Low‐Defect and Low‐Porosity Hard Carbon with High Coulombic Efficiency and High Capacity for Practical Sodium Ion Battery Anode

Hard carbon is regarded as the most promising anode material for commercialization of Na ion batteries because of its high capacity and low cost. At present, the practical utilization of hard carbon anodes is largely limited by the low initial Coulombic efficiency (ICE). Na ions have been found to adopt an adsorption–insertion storage mechanism. In this paper a systematic way to control the defect concentration and porosity of hard carbon with similar overall architectures is shown. This study elucidates that the defects in the graphite layers are directly related to the ICE as they would trap Na ions and create a repulsive electric field for other Na ions so as to shorten the low‐voltage intercalation capacity. The obtained low defect and porosity hard carbon electrode has achieved the highest ICE of 86.1% (94.5% for pure hard carbon material by subtracting that of the conductive carbon black), reversible capacity of 361 mA h g^?1, and excellent cycle stability (93.4% of capacity retention over 100 cycles). This result sheds light on feasible design principles for high performance Na storage hard carbon: suitable carbon layer distance and defect free graphitic layers.     

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g^?1 specific capacity, twice of the capacity (≈100 mAh g^?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g^?1 current density (4 C rate, 1 C = 250 mA g^?1) with a specific capacity of ≈150 mAh g^?1, ≈15 times of the capacity (10 mAh g^?1) in carbonate. The full cell of Na₃V₂(PO₄)₃‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g^?1 based on Na₃V₂(PO₄)₃ cathode, ≈2.5 times of the value (≈40 mAh g^?1) with nontreated HC. This work provides new perception on the anode development for SIBs.     

Silicon Anode with High Initial Coulombic Efficiency by Modulated Trifunctional Binder for High‐Areal‐Capacity Lithium‐Ion Batteries

High‐capacity electrode materials play a vital role for high‐energy‐density lithium‐ion batteries. Silicon (Si) has been regarded as a promising anode material because of its outstanding theoretical capacity, but it suffers from an inherent volume expansion problem. Binders have demonstrated improvements in the electrochemical performance of Si anodes. Achieving ultrahigh‐areal‐capacity Si anodes with rational binder strategies remains a significant challenge. Herein, a binder‐lithiated strategy is proposed for ultrahigh‐areal‐capacity Si anodes. A hard/soft modulated trifunctional network binder (N‐P‐LiPN) is constructed by the partially lithiated hard polyacrylic acid as a framework and partially lithiated soft Nafion as a buffer via the hydrogen binding effect. N‐P‐LiPN has strong adhesion and mechanical properties to accommodate huge volume change of the Si anode. In addition, lithium‐ions are transferred via the lithiated groups of N‐P‐LiPN, which significantly enhances the ionic conductivity of the Si anode. Hence, the Si@N‐P‐LiPN electrodes achieve the highest initial Coulombic efficiency of 93.18% and a stable cycling performance for 500 cycles at 0.2 C. Specially, Si@N‐P‐LiPN electrodes demonstrate an ultrahigh‐areal‐capacity of 49.59 mAh cm^?2. This work offers a new approach for inspiring the battery community to explore novel binders for next‐generation high‐energy‐density storage devices.     

Soft Carbon as Anode for High‐Performance Sodium‐Based Dual Ion Full Battery

Sodium‐based dual ion full batteries (NDIBs) are reported with soft carbon as anode and graphite as cathode for the first time. The NDIBs operate at high discharge voltage plateau of 3.58 V, with superior discharge capacity of 103 mA h g^?1, excellent rate performance, and long‐term cycling stability over 800 cycles with capacity retention of 81.8%. The mechanism of Na⁺ and PF₆^? insertion/desertion during the charging/discharging processes is proposed and discussed in detail, with the support of various spectroscopies.     

