Sodium-ion Capacitors Research Articles

Local Oxygen Reconstruction Enables Dual‐Ion Active Sites in Carbon Cathode for High Energy Density Sodium‐Ion Capacitors

AbstractCarbon materials are the promising cathode material for sodium‐ion capacitors (SICs) with high energy/power density, however, clarifying the evolution processes of functional groups in carbon materials and revealing their energy storage mechanisms are full of challenges. Inspired by the ancient practice of alchemy, which sought to purify Dan medicine and remove impurities through precise control of the refining temperature, the local oxygen reconstruction strategy, to alter the functional groups species in SP3‐C, is pioneeringly utilized, achieving targeted regulation of carbonyl groups with increase from 27.9 to 43.3 at%, which efficiently change the electronic structure of the carbon framework and realize the dual‐ion adsorption of Na+ and ClO4−, according well with the theoretical calculations. As expected, the obtained carbon cathode delivers a specific capacity of 145 mAh g−1, higher than that of the parent carbon material (95 mAh g−1). Impressively, the ex situ X‐ray Photoelectron Spectroscopy and in situ Raman reveals that carbonyl can act as dual‐ion active sites for Na+ and ClO4− through pseudocapacitive behavior under different voltage states. Notably, the assembled SIC using the carbonyl‐rich carbon cathode exhibits an ultrahigh energy density of 162 Wh kg−1. This work opens a novel avenue for regulating the carbonyl content of carbon materials.

A Novel Hierarchical Porous Covalent Organic Framework as Multi‐Active‐Center Anode for High‐Performance Sodium Ion Capacitors

A Novel Hierarchical Porous Covalent Organic Framework as Multi‐Active‐Center Anode for High‐Performance Sodium Ion Capacitors

Pseudocapacitive Jarosite Cathode Enabling High-Energy-Density Sodium-Ion Capacitors

Pseudocapacitive Jarosite Cathode Enabling High-Energy-Density Sodium-Ion Capacitors

Experimental and theoretical investigation of high-performance green-synthesized NaTiO2/AC nanocomposite as high-capacity electrodes for next-generation sodium-ion capacitors

Experimental and theoretical investigation of high-performance green-synthesized NaTiO2/AC nanocomposite as high-capacity electrodes for next-generation sodium-ion capacitors

Surface coating engineering of titanate anodes based on tannic acid-formaldehyde polymer chelating bismuth ions for advanced sodium-ion capacitors

As a battery-type anode material for sodium ion capacitors (SICs), titanate (H2Ti2O5·H2O, HTO) exhibits good rate capability due to its layered structure, easy to insert Na+ ions and low potential during sodium-ion storage. However, the structure is unstable due to the lattice distortion resulting from the irreversible embedment of Na+ in the process of sodium storage. So there is a significant mismatch between the dynamic reaction of the HTO anode and the capacitive cathode. Surface coating engineering is a useful strategy for stabilizing the HTO structure, which is critical for improving the kinetic response. In this work, a surface coating technique is designed to enhance the surface of HTO nanoarrays on titanium foil by using the oligomers of tannic acid formaldehyde polymer (TAF) chelated Bi3+ ions (Bi-TAF). As a binder-free anode, HTO coated with Bi-TAF (HTO@Bi-TAF) exhibits more excellent capacity (335.2 mA h g−1, 0.1 A g−1), rate capability (212.3 mA h g−1, 2.0 A g−1), and cycle stability (97 % capacity maintenance following 2000 cycles at 1.0 A g−1) than HTO and HTO coated with TAF (HTO@TAF). At the sweep rate of 1.0 mV s−1, the kinetic investigation reveals that the capacitance contribution of HTO@Bi-TAF is 86 %. The SICs exhibit a significant energy/power density (89.4 Wh kg−1/250 W kg−1). This work shows that the Bi-TAF polymer coating has a dual effect of rate capability improvement and structural protection on the prepared HTO. This results in a reasonable and effective surface coating strategy that provides outstanding rate capability and extended cycle performance of titanium-based anode materials for SICs.

