Enhanced Capacity and Rate Capability of Nitrogen/Oxygen Dual‐Doped Hard Carbon in Capacitive Potassium‐Ion Storage

The intercalation of potassium ions into graphite is demonstrated to be feasible, while the electrochemical performance of potassium‐ion batteries (KIBs) remains unsatisfying. More effort is needed to improve the specific capacity while maintaining a superior rate capability. As an attempt, nitrogen/oxygen dual‐doped hierarchical porous hard carbon (NOHPHC) is introduced as the anode in KIBs by carbonizing and acidizing the NH₂‐MIL‐101(Al) precursor. Specifically, the NOHPHC electrode delivers high reversible capacities of 365 and 118 mA h g^?1 at 25 and 3000 mA g^?1, respectively. The capacity retention reaches 69.5% at 1050 mA g^?1 for 1100 cycles. The reasons for the enhanced electrochemical performance, such as the high capacity, good cycling stability, and superior rate capability, are analyzed qualitatively and quantitatively. Quantitative analysis reveals that mixed mechanisms, including capacitance and diffusion, account for the K‐ion storage, in which the capacitance plays a more important role. Specifically, the enhanced interlayer spacing (0.39 nm) enables the intercalation of large K ions, while the high specific surface area of ≈1030 m² g^?1 and the dual‐heteroatom doping (N and O) are conducive to the reversible adsorption of K ions.     

Reactive Oxygen‐Doped 3D Interdigital Carbonaceous Materials for Li and Na Ion Batteries

Carbonaceous materials as anodes usually exhibit low capacity for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Oxygen‐doped carbonaceous materials have the potential of high capacity and super rate performance. However, up to now, the reported oxygen‐doped carbonaceous materials usually exhibit inferior electrochemical performance. To overcome this problem, a high reactive oxygen‐doped 3D interdigital porous carbonaceous material is designed and synthesized through epitaxial growth method and used as anodes for LIBs and SIBs. It delivers high reversible capacity, super rate performance, and long cycling stability (473 mA h g^?1after 500 cycles for LIBs and 223 mA h g^?1 after 1200 cycles for SIBs, respectively, at the current density of 1000 mA g^?1), with a capacity decay of 0.0214% per cycle for LIBs and 0.0155% per cycle for SIBs. The results demonstrate that constructing 3D interdigital porous structure with reactive oxygen functional groups can significantly enhance the electrochemical performance of oxygen‐doped carbonaceous material.     

Capillary‐Induced Ge Uniformly Distributed in N‐Doped Carbon Nanotubes with Enhanced Li‐Storage Performance

Germanium (Ge) is a prospective anode material for lithium‐ion batteries, as it possesses large theoretical capacity, outstanding lithium‐ion diffusivity, and excellent electrical conductivity. Ge suffers from drastic capacity decay and poor rate performance, however, owing to its low electrical conductivity and huge volume expansion during cycling processes. Herein, a novel strategy has been developed to synthesize a Ge@N‐doped carbon nanotubes (Ge@N‐CNTs) composite with Ge nanoparticles uniformly distributed in the N‐CNTs by using capillary action. This unique structure could effectively buffer large volume expansion. When evaluated as an anode material, the Ge@N‐CNTs demonstrate enhanced cycling stability and excellent rate capabilities.     

Self‐Supporting,Flexible, Additive‐Free,and Scalable Hard Carbon Paper Self‐Interwoven by 1D Microbelts: Superb Room/Low‐Temperature Sodium Storage and Working Mechanism

Hard carbon is regarded as a promising anode material for sodium‐ion batteries (SIBs). However, it usually suffers from the issues of low initial Coulombic efficiency (ICE) and poor rate performance, severely hindering its practical application. Herein, a flexible, self‐supporting, and scalable hard carbon paper (HCP) derived from scalable and renewable tissue is rationally designed and prepared as practical additive‐free anode for room/low‐temperature SIBs with high ICE. In ether electrolyte, such HCP achieves an ICE of up to 91.2% with superior high‐rate capability, ultralong cycle life (e.g., 93% capacity retention over 1000 cycles at 200 mA g^?1) and outstanding low‐temperature performance. Working mechanism analyses reveal that the plateau region is the rate‐determining step for HCP with a lower electrochemical reaction kinetics, which can be significantly improved in ether electrolyte.     