Hard Carbon Microtubes Made from Renewable Cotton as High‐Performance Anode Material for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have attracted more and more attention for scalable electrical energy storage due to the abundance and wide distribution of Na resources. However, the anode still remains a great challenge for the application of SIBs. Here the production of uniform hard carbon microtubes (HCTs) made from natural cotton through one simple carbonization process and their application as an anode are reported. The study shows that the electrochemical performance of the HCTs is seriously affected by the carbonization temperature due to the difference in their microstructure and heteroatomic content. The HCTs carbonized at 1300 °C deliver the highest reversible capacity of 315 mAh g^?1 and good rate capability due to their unique tubular structure. This contribution not only provides a new approach for the preparation of hard carbon materials with unique tubular microstructure using natural inspiration, but it also deepens the fundamental understanding of the sodium storage mechanism.     

Manipulating Adsorption–Insertion Mechanisms in Nanostructured Carbon Materials for High‐Efficiency Sodium Ion Storage

Hard carbon is one of the most promising anode materials for sodium‐ion batteries, but the low Coulombic efficiency is still a key barrier. In this paper, a series of nanostructured hard carbon materials with controlled architectures is synthesized. Using a combination of in situ X‐ray diffraction mapping, ex situ nuclear magnetic resonance (NMR), electron paramagnetic resonance, electrochemical techniques, and simulations, an “adsorption–intercalation” mechanism is established for Na ion storage. During the initial stages of Na insertion, Na ions adsorb on the defect sites of hard carbon with a wide adsorption energy distribution, producing a sloping voltage profile. In the second stage, Na ions intercalate into graphitic layers with suitable spacing to form NaC _x compounds similar to the Li ion intercalation process in graphite, producing a flat low voltage plateau. The cation intercalation with a flat voltage plateau should be enhanced and the sloping region should be avoided. Guided by this knowledge, nonporous hard carbon material has been developed which has achieved high reversible capacity and Coulombic efficiency to fulfill practical application.     

An Ultralong Lifespan and Low‐Temperature Workable Sodium‐Ion Full Battery for Stationary Energy Storage

Presently, commercialization of sodium‐ion batteries (SIBs) is still hindered by the relatively poor energy‐storage performance. In addition, low‐temperature (low‐T) Na storage is another principal concern for the wide application of SIBs. Unfortunately, the Na‐transfer kinetics is extremely sluggish at low‐T, as a result, there are few reports on low‐T SIBs. Here, an advanced low‐T sodium‐ion full battery (SIFB) assembled by an anode of 3D Se/graphene composite and a high‐voltage cathode (Na₃V₂(PO₄)₂O₂F) is developed, exhibiting ultralong lifespan (over even 15 000 cycles, the capacity retention is still up to 86.3% at 1 A g^?1), outstanding low‐T energy storage performance (e.g., all values of capacity retention are >75% after 1000 cycles at temperatures from 25 to ?25 °C at 0.4 A g^?1), and high‐energy/power properties. Such ultralong lifespan signifies that the developed sodium‐ion full battery can be used for longer than 60 years, if batteries charge/discharge once a day and 80% capacity retention is the standard of battery life. As a result, the present study not only promotes the practicability and commercialization of SIBs but also points out the new developing directions of next‐generation energy storage for wider range applications.     

An Ultrafast Rechargeable Hybrid Sodium‐Based Dual‐Ion Capacitor Based on Hard Carbon Cathodes

Hybrid sodium‐based dual‐ion capacitors (NDICs), which integrate the advantages of supercapacitors and sodium‐ion batteries, have attracted tremendous attention recently. In this work, hybrid sodium‐based dual‐ion capacitors are successfully developed with nitrogen‐doped microporous hard carbon as the cathode and soft carbon as the anode. N‐doping is beneficial to the functional groups, porous structure, and electric conductivity of hard carbon. Hybrid NDICs possess a wide voltage range (0.01–4.7 V), high‐energy density of 245.7 W h kg^?1 at a power density of 1626 W kg^?1, long cycle life (1000 cycles), and outstanding rate performance.     

