Sodium-ion Hybrid Capacitors Research Articles

High-Energy and High-Power Pseudocapacitor–Battery Hybrid Sodium-Ion Capacitor with Na+ Intercalation Pseudocapacitance Anode

HighlightsLayered iron vanadate ultrathin nanosheets (FeVO UNSs) with a thickness of ~ 2.2 nm were synthesized by a sonicate-assisted method.Pseudocapacitive Na+ intercalation of FeVO UNSs anode delivers high initial coulombic efficiency (93.86%), high reversible capacity (292 mAh g−1), excellent rate capability, and remarkable cycling stability.A pseudocapacitor–battery hybrid SIC is assembled with the elimination of presodiation and delivers high energy and power densities.

Significant contribution of single atomic Mn implanted in carbon nanosheets to high-performance sodium–ion hybrid capacitors

Single Mn atoms in carbon nanosheets with compatible properties can compromise the kinetics and capacity mismatches between the anode and cathode for sodium–ion hybrid capacitors.

Coupling anodic/cathodic energy storage through in situ heterostructure regulation of ordered microporous carbon for sodium-ion hybrid capacitors

Two types of ordered microporous carbon are obtained through in situ heterostructure regulation and can realize anodic/cathodic energy storage. The assembled sodium-ion hybrid capacitor achieves high energy and power densities.

Pseudocapacitive porous hard carbon anode with controllable pyridinic nitrogen and thiophene sulfur co-doping for high-power dual-carbon sodium ion hybrid capacitors

A new and efficient method to regulate the configuration of nitrogen dopants, increase the content of thiophene sulfur, create micropores and adjust the defect intensity synchronously.

Sodium Ion Hybrid Capacitor in Poly-Acrylic Acid with Vinyl Silica Nano Particle Gel Electrolyte

Sodium ion hybrid capacitor (SIHC) has much attention because of abundance of sodium source and low cost. To improve the performance of SIHC stability, the poly-Acrylic Acid (PAA) cross-linked with Vinyl Silica Nano Particle (VSNP) was used as gel electrolyte. The VSNP was used as cross-linker and synthesized by Sol-Gel method with Vinyltriethoxysilane (VTES) to improve the mechanical strength of gel. Fourier-Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscope (SEM) was used to analyze C=C bond and morphology of VSNP. PAA gel was polymerized by radical polymerizaiotn with VSNP cross-linker. To measure electrochemical property, SIHC was fabricated with Na3V2(PO4)3 (NVP) cathode material and Activated Carbon (YP50F) anode material. Electrochemical Impedance Spectroscopy (EIS) was used to analyze interfaces-contact with electrode and electrolyte. After measure electrochemical property, X-ray Diffraction was measured to characterize the NVP crystallinity. By this research, It can propose the way how apply to flexible sodium ion hybrid capacitor and gel electrolyte SIHC

Mesoporous Mn-doped and carbon-coated NaTi2(PO4)3 nanocrystals as an anode material for improved performance of sodium-ion hybrid capacitors

Sodium electrochemical energy storage systems including sodium-ion battery and hybrid capacitor are attracting increasing interest in large-scale electrical energy storage due to low cost and abundant sodium resources. In particular, sodium-ion hybrid capacitor with the merits of high energy and power densities as a typical next-generation energy storage device provides a promising alternative to the currently commercial lithium-ion battery. It is highly challenging to design and prepared suitable anode materials with extraordinary performance, thereby spurring its large-scale application. Herein, mesoporous Mn-doped and carbon-coated NaTi2(PO4)3 nanocrystals are synthesized via a three-step process of solvothermal reaction, serum albumin decoration and thermal annealing. Synergistic effect rendered by NaTi2(PO4)3 particles with mesoporous structure, Mn2+ doping and ultra-thin carbon coating endows the prepared composite with facile ion/electron transportation as well as excellent reaction kinetics as an anode material for sodium-ion hybrid capacitors. In the half-cell tests, the prepared composite exhibits high reversible capacity of 116 mA h g−1 at 1 C, high-rate capability of 95 mA h g−1 at 50 C, and long-term cycling stability with high capacity of 92 mAh g−1 (88% capacity retention) after 1000 cycles at 20 C. Using the prepared composite as anode and activated carbon as cathode, the sodium-ion hybrid capacitor is assembled and it exhibits high energy/power density of 85.5 WhKg−1/5531 WKg−1. Our results indicate that Mn-doped and carbon-coated NASICON-type anodes have great potential in the sodium-based electrochemical energy storage systems.