Design Nitrogen (N) and Sulfur (S) Co‐Doped 3D Graphene Network Architectures for High‐Performance Sodium Storage

To develop high‐performance sodium‐ion batteries (NIBs), electrodes should possess well‐defined pathways for efficient electronic/ionic transport. In this work, high‐performance NIBs are demonstrated by designing a 3D interconnected porous structure that consists of N, S co‐doped 3D porous graphene frameworks (3DPGFs‐NS). The most typical electrode materials (i.e., Na₃V₂(PO₄)₃ (NVP), MoS₂, and TiO₂) are anchored onto the 3DPGFs‐NS matrix (denoted as NVP@C@3DPGFs‐NS; MoS₂@C@3DPGFs‐NS and TiO₂@C@3DPGFs‐NS) to demonstrate its general process to boost the energy density of NIBs. The N, S co‐doped porous graphene structure with a large surface area offers fast ionic transport within the electrode and facilitates efficient electron transport, and thus endows the 3DPGFs‐NS‐based composite electrodes with excellent sodium storage performance. The resulting NVP@C@3DPGFs‐NS displays excellent electrochemical performance as both cathode and anode for NIBs. The MoS₂@C@3DPGFs‐NS and TiO₂@C@3DPGFs‐NS deliver capacities of 317 mAhg^?1 at 5 Ag^?1 after 1000 cycles and 185 mAhg^?1 at 1 Ag^?1 after 2000 cycles, respectively. The excellent long cycle life is attributed to the 3D porous structure that could greatly release mechanical stress from repeated Na⁺ extraction/insertion. The novel structure 3D PGFs‐NS provides a general approach to modify electrodes of NIBs and holds great potential applications in other energy storage fields.     

Metal Cation‐Assisted Synthesis of Amorphous B,N Co‐Doped Carbon Nanotubes for Superior Sodium Storage

Nearly inexhaustible sodium sources on earth make sodium ion batteries (SIBs) the best candidate for large‐scale energy storage. However, the main obstacles faced by SIBs are the low rate performance and poor cycle stability caused by the large size of Na⁺ ions. Herein, a universal strategy for synthesizing amorphous metals encapsulated into amorphous B, N co‐doped carbon (a‐M@a‐BCN; M = Co, Ni, Mn) nanotubes by metal cation‐assisted carbonization is explored. The methodology allows tailoring the structures (e.g., length, wall thickness, and metals doping) of a‐M@a‐BCN nannotubes at the molecular level. Furthermore, the amorphous metal sulfide encapsulated into a‐BCN (a‐MS_x@a‐BCN; MS_x: CoS, Ni₃S₂, MnS) nanotubes are obtained by one‐step sulfidation process. The a‐M@a‐BCN and a‐MS_x@a‐BCN possess the larger interlayer spacing (0.40 nm) amorphous carbon nanotube rich in heteroatoms active sites, making them exhibit excellent Na⁺ ions diffusion kinetics and capacitive storage behavior. As SIBs anodes, they show high capacity, excellent rate performance, and long cycle stability.     

The State and Challenges of Anode Materials Based on Conversion Reactions for Sodium Storage

Sodium‐ion batteries (SIBs) have huge potential for applications in large‐scale energy storage systems due to their low cost and abundant sources. It is essential to develop new electrode materials for SIBs with high performance in terms of energy density, cycle life, and cost. Metal binary compounds that operate through conversion reactions hold promise as advanced anode materials for sodium storage. This Review highlights the storage mechanisms and advantages of conversion‐type anode materials and summarizes their recent development. Although conversion‐type anode materials have high theoretical capacities and abundant varieties, they suffer from multiple challenging obstacles to realize commercial applications, such as low reversible capacity, large voltage hysteresis, low initial coulombic efficiency, large volume changes, and low cycling stability. These key challenges are analyzed in this Review, together with emerging strategies to overcome them, including nanostructure and surface engineering, electrolyte optimization, and battery configuration designs. This Review provides pertinent insights into the prospects and challenges for conversion‐type anode materials, and will inspire their further study.     

