‐Ge has a high‐capacity retention of 80% even after 180 cycles (1375 mAh g−1). When employed as the anode for SIBs, two‐dimensional composites with the a‐Ge supported on the graphite nanosheets (a‐Ge@GNS) is configured, and a high reversible capacity of 526 mAh g−1 after 120 cycles is achieved. The preparation of such high‐performance amorphous Ge nanomaterials demonstrated in this work is low‐cost and environmentally‐friendly, and compared with other methods it is especially suitable for scaling‐up or mass production.

Enabling intercalation‐type TiNb24O62 anode for sodium‐ and potassium‐ion batteries via a synergetic strategy of oxygen vacancy and carbon incorporation

AbstractThe key to develop earth‐abundant energy storage technologies sodium‐ and potassium‐ion batteries (SIBs and PIBs) is to identify low‐cost electrode materials that allow fast and reversible Na+/K+ intercalation. Here, we report an intercalation‐type material TiNb24O62 as a versatile anode for SIBs and PIBs, via a synergistic strategy of oxygen vacancy and carbon incorporation to enhance ion and electron diffusion. The TiNb24O62−x/reduced graphene oxide (rGO) composite anode delivers high reversible capacities (130 mA h g−1 for SIBs and 178 mA h g−1 for PIBs), great rate performance (54 mA h g−1 for SIBs and 37 mA h g−1 for PIBs at 1 A g−1), and superior cycle stability (73.7% after 500 cycles for SIBs and 84% after 300 cycles for PIBs). The performance is among the best results of intercalation‐type metal oxide anodes for SIBs and PIBs. The better performance of TiNb24O62−x/rGO in SIBs than PIBs is due to the better reaction kinetics of the former. Moreover, mechanistic study confirms that the redox activity of Nb4+/5+ is responsible for the reversible intercalation of Na+/K+. Our results suggest that TiNb24O62−x/rGO is a promising anode for SIBs and PIBs and may stimulate further research on intercalation‐type compounds as candidate anodes for large ion batteries.