Unveiling the Microscopic Origin of Ultrahigh Initial Coulombic Efficiency of High-Entropy Metal-Organic Frameworks for Sodium Storage.

The initial irreversible capacity loss during the first charging process largely reduces the affordable energy and power density of sodium storage devices, and developing advanced materials is the efficient way to solve this problem, which is fraught with challenges. Herein, inspired by theoretical calculations and the high-entropy concept, a series of fewer layers of high-entropy metal-organic frameworks (FLHE-MOFs) are successfully fabricated, delivering an ultrahigh initial Coulombic efficiency (ICE) of 86.1% and excellent cycling performance, which is far more than that of the other electrode materials (generally <70%). Greatly, the storage behavior of high-, medium-, and low-entropy MOFs is clarified by theoretical calculations and in-/ex-situ characterization, revealing that Co and Fe species can provide substantial sodium storage sites and largely enhance the charge transfer rate, whereas high-entropy effect can enable structural reversibility. Sodium ion capacitors constructed with FLHE-MOFs as the anode can provide an ultrahigh energy density of 121.8 W h kg-1 (200 W kg-1) and an extremely long-term cycle lifespan. This work not only breaks the limitation of MOF materials with poor performance for sodium storage but also provides an effective strategy for the fabrication and application of high-performance MOF-based anode materials with high ICE, in which this idea may also be applied in other fields.

Hollow porous Co0.85Se/MoSe2@MXene heterostructured anode for sodium-ion hybrid capacitors

Metal selenides have garnered significant attention as promising anode materials for sodium-ion hybrid capacitors (SIHCs), yet its sluggish reaction kinetics as the battery-type anodes pose a challenge for developing high power SIHCs when coupled with capacitor-type cathodes. To overcome this limitation, constructing heterostructured metal selenides anodes has emerged as a promising strategy to balance the reaction kinetics between two different types of electrodes. Herein, the hollow porous TA-Co0.85Se/MoSe2@MXene anode with multiple heterostructures for sodium storage has been engineered via facile double-etching and self-assembly approach. The well-tailored void space and abundant heterointerfaces may effectively mitigate volumetric changes and enhance structural stability. Density functional theory (DFT) calculations further reveal that the local multilevel built-in electric fields induced by the heterointerfaces can effectively accelerate charge transfer and reduce the migration energy barrier of Na+, thus boosting the reaction kinetics. The fabricated anode demonstrates superior long-term cycling performance with a reversible capacity of 414 mA h/g after 1000 cycles at 1 A/g and remarkable rate capability of 425 mA h/g at 5 A/g. Benefiting from the ingenious structure and excellent sodium storage performance, the as-built SIHCs achieves an impressive energy density of 193 W h kg−1 and high power output of 18 kW kg−1 with outstanding capacitance retention of 90 % at 2 A/g after 10,000 cycles. This study provides valuable insights into the rational design of multiple heterostructured anode materials with multilevel built-in electric fields for high-performance SIHCs.

Hollow carbon nanofibers with self-induced internal electric field for high-performance full-carbon sodium ion capacitors

Self-induced internal electric field (SIEF) is crucial to achieve high capacity, high rate and long cycle life of carbon anodes in Na+ storage, but it is also a huge challenge currently. Herein, a template-assisted electrospinning process and subsequent low-temperature pyrolysis method is employed to synthesize S, N co-doped hollow carbon nanofibers (SNHCF) with rich micropores and chemisorption sites. The rich micropores and interconnected macroporous in SNHCF provide large internal availability that effectively exposing the active sites, inhibiting the volume expansion and shortening the Na+ diffusion distance. Besides, S, N co-doping in the carbon skeleton can act as an electron acceptor and electron donor respectively to form a SIEF to boost adsorption of Na+. Theoretical calculation and ex-situ characterizations confirmed that S, N co-doping can regulate the electronic configuration and reduce the diffusion barrier of Na+. As a result, SNHCF anode has ultra-high specific capacity (588.2mAh g−1 at 0.05 A/g) and impressive rate performance (264.3mAh g−1 at 20 A/g). The full-carbon sodium ion capacitors assembled with SNHCF anode and activated carbon cathode exhibits high energy density (119 Wh kg−1) and ultra-long cycle stability (80.06 % capacity retention after 12,000 cycles).