A Flexible Sulfur‐Enriched Nitrogen Doped Multichannel Hollow Carbon Nanofibers Film for High Performance Sodium Storage

Heteroatom doping is regarded as a promising method to enhance the sodium storage performance of carbon materials. In this work, a sulfur‐enriched N‐doped multichannel hollow carbon nanofiber (denoted as S‐NCNF) film is prepared through electrospinning technology and heat treatment with sublimed sulfur as the flexible anode for sodium ion batteries (NIBs). The S‐NCNF film displays outstanding electrochemical performance, particularly with a high rate capacity (132 mA h g^?1 at the current density of 10 A g^?1) and remarkable long cycling stability (reversible specific capacity of 187 mA h g^?1 at 2 A g^?1 over 2000 cycles). The improved sodium storage performance results from the unique 3D structure, abundant defects, and increased interlayer spacing of S‐NCNFs. The density functional theory calculations demonstrate that nitrogenous carbon nanofibers doping with sulfur could not only promote the adsorption of sodium but also favor electrons' transfer. This strategy has been demonstrated as a general process to design free‐standing carbon‐based thin film with other heteroatom doping.     

Rational Design and General Synthesis of S‐Doped Hard Carbon with Tunable Doping Sites toward Excellent Na‐Ion Storage Performance

Heteroatom‐doping is a promising strategy to tuning the microstructure of carbon material toward improved electrochemical storage performance. However, it is a big challenge to control the doping sites for heteroatom‐doping and the rational design of doping is urgently needed. Herein, S doping sites and the influence of interlayer spacing for two kinds of hard carbon, perfect structure and vacancy defect structure, are explored by the first‐principles method. S prefers doping in the interlayer for the former with interlayer distance of 3.997 Å, while S is doped on the carbon layer for the latter with interlayer distance of 3.695 Å. More importantly, one step molten salts method is developed as a universal synthetic strategy to fabricate hard carbon with tunable microstructure. It is demonstrated by the experimental results that S‐doping hard carbon with fewer pores exhibits a larger interlayer spacing than that of porous carbon, agreeing well with the theoretical prediction. Furthermore, the S‐doping carbon with larger interlayer distance and fewer pores exhibits remarkably large reversible capacity, excellent rate performance, and long‐term cycling stability for Na‐ion storage. A stable and reversible capacity of ≈200 mAh g^?1 is steadily kept even after 4000 cycles at 1 A g^?1.     

生物质玉米秸秆衍生碳材料的制备及其储钠性能

当代农业产生大量农作物秸秆残渣,对环境和生活产生极大影响,尤其是大量的焚烧。因此,农作物残渣的有效利用受到广泛关注。利用玉米秸秆茎髓为碳源,通过简单的高温碳化和化学膨化处理成功地合成了性能优异的碳片。物性结构研究表明,得到的碳材料呈现出天然蜂窝状截面和中空管状阵列结构的纵截面,并具有丰富的孔洞,有利于钠离子传输和扩散。(002)晶面表明,碳片的层间距为0.376nm(石墨为0.335nm),这有利于钠离子的脱嵌,从而提高电池的电化学性能。经1 200℃碳化合成的茎髓碳片(SPCS-1200)比900℃碳化合成的碳材料(SPC-900)表现出更好的储钠性能。在50mA·g-1电流密度下,循环100圈后SPCS-1200可以提供稳定的可逆比容量(203mAh·g-1),而SPC-900的可逆比容量仅为173mAh·g-1。此外,SPCS-1200也显示出优异的倍率性能,在1 000mA·g-1电流密度下比容量为100.7mAh·g-1,在2 000mA·g-1电流密度下表现出65.9mAh·g-1的比容量。然而,在相应的电流密度下,SPC-900分别表现出45.7mAh·g-1和31.2mAh·g-1的比容量。     