Defect‐Rich Soft Carbon Porous Nanosheets for Fast and High‐Capacity Sodium‐Ion Storage

Soft carbon has attracted tremendous attention as an anode in rocking‐chair batteries owing to its exceptional properties including low‐cost, tunable interlayer distance, and favorable electronic conductivity. However, it fails to exhibit decent performance for sodium‐ion storage owing to difficulties in the formation of sodium intercalation compounds. Here, microporous soft carbon nanosheets are developed via a microwave induced exfoliation strategy from a conventional soft carbon compound obtained by pyrolysis of 3,4,9,10‐perylene tetracarboxylic dianhydride. The micropores and defects at the edges synergistically leads to enhanced kinetics and extra sodium‐ion storage sites, which contribute to the capacity increase from 134 to 232 mAh g^?1 and a superior rate capability of 103 mAh g^?1 at 1000 mA g^?1 for sodium‐ion storage. In addition, the capacitance‐dominated sodium‐ion storage mechanism is identified through the kinetics analysis. The in situ X‐ray diffraction analyses are used to reveal that sodium ions intercalate into graphitic layers for the first time. Furthermore, the as‐prepared nanosheets can also function as an outstanding anode for potassium‐ion storage (reversible capacity of 291 mAh g^?1) and dual‐ion full cell (cell‐level capacity of 61 mAh g^?1 and average working voltage of 4.2 V). These properties represent the potential of soft carbon for achieving high‐energy, high‐rate, and low‐cost energy storage systems.     

Elucidation of the Sodium‐Storage Mechanism in Hard Carbons

Hard carbons (HCs) are the most promising candidate anode materials for emerging Na‐ion batteries (NIBs). HCs are composed of misaligned graphene sheets with plentiful nanopores and defects, imparting a complex correlation between its structure and sodium‐storage behavior. The currently debated mechanism of Na⁺‐ion insertion in HCs hinders the development of high‐performance NIBs. In this article, ingenious and reliable strategies are used to elaborate the correlation between the structure and electrochemical performance and further illuminate the sodium‐storage mechanism in HCs. First, filling sulfur into the micropores of HCs can remove the low‐voltage plateau, providing solid evidence for its association with the pore‐filling mechanism. Along with the decreased concentration of defects/heteroatoms at higher treatment temperature, the reduced sloping capacity confirms the adsorption mechanism in the sloping region. Finally, the similar sodium‐insertion behaviors of HCs with ether‐based and ester‐based electrolytes indicate that no Na⁺ ions intercalate between the graphene layers. The determined adsorption‐pore‐filling mechanism encourages the design of more efficient HC anode materials with high capacity for high‐energy NIBs.     

In Situ Subangstrom‐Thick Organic Engineering Enables Mono‐scale,Ultrasmall ZnO Nanocrystals for a High Initial Coulombic Efficiency,Fully Reversible Conversion,and Cycle‐Stable Li‐Ion Storage

A solid electrolyte interphase (SEI)‐free surface and fully reversible conversion are simultaneously realized in the Li‐ion storage of a specially designed ZnO porous nanocomposite with in situ surfaces/interfaces organic encapsulation for the first time. The built‐in oxygen‐ and/or moisture‐isolating organic layer of subangstrom thickness not only avoids the SEI formation, but also guarantees monodisperse and ultrasmall dimensions of ZnO nanocrystals, which are crucial for the high initial Coulombic efficiency (ICE) and fully reversible conversion. Benefiting from the high ICE up to 91.4%, stable long‐term cyclibility (95% capacity retention at 1 A g^?1 after 1400 cycles), and no sacrificing Li‐ion storage capability (868 mAh g^?1 at 0.1 A g^?1), the ZnO nanocomposite demonstrates the highest initial Li‐ion utilization efficiency (ILUE, ≈85.4%) among previous transition metal oxide–based full cells.     

Sodium‐Ion Batteries: From Academic Research to Practical Commercialization

Sodium‐ion batteries (SIBs) have been considered as the most promising candidate for large‐scale energy storage system owing to the economic efficiency resulting from abundant sodium resources, superior safety, and similar chemical properties to the commercial lithium‐ion battery. Despite the long period of academic research, how to realize sodium‐ion battery commercialization for market applications is still a great challenge. Thus, from the perspective of future practical application, this review will identify the factors that are restricting commercialization, and evaluate the existing active materials and sodium‐ion‐based full‐cell system. The design and development trends that are needed for SIBs to meet the requirements of practical applications in large‐scale energy storage will also be discussed in detail.     