S/N Co-Doped Ultrathin TiO2 Nanoplates as an Anode Material for Advanced Sodium-Ion Hybrid Capacitors.

Anatase titanium dioxide (TiO2) has emerged as a potential anode material for sodium-ion hybrid capacitors (SICs) in terms of its nontoxicity, high structure stability and cost-effectiveness. However, its inherent poor electrical conductivity and limited reversible capacity greatly hinder its practical application. Here, ultrathin TiO2 nanoplates were synthesized utilizing a hydrothermal technique. The electrochemical kinetics and reversible capacity were significantly improved through sulfur and nitrogen co-doping combined with carbon coating (SN-TiO2/C). Sulfur and nitrogen co-doping generated oxygen vacancies and introduced additional active sites within TiO2, facilitating accelerated Na-ion diffusion and enhancing its reversible capacity. Furthermore, carbon coating provided stable support for electron transfer in SN-TiO2/C during repeated cycling. This synergistic strategy of sulfur and nitrogen co-doping with carbon coating for TiO2 led to a remarkable capacity of 335.3 mAh g-1 at 0.1 A g-1, exceptional rate property of 148.3 mAh g-1 at 15 A g-1 and a robust cycling capacity. Thus, the SN-TiO2/C//AC SIC delivered an impressive energy density of 177.9 W h kg-1. This work proposes an idea for the enhancement of reaction kinetics for energy storage materials through a synergistic strategy.

Enhancing the stability of sodium-ion capacitors by introducing glyoxylic-acetal based electrolyte

Sodium-ion Capacitors (SICs) are becoming increasingly important energy storage devices. This study presents an in-depth comparison of a largely used electrolyte for said application, sodium hexafluorophosphate in ethylene carbonate:propylene carbonate (NaPF6 in EC:PC), with the novel electrolyte sodium bis(trifluoromethanesulfonyl)imide in 1,1,2,2-tetraethoxyethane:propylene carbonate (NaTFSI in TEG:PC). Firstly, half-cells of the SIC standard electrode materials, hard carbon (HC) and activated carbon (AC), are shown to perform comparably well with the two electrolytes. However, the use of the novel electrolyte in SICs allows for an improved stability during float tests. All in all, the novel electrolyte NaTFSI in TEG:PC appears to be a very promising alternative electrolyte for SIC application.

Organic-inorganic coupled Ti3CN MXene achieving the excellent sodium-ion storage performance

Two-dimensional (2D) transition metal carbides/nitrides (MXenes) are attracting considerable attention due to their unique multilayered structure. However, the practical application of MXenes as electrode materials is hampered by sluggish ions diffusion kinetics and serious volume variation during charging and discharging cycles. Herein, the organic-inorganic coupled Ti3CN (Ti3CNNHSA) composites were constructed by anchoring succinic acid (SA) molecules into the interlayer of Ti3CN. The anchored SA molecules contribute pillar effects to increase interlayer spacing and inhibit the volume contraction during Na+ ions extraction processes, as well as strain effects to mitigate volume expansion during Na+ ions insertion processes. Consequently, the Ti3CNNHSA composites not only exhibit the increased interlayer spacing and rapid ions transfer paths but also deliver the enhanced structural stability and maximum utilization of layered structure, realizing extraordinary cycle stability and high rate capability. The Ti3CNNHSA exhibits a superior capacity retention of 95.2% after 400 cycles at 0.1 A g-1. The Ti3CNNHSA//AC sodium-ion capacitor (SIC) also displays a capacity retention of 84.1% after 1200 cycles at 1.0 A g-1 and a high energy density of 76 Wh kg-1 at the power density of 200 W kg-1. Such an organic-inorganic coupled Ti3CNNHSA sheds light on the development of 2D layered materials.

Zinc selenide/cobalt selenide in nitrogen-doped carbon frameworks as anode materials for high-performance sodium-ion hybrid capacitors

Zinc selenide/cobalt selenide in nitrogen-doped carbon frameworks as anode materials for high-performance sodium-ion hybrid capacitors

Pseudocapacitive Na ion storage in binder-less, carbon additive-free Nb2O5-x electrode synthesised via solvothermal-assisted electro-coating with enhanced areal capacitance and lowered impedance parameters

Negatrodes with wide negative operating voltage, high electrochemical storage capacity, and intrinsic metal ion intercalation abilities are vital to the continuous development of storage devices with simultaneous energy and power density improvement. Herein, we report binder-less coating of non-stoichiometric vacancy-implanted Nb2O5-x as carbon additive-free negatrode on FTO substrate for asymmetric supercapacitor and sodium ion capacitor applications. The negatrode was fabricated through vacuum-less and low-temperature solvothermal-assisted electro-coating technique and yielded several orders of enhancement in its areal capacitance and retained ca. 90 % of its capacity after 5000 cycles of charge-discharge in aqueous Na+ electrolyte. The solvothermal treated electro-coated electrode (STT_Nb2O5-x) achieved an areal capacitance of 22.58 mF/cm2, which was far higher than those of hydrothermal-treated electro-coated HTT_Nb2O5 and Nb2O5 electrodes. The solvothermal treatment simultaneously enhanced the electro-coated samples' impedance properties and mass load through oxygen vacancy implantation and re-crystallization of the electro-coated Nb2O5 layer, respectively. This study presented a facile and energy-efficient technique of direct coating of defect-enhanced pseudocapacitive nanomaterials for the fabrication of electrochemical storage devices.

An Engineering Porous Spherical Carbon Cathode for High-Energy Sodium-Ion Capacitor.

Sodium-ion hybrid capacitors (SICs) are emerging as promising devices that can balance energy and power output. However, the lack of a high-capacity cathode that can match the anode has limited its further application. In this work, we develop an efficient method to prepare spherical porous carbons (SPCs) with great specific surface area and narrow pore size distribution from coal-based humic acid via spray drying and a subsequent chemical activation process. Thanks to this unique porous structure, the SPC cathode has a superb capacity of 223 F g-1 at 0.05 A g-1, as well as splendid rate performance and cycling stability. SICs constructed by an SPC cathode and hard carbon anode can exhibit a high energy density of 179.8 Wh kg-1 at 155 W kg-1 and achieved 89.4% capacity retention after 10 000 cycles at 0.5 A g-1. This outcome presents a viable approach to attaining high-capacity cathodes for constructing outstanding performance hybrid capacitors.

A novel hybrid sodium ion capacitor based on Na [Ni0.60Mn0.35Co0.05] O2 battery type cathode and presodiated D-Ti3C2Tx pseudocapacitive anode

The combination of the high-power density of supercapacitors and the high energy density of batteries makes hybrid sodium-ion capacitors (HSICs) a promising device. HSICs can provide better performance characteristics by harnessing both ion adsorption/desorption in the capacitor-type electrode and sodium-ion intercalation in the battery-type electrode. Here, the synthesis of MXene (Ti3C2Tx), a two-dimensional (2D) carbide and nitride is reported. Delaminated MXene (D-Ti3C2Tx) is a promising candidate for anode material in HSIC due to its large surface area (∼ 42 m2/g) and good electronic conductivity. Electrochemical study indicates that D-Ti3C2Tx anode exhibits a high discharge capacity of ∼213 mAh/g at a current rate of 20 mA/g. Further the presodiated D-Ti3C2Tx anode is paired with Na [Ni0.60Mn0.35Co0.05] O2 (P2-NMC) cathode to obtain the configuration of HSIC. The HSIC exhibits good specific capacitance of ∼187 F/g and specific discharge capacity of ∼110 mAh/g at a current density of 10 mA/g, according to the electrochemical analysis. A notable improvement in specific energy density (∼ 256 Wh/kg) and specific power density (∼579 W/kg) is also demonstrated by the HSIC. With P2-NMC being used as the cathode material rather than traditional activated carbon, there has been a rise in specific energy density.