Synergistical Coupling Interconnected ZnS/SnS2 Nanoboxes with Polypyrrole‐Derived N/S Dual‐Doped Carbon for Boosting High‐Performance Sodium Storage

Metal sulfides possess tremendous potentials owing to their high specific capacity for sodium storage. However, the huge volume expansion, accompanied with structural collapse and unsatisfied electric conductivity upon continuous cycling, always lead to inferior rate capability and severe cycling fading. In this work, binary metal sulfide (ZnS/SnS₂) nanoboxes confined in N/S dual‐doped carbon shell (ZSS@NSC) are fabricated through a facile co‐precipitation method involving the wrapping of polypyrrole, and subsequent in situ sulfidation process. Such a well‐designed heterogeneity between ZnS and SnS₂ provides rapid Na⁺ insertion and enhanced charge transport by creating an electric field at the heterointerface. More significantly, the formation of polypyrrole‐derived N/S dual‐doped carbon is synergistically coupled with the ZnS/SnS₂ to create a unique and robust architecture, further strengthening the interconnect function at the heterointerface, which improves electric/ion transfer and mitigates the volume variation during the long‐term cycling process. Herein, this as‐prepared ZSS@NSC exhibits satisfied specific capacity, excellent rate property, and superior cyclic stability (a reversible capacity of 456.2 mAh g^?1 with excellent capacity retention of 97.2% after 700 stable cycles at ultrahigh rate of 5 A g^?1). The boosted Na‐storage properties demonstrate that the optimized strategy of structure‐engineering has a broad prospect to promote energy storage applications.     

Boosting the Reversibility of Sodium Metal Anode via Heteroatom‐Doped Hollow Carbon Fibers

Sodium (Na) metal anodes stand out with their remarkable capacity and natural abundance. However, the dendritic Na growth, infinite dimensional changes, and low Coulombic efficiency (CE) present key bottlenecks plaguing practical applications. Here, heteroatom‐doped (nitrogen, sulfur) hollow carbon fibers (D‐HCF) are rationally synthesized as a nucleation‐assisting host to enable a highly reversible Na metal. The “sodiophilic” functional groups introduced by the heteroatom‐doping and large surface area (≈1052 m² g^?1) synchronously contribute to a homogenous plating morphology with dissipated local current density. High “sodiophilicity” of the D‐HCF is confirmed by first‐principle calculations and experimental results, where strong adsorption energy of ?3.52 eV with low Na⁺ nucleation overpotential of 3.2 mV at 0.2 mA cm^?2 is realized. As such, highly reversible plating/stripping is achieved at 1.0 mA cm^?2 with average CE approximating 99.52% over 600 cycles. The as‐assembled Na@D‐HCF symmetric cells exhibit a prolonged lifetime for 1000 h. A full‐cell paired with Na₃V₂(PO₄)₃ cathode further demonstrates stable electrochemical behavior for 200 cycles at 1 C along with excellent rate performance (102 mAh g^?1 at 5 C). The results clearly show the effectiveness of the D‐HCF in manipulating Na⁺ deposition and thus the significance of nucleation control in realizing dendrite‐free metal anodes.     

3D Interconnected Carbon Fiber Network‐Enabled Ultralong Life Na3V2(PO4)3@Carbon Paper Cathode for Sodium‐Ion Batteries

Sodium‐ion batteries (NIBs) are an emerging technology, which can meet increasing demands for large‐scale energy storage. One of the most promising cathode material candidates for sodium‐ion batteries is Na₃V₂(PO₄)₃ due to its high capacity, thermal stability, and sodium (Na) Superionic Conductor 3D (NASICON)‐type framework. In this work, the authors have significantly improved electrochemical performance and cycling stability of Na₃V₂(PO₄)₃ by introducing a 3D interconnected conductive network in the form of carbon fiber derived from ordinary paper towel. The free‐standing Na₃V₂(PO₄)₃‐carbon paper (Na₃V₂(PO₄)₃@CP) hybrid electrodes do not require a metallic current collector, polymeric binder, or conducting additives to function as a cathode material in an NIB system. The Na₃V₂(PO₄)₃@CP cathode demonstrates extraordinary long term cycling stability for 30 000 deep charge–discharge cycles at a current density of 2.5 mA cm^?2. Such outstanding cycling stability can meet the stringent requirements for renewable energy storage.     