Gas expansion-assisted preparation of 3D porous carbon nanosheet for high-performance sodium ion hybrid capacitor

Sodium ion hybrid capacitors (SIHCs) have attracted considerable attentions due to their high-energy density of batteries and high-power output of supercapacitors. However, the slow intercalation kinetics of anode and low specific capacity of cathode greatly hinder the high-performance output of the SIHCs. Herein, we develop a facile chemical gas expansion method with chemical etching to prepare 3D nitrogen and sulfur co-doped porous carbon nanosheet (PCNS). As an anode material of SIBs, the PCNS displays a high reversible capacity of 205 mAh g−1 at 0.5 A g−1, outstanding rate capability of 96 mAh g−1 at 20 A g−1, and excellent cycle performance of 180 mAh g−1 at 7 A g−1 after 10 000 cycles. Based on this good performance, a dual-carbon SIHC is assembled by battery-type anode material (PCNS) and capacitive-type cathode material (hierarchically porous carbon). This device exhibits high energy densities of 119 Wh kg−1 and 53 Wh kg−1 at power densities of 200 W kg−1 and 20 kW kg−1, respectively. Besides, it possesses a superior cycle life of 82% capacity retention after 8000 cycles. Moreover, this work provides a new idea for the synthesis of carbon materials as high-performance SIBs and SIHCs electrode materials.

Edge-Plane Exposed N-Doped Carbon Nanofibers Toward Fast K-Ion Adsorption/Diffusion Kinetics for K-Ion Capacitors

Sluggish kinetics severely limit the development of potassium-ion hybrid capacitors (PIHCs). Exposing active sites is recognized as an ideal strategy to resolve this issue, but the corresponding ma...

Carbon Nanosheet Anode for Sodium‐Ion Storage and Its Application in Sodium‐Ion Hybrid Capacitors

AbstractIn this study, sodium ion hybrid capacitors (SIHCs) constructed by using battery‐type carbon nanosheet (CNS) as anode and capacitive activated carbon (AC) as cathode are reported. The CNSs with large interlayer spacing were deposited on Na2CO3 powder by using chemical vapor deposition method. The CNS anode for sodium ion storage exhibits outstanding rate capability (138 mAh g−1 at 10 A g−1, 63 % retention of the capacity at 0.05 A g−1) and excellent long‐term cyclability at 10 A g−1 after 12500 cycles. Benifting from high performance of anodes abovemensioned, the assembled SIHC based on CNS and AC, operated in a voltage window of 1.0∼4.0 V, delivers a high specific energy of 135 Wh kg−1 at 250 W kg−1 and a maximum power of 25 kW kg−1 with the output 69 Wh kg−1.

Nb2O5 nanotubes on carbon cloth for high performance sodium-ion capacitors

Hybrid sodium-ion capacitors (SICs) bridge the gap between the supercapacitors (SCs) and batteries and have huge potential applications in large-scale energy storage. However, designing appropriate anode materials with fast kinetics behavior as well as long cycle life to match with the cathode electrodes remains a crucial challenge. Herein, Nb2O5 nanotubes and nanowire-to-nanotube homo-junctions were directly grown on the carbon cloth (CC) via a simple hydrothermal process through regulating the pH value of solution. The as-prepared Nb2O5@CC nanotubes displayed a high reversible capacity of 175 mA h g−1 at the current density of 1 A g−1 with the coulombic efficiency of 97% after 1500 cycles. Besides, the SICs fabricated with Nb2O5@CC and activated carbon (AC) electrode materials showed a high energy density of 195 W h kg−1 at 120 W kg−1, a power density of 7328 W kg−1 at 28 W h kg−1 and 80% of the capacitance retention after 5000 cycles. Additionally, the flexible SIC devices can operate normally at various bendable conditions. The Nb2O5@CC nanotubes in this work can be promising electrode materials in flexible and wearable energy storage devices.