CuS modified graphite from spent Li-ion batteries towards building high energy Na-ion capacitors via solvent-co-intercalation process

Sodium-ion capacitors (NICs) are one of the most modern hybrid energy storage devices, and they involve two different energy storage mechanisms (faradaic and non-faradaic). The NICs are bridging the gap between the Na-ion batteries and the capacitors with enhanced power and energy densities. This work explores a new combination electrode material, i.e., recovered graphite (RG) decorated with copper sulphide (CuS, CS) as the anode for the NIC application, in which graphite undergoes the solvent-co-intercalation process, and CuS adopts the conversion reaction. We also report the possibility of efficient direct recovery of the anode of dead/spent Li-ion batteries and upcycling as a battery-type component for NIC with commercially available activated carbon (AC) as the capacitor-type cathode. First, the Na-storage property is analyzed in the half-cell configuration, where the Na/RG-CS half-cell displayed excellent cyclic stability with a stable specific capacity of 113 mAh g−1 after 500 cycles with >96% coulombic efficiency in ether solutions. With a pre-sodiated form of RG-CS as anode and mass-balanced AC as a cathode, the NIC is fabricated. The NIC displayed a superior energy density of 64.6 Wh kg−1 with ultra-long cyclability for more than 10,000 cycles with >85% capacity retention. The compatibility of the NIC in different environmental conditions is also studied, and the cell renders better performance in all temperature conditions.

Synergetic interface engineering and space-confined effect in CoSe2@Ti3C2Tx heterostructure for high power and long life sodium ion capacitors

The intriguing characteristics of two-dimensional (2D) heterostructures stem from their unique interfaces, which can improve ion storage capability and rate performance. However, there are still challenges in increasing the proportion of heterogeneous interfaces in materials and understanding the complex interaction mechanisms at these interfaces. Here, we have successfully synthesized confined CoSe2 within the interlayer space of Ti3C2Tx through a simple solvothermal method, resulting in the formation of a superlattice-like heterostructures of CoSe2@Ti3C2Tx. Both density functional theory (DFT) calculations and experimental results show that compared with CoSe2 and Ti3C2Tx, CoSe2@Ti3C2Tx can significantly improve adsorption of Na+ ions, while maintaining low volume expansion and high Na+ ions migration rate. The heterostructure formed by MXene and CoSe2 is a Schottky heterostructure, and its interfacial charge transfer induces a built-in electric field that promotes rapid ion transport. When CoSe2@Ti3C2Tx was used as an anode material, it exhibits a high specific capacity of up to 600.1 mAh/g and an excellent rate performance of 206.3 mAh/g at 20 A/g. By utilizing CoSe2@Ti3C2Tx as the anode and activated carbon (AC) as the cathode, the sodium-ion capacitor of CoSe2@Ti3C2Tx//AC exhibits excellent energy and power density (125.0 Wh kg−1 and 22.5 kW kg−1 at 300.0 W kg−1 and 37.5 Wh kg−1, respectively), as well as a long service life (86.3 % capacity retention over 15,300 cycles at 5 A/g), demonstrating its potential for practical applications.