3D Interconnected and Multiwalled Carbon@MoS2@Carbon Hollow Nanocables as Outstanding Anodes for Na‐Ion Batteries

Currently, the specific capacity and cycling performance of various MoS₂/carbon‐based anode materials for Na‐ion storage are far from satisfactory due to the insufficient structural stability of the electrode, incomplete protection of MoS₂ by carbon, difficult access of electrolyte to the electrode interior, as well as inactivity of the adopted carbon matrix. To address these issues, this work presents the rational design and synthesis of 3D interconnected and hollow nanocables composed of multiwalled carbon@MoS₂@carbon. In this architecture, (i) the 3D nanoweb‐like structure brings about excellent mechanical property of the electrode, (ii) the ultrathin MoS₂ nanosheets are sandwiched between and doubly protected by two layers of porous carbon, (iii) the hollow structure of the primary nanofibers facilitates the access of electrolyte to the electrode interior, (iv) the porous and nitrogen‐doping properties of the two carbon materials lead to synergistic Na‐storage of carbon and MoS₂. As a result, this hybrid material as the anode material of Na‐ion battery exhibits fast charge‐transfer reaction, high utilization efficiency, and ultrastability. Outstanding reversible capacity (1045 mAh g^?1), excellent rate behavior (817 mAh g^?1 at 7000 mA g^?1), and good cycling performance (747 mAh g^?1 after 200 cycles at 700 mA g^?1) are obtained.     

MOF‐Derived Hollow Co9S8 Nanoparticles Embedded in Graphitic Carbon Nanocages with Superior Li‐Ion Storage

Novel electrode materials consisting of hollow cobalt sulfide nanoparticles embedded in graphitic carbon nanocages (HCSP?GCC) are facilely synthesized by a top‐down route applying room‐temperature synthesized Co‐based zeolitic imidazolate framework (ZIF‐67) as the template. Owing to the good mechanical flexibility and pronounced structure stability of carbon nanocages‐encapsulated Co₉S₈, the as‐obtained HCSP?GCC exhibit superior Li‐ion storage. Working in the voltage of 1.0?3.0 V, they display a very high energy density (707 Wh kg^?1), superior rate capability (reversible capabilities of 536, 489, 438, 393, 345, and 278 mA h g^?1 at 0.2, 0.5, 1, 2, 5, and 10C, respectively), and stable cycling performance (≈26% capacity loss after long 150 cycles at 1C with a capacity retention of 365 mA h g^?1). When the work voltage is extended into 0.01–3.0 V, a higher stable capacity of 1600 mA h g^?1 at a current density of 100 mA g^?1 is still achieved.     

Tuning the Solid Electrolyte Interphase for Selective Li‐ and Na‐Ion Storage in Hard Carbon

Solid‐electrolyte interphase (SEI) films with controllable properties are highly desirable for improving battery performance. In this paper, a combined experimental and theoretical approach is used to study SEI films formed on hard carbon in Li‐ and Na‐ion batteries. It is shown that a stable SEI layer can be designed by precycling an electrode in a desired Li‐ or Na‐based electrolyte, and that ionic transport can be kinetically controlled. Selective Li‐ and Na‐based SEI membranes are produced using Li‐ or Na‐based electrolytes, respectively. The Na‐based SEI allows easy transport of Li ions, while the Li‐based SEI shuts off Na‐ion transport. Na‐ion storage can be manipulated by tuning the SEI layer with film‐forming electrolyte additives, or by preforming an SEI layer on the electrode surface. The Na specific capacity can be controlled to < 25 mAh g^?1; ≈ 1/10 of the normal capacity (250 mAh g^?1). Unusual selective/preferential transport of Li ions is demonstrated by preforming an SEI layer on the electrode surface and corroborated with a mixed electrolyte. This work may provide new guidance for preparing good ion‐selective conductors using electrochemical approaches.