Spontaneous Growth of 3D Framework Carbon from Sodium Citrate for High Energy‐ and Power‐Density and Long‐Life Sodium‐Ion Hybrid Capacitors

Carbon sheets with 3D architectures, large graphitic interlayer spacing, and high electrical conductivity are highly expected to be an ideal anode material for sodium‐ion hybrid capacitors (SIHCs). Pursuing a simple synthesis methodology and advancing it from the laboratory to industry is of great importance. In this study, a new approach is presented to prepare 3D framework carbon (3DFC) with the above integrated advantages by a direct calcination of sodium citrate without aid of any additional carbon source, template, or catalyst. The first‐principle calculations verify that the large interlayer spacing and the curvature structure of 3DFC facilitate the sodium ion insertion/extraction. As a consequence, the optimal 3DFC sample exhibits high reversible capacity as well as excellent rate and cycling performance. On this basis, a dual‐carbon SIHC is fabricated by employing 3DFC as battery‐type anode and 3DFC‐derived nanoporous carbon as capacitor‐type cathode. It is able to deliver high energy‐ and power‐density feature as well as outstanding long‐term cycling stability in the potential range of 0–4.0 V. This study may open an avenue for developing high‐performance carbon electrode materials and pushes the practical applications of SIHCs a decisive step forward.     

Fabrication of Hierarchical Potassium Titanium Phosphate Spheroids: A Host Material for Sodium‐Ion and Potassium‐Ion Storage

Identifying suitable electrode materials for sodium‐ion and potassium‐ion storage holds the key to the development of earth‐abundant energy‐storage technologies. This study reports an anode material based on self‐assembled hierarchical spheroid‐like KTi₂(PO₄)₃@C nanocomposites synthesized via an electrospray method. Such an architecture synergistically combines the advantages of the conductive carbon network and allows sufficient space for the infiltration of the electrolyte from the porous structure, leading to an impressive electrochemical performance, as reflected by the high reversible capacity (283.7 mA h g^?1 for Na‐ion batteries; 292.7 mA h g^?1 for K‐ion batteries) and superior rate capability (136.1 mA h g^?1 at 10 A g^?1 for Na‐ion batteries; 133.1 mA h g^?1 at 1 A g^?1 for K‐ion batteries) of the resulting material. Moreover, the different ion diffusion behaviors in the two systems are revealed to account for the difference in rate performance. These findings suggest that KTi₂(PO₄)₃@C is a promising candidate as an anode material for sodium‐ion and potassium‐ion batteries. In particular, the present synthetic approach could be extended to other functional electrode materials for energy‐storage materials.     

Mechanism of Na‐Ion Storage in Hard Carbon Anodes Revealed by Heteroatom Doping

Hard carbon is the leading candidate anode for commercialization of Na‐ion batteries. Hard carbon has a unique local atomic structure, which is composed of nanodomains of layered rumpled sheets that have short‐range local order resembling graphene within each layer, but complete disorder along the c‐axis between layers. A primary challenge holding back the development of Na‐ion batteries is that a complete understanding of the structure–capacity correlations of Na‐ion storage in hard carbon has remained elusive. This article presents two key discoveries: first, the characteristics of hard carbons structure can be modified systematically by heteroatom doping, and second, that these structural changes greatly affect Na‐ion storage properties, which reveals the mechanisms for Na storage in hard carbon. Specifically, via P or S doping, the interlayer spacing is dilated, which extends the low‐voltage plateau capacity, while increasing the defect concentrations with P or B doping leads to higher sloping sodiation capacity. The combined experimental studies and first principles calculations reveal that it is the Na‐ion‐defect binding that corresponds to the sloping capacity, while the Na intercalation between graphenic layers causes the low‐potential plateau capacity. The understanding suggests a new design principle of hard carbon anode: more reversibly binding defects and dilated turbostratic domains, given that the specific surface area is maintained low.