Engineering multiple heterogeneous Co/CoSe/MoSe2 embedded in carbon nanofibers with Co/Mo–Se–C bonding towards high performance sodium ion capacitors

MoSe2, as a representative two-dimensional transition selenide with a broad interlayer distance of 0.65 nm and a high theoretical capacity of 422 mAh g−1, is considered an optimal anode material for sodium-ion batteries (SIBs). However, its unsatisfactory electrical conduction and structural instability often lead to severe capacity decay during cycling, hindering its large-scale application in SIBs. To overcome these challenges, coupling heterostructures has been identified as an effective solution. The establishment of multiple heterointerfaces can minimize interface diffusion resistance, significantly enhancing ion and electron delivery dynamics compared to a single component. In this work, multiple heterogeneous Co/CoSe/MoSe2 uniformly distributed in carbon nanofibers (CNF) via Co/Mo–Se–C bonding are successfully synthesized using electrospinning and subsequent calcination. Importantly, the Co/CoSe and Co/MoSe2 heterointerfaces can greatly accelerate charge transfer and improve Na + adsorption capability compared to the CoSe/MoSe2 heterostructure, as corroborated by theoretical calculations. Given the high rate performance of Co/CoSe/MoSe2@CNF as an anode in SIBs (267.9 mAh g−1 at 5 A g−1), a rocking-chair sodium-ion capacitor (SIC) incorporating a Co/CoSe/MoSe2@CNF anode and a Na3V2(PO4)3 cathode is proposed, delivering high energy densities of 199.1 Wh kg−1 at 180 W kg−1 and 126.8 Wh kg−1 at 3280 W kg−1.

Coal-derived boron and phosphorus co-doped activated carbon with expanded interlayer space for high performance sodium ion capacitor anode

Aiming at the key problem of Na+ insertion difficulty and low charge transfer efficiency of activated carbon materials. It is an effective strategy to increase the lattice spacing and defect concentration by doping to reduce the ion diffusion resistance and improve the kinetics. Hence, anthracitic coal is used to prepare activated carbon (AC) and B,P-doped activated carbon (B,P-AC) as the cathode and anode materials for high-performance all-carbon SICs, respectively. AC cathode material has high specific surface area and reasonable micropore structure, which shows excellent capacitance performance. B,P-AC anode material has the advantages of extremely high specific surface area (1856.1 m2/g), expanded interlayer spacing (0.40 nm) and uniform distribution of B and P heteroatoms. Hence, B,P-AC anode achieves a highly reversible Na+ storage capacity of 243 mAh/g at a current density of 0.05 A/g. Density functional theory (DFT) calculations further verify that B,P-AC has stronger Na+ storage performance. The final assembled B,P-AC//AC SIC offers a high energy density of 109.78 Wh kg−1 and a high-power density of 10.03 kW kg−1. The high-performance coal-derived activated carbon of this work provides a variety of options for industrial production of electrode materials for sodium ion capacitors.

Nanocrystalline Heterostructure with Low Voltage Hysteresis for Ultrahigh-Power Sodium-Ion Capacitors

Heterostructures have garnered widespread attention for their ability to facilitate additional charge transfer, enhancing reaction kinetics and providing unprecedented effects at the interface. However, the majority of synthesized heterostructures exhibit non-uniform distribution and a scarcity of heterointerfaces, imposing significant constraints on their efficacy in sodium storage. In this study, a novel conceptualization of doping-reconstructed nanocrystalline heterostructures is introduced for the first time. Building upon this innovative concept, heterostructures characterized by uniform distribution and an abundance of heterointerfaces were successfully synthesized by reconstructing different Fe-doped Cu-based precursor into Cu2S/Cu5FeS4. Benefit by higher conductivity, a smaller sodium ion diffusion barrier, and lower voltage hysteresis, MOF-derived heterostructures maintained a capacity of 274.2 mAh g−1 after 2800 cycles at 30 A g−1. Furthermore, mineral-derived nanocrystalline heterostructures Cu2S/Cu5FeS4 (CFCS) with high tap density (3.71 g cm−3), prepared from Fe-containing copper smelting slag, exhibited a volumetric capacity 8.3 times higher than that of MOF-derived nanocrystalline heterostructures at 5.0 A g−1. The sodium-ion capacitor assembled with CFCS and activated carbon provided a high energy density of 60.1 Wh kg−1 at a high power density of 43.2 kW kg−1. This work presents a method for the controllable synthesis of uniform heterostructure with rich heterointerfaces, offering applicability.