Na2CoPO4F as a pseudocapacitive anode for high-performance and ultrastable hybrid sodium-ion capacitors

Sodium-ion capacitors (NICs) reported in the literature demonstrate relatively poor cycle retention (<90% after 10,000 cycles) and rate performance, which is not ideal for proposed applications such as regenerative brake charging. In this work, a 3 V NIC was fabricated using Na2CoPO4F (NCPF) as a next-generation anode and commercial activated carbon (AC) as the cathode in an organic electrolyte. The constructed NCPF//AC NIC exhibited exceptional rate performance, retaining 78% of its energy density (corresponding to 24 Wh kg−1) when the power density was ramped from 125 to 5000 W kg−1. In addition, its long-term stability when cycled from 0 to 3 V is among the highest reported in the literature, retaining 93% of its energy density (24 Wh kg−1) after 100,000 cycles at 1 kW kg−1. Furthermore, at an elevated voltage range of 0–3.25 V, the NIC retained 80% of its energy density (26 Wh kg−1) after 30,000 cycles at 375 W kg−1. The performance is ascribed to the kinetic compatibility between the adsorptive cathode and pseudocapacitive anode, where pseudocapacitance is enhanced by the nanosized morphology on the surface of NCPF. The NIC system reported herein demonstrates supercapacitor-type benchmarks while also possessing a higher energy density.

Coupling of bowl-like VS2 nanosheet arrays and carbon nanofiber enables ultrafast Na+-Storage and robust flexibility for sodium-ion hybrid capacitors

Sodium-ion hybrid capacitors (SIHCs) show great promise due to their combination of high energy-storage properties and low cost of Na resources. Yet most anodes in SIHCs suffer from sluggish Na+-diffusion kinetics and relatively low specific capacity, which restrict their widespread development. Herein, bowl-like VS2 nanosheet arrays are uniformly and robustly anchored on a carbon nanofiber (CNF) substrate through a one-step solvothermal method. The bowl-like VS2 is featured with an ultrathin thickness (several atomic layers), intrinsically metallic conductivity and an interconnected array architecture. This unique structural design can not only facilitate ultrafast Na+ ion-diffusion, but also suppress capacity decay of VS2 that is caused by the conversion process below 0.3 ​V. DFT calculations demonstrate a faster Na+ transport rate and a lower diffusion energy barrier for the VS2/C interface than for the VS2/VS2 bilayer. The quasi-solid-state SIHC full cell that integrates the CNF@VS2 anode and the graphene sheets-wrapped carbon nanofiber (CNF@GS) cathode, displays prominent energy//power densities in the voltage range of 0.0–4.0 ​V (116 ​Wh kg−1 ​at 0.4 ​kW ​kg−1; 66 ​Wh kg−1 ​at 40 ​kW ​kg−1 based on the total mass of both electrodes), outperforming recent SIHCs.

Three-dimensional honeycomb-like MoSe2/rGO as high performance sodium ions storage materials with long cycle stability and high rate capability

Transition metal dichalcogenides (TMDs) caused widespread concern because of their possess graphite-like two-dimensional structure, which allows Na+ reversible de-intercalation between the interlayers and contributes high theoretical capacity. However, the poor conductivity and structural instability greatly limited their application to sodium ion batteries (SIBs). Herein, three-dimensional (3D) honeycomb MoSe2/rGO nanocomposites with outstanding sodium ion storage performance were prepared. The MoSe2/rGO combined the advantages of MoSe2 and rGO. The typical layered structure of MoSe2 provide Na+ diffusion pathways and sufficient active sites, while the rGO increase conductivity and alleviate structural change during Na+ insertion/extraction process. The stable discharge capacity of MoSe2/rGO reaches 300 mAh g−1 at 0.1 A g−1 and retains 247 mAh g−1 after 100 times. It retains a high capacity of 214.7 mAh g−1 at 1 A g−1 and shows outstanding rate capability. The MoSe2/rGO//AC hybrid sodium-ion capacitors (HSIC) achieves a high capacitance of 56.7 F g−1 at 0.1 A g−1, it exhibits an energy density of 87.7 W kg−1 at a power density of 208.8 W h kg−1 and retains 50.5 W h kg−1 when it increases to 1051.4 W kg−1. The article brings up a novel opinion for designing porous TMDs based composites as ideal energy storage materials.

High-Energy-Density Sodium-Ion Hybrid Capacitors Enabled by Interface-Engineered Hierarchical TiO2 Nanosheet Anodes.

Sodium-ion hybrid capacitors are known for their high power densities and superior cycle life compared to Na-ion batteries. However, low energy densities (<100 Wh kg-1) due to the lack of high-capacity (>150 mAh g-1) anodes capable of fast charging are delaying their practical implementation. Herein, we report a high-performance Na-ion hybrid capacitor based on an interface-engineered hierarchical TiO2 nanosheet anode consisting of bronze (∼15%) and anatase (∼85%) crystallites (∼10 nm). This pseudocapacitive dual-phase anode demonstrated exceptional specific capacity of 289 mAh g-1 at 0.025 A g-1 and excellent rate capability (110 mAh g-1 at 1.0 A g-1). The Na-ion hybrid capacitor integrating a dual-phase hierarchical TiO2 nanosheet anode and an activated carbon cathode exhibited a high energy density of 200 Wh kg-1 (based on the total mass of active materials in both electrodes) and power density of 6191 W kg-1. These values are in the energy and power density range of Li-ion batteries (100-300 Wh kg-1) and supercapacitors (5000-15 000 W kg-1), respectively. Furthermore, exceptional capacity retention of 80% is observed after 5000 charge-discharge cycles. Outstanding electrochemical performance of the demonstrated Na-ion hybrid capacitor is credited to the enhanced pseudocapacitive Na-ion intercalation of the two-dimensional TiO2 anode resulting from nanointerfaces between bronze and anatase crystallites. Mechanistic investigations evidenced Na-ion storage through intercalation pseudocapacitance with minimal structural changes. This approach of nanointerface-induced pseudocapacitance presents great opportunities toward developing advanced electrode materials for next-generation Na-ion hybrid capacitors.

3D Printing of Porous Nitrogen-Doped Ti3C2 MXene Scaffolds for High-Performance Sodium-Ion Hybrid Capacitors.

3D printing technology has stimulated a burgeoning interest to fabricate customized architectures in a facile and scalable manner targeting wide ranged energy storage applications. Nevertheless, 3D-printed hybrid capacitor devices synergizing favorable energy/power density have not yet been explored thus far. Herein, we demonstrate a 3D-printed sodium-ion hybrid capacitor (SIC) based on nitrogen-doped MXene (N-Ti3C2Tx) anode and activated carbon cathode. N-Ti3C2Tx affording a well-defined porous structure and uniform nitrogen doping can be obtained via a sacrificial template method. Thus-formulated ink can be directly printed to form electrode architecture without the request of a conventional current collector. The 3D-printed SICs, with a large areal mass loading up to 15.2 mg cm-2, can harvest an areal energy/power density of 1.18 mWh cm-2/40.15 mW cm-2, outperforming the state-of-the-art 3D-printed energy storage devices. Furthermore, our SIC also achieves a gravimetric energy/power density of 101.6 Wh kg-1/3269 W kg-1. This work demonstrates that the 3D printing technology is versatile enough to construct emerging energy storage systems reconciling high energy and power density.

Bacterial cellulose-derived carbon nanofibers as both anode and cathode for hybrid sodium ion capacitor.

Hybrid ion capacitors (HICs) based on insertion reactions have attracted considerable attention due to their energy density being much higher than that of the electrical double-layer capacitors (EDLCs). However, the development of hybrid ion capacitors with high energy density at high power density is a big challenge due to the mismatch of charge storage capacities and electrode kinetics between the battery-type anode and capacitor-type cathode. In this work, N and O dual doped carbon nanofibers (N,O-CNFs) were combined with carbon nanotubes (CNTs) to compose a complex carbon anode. N,O dual doping effectively tuned the functional group and surface activity of the CNFs while the integration of CNTs increased the extent of graphitization and electrical conductivity. The carbon cathode with high specific surface area and high capacity was obtained by the activation of CNFs (A-CNFs). Finally, a hybrid sodium ion capacitor was constructed by the double carbon electrode, which showed a superior electrochemical capacitive performance. The as-assembled HIC device delivers a maximum energy density of 59.2 W h kg−1 at a power density of 275 W kg−1, with a high energy density of 38.7 W h kg−1 at a power density of 5500 W kg−1.

High-performance nitrogen and sulfur co-doped nanotube-like carbon anodes for sodium ion hybrid capacitors

Sodium ion hybrid capacitors are of great concern in large-scale and cost-effective electrical energy storage owing to their high energy and power densities, as well as natural abundance and wide distribution of sodium. However, it is difficult to find a well-pleasing anode material that matches the high-performance cathode materials to achieve good energy and power output for sodium ion hybrid capacitors. In this paper, nitrogen and sulfur co-doped nanotube-like carbon prepared by a simple carbonization process of high sulfur-loaded polyaniline nanotubes is introduced as the anode. The assembled sodium ion half cell based on the optimal nanotube-like carbon delivers a high reversible capacity of ∼304.8 mAh/g at 0.2 A/g and an excellent rate performance of ∼124.8 mAh/g at 10 A/g in a voltage window of 0.01–2.5 V (versus sodium/sodium ion). For the hybrid capacitors assembled using the optimal nanotube-like carbon as the anode and high-capacity activated carbon as the cathode, high energy densities of ∼100.2 Wh/kg at 250 W/kg and ∼50.69 Wh/kg at 12,500 W/kg are achieved.

Confining MOF-derived SnSe nanoplatelets in nitrogen-doped graphene cages via direct CVD for durable sodium ion storage

Tin-based compounds are deemed as suitable anode candidates affording promising sodium-ion storages for rechargeable batteries and hybrid capacitors. However, synergistically tailoring the electrical conductivity and structural stability of tin-based anodes to attain durable sodium-ion storages remains challenging to date for its practical applications. Herein, metal-organic framework (MOF) derived SnSe/C wrapped within nitrogen-doped graphene (NG@SnSe/C) is designed targeting durable sodium-ion storage. NG@SnSe/C possesses favorable electrical conductivity and structure stability due to the “inner” carbon framework from the MOF thermal treatment and “outer” graphitic cage from the direct chemical vapor deposition synthesis. Consequently, NG@SnSe/C electrode can obtain a high reversible capacity of 650 mAh·g−1 at 0.05 A·g−1, a favorable rate performance of 287.8 mAh·g−1 at 5 A·g−1 and a superior cycle stability with a negligible capacity decay of 0.016% per cycle over 3,200 cycles at 0.4 A·g−1. Theoretical calculations reveal that the nitrogen-doping in graphene can stabilize the NG@SnSe/C structure and improve the electrical conductivity. The reversible Na-ion storage mechanism of SnSe is further investigated by in-situ X-ray diffraction/ex-situ transmission electron microscopy. Furthermore, assembled sodium-ion hybrid capacitor full-cells comprising our NG@SnSe/C anode and an active carbon cathode harvest a high energy/power density of 115.5 Wh·kg−1/5,742 W·kg−1, holding promise for next-generation energy storages.

Integration of flexibility, cyclability and high-capacity into one electrode for sodium-ion hybrid capacitors with low self-discharge rate

Metal-ion hybrid capacitors are regarded as promising power sources for portable electronics because of numerous opportunities in designing the anode/cathode couple to realize high performance and device flexibility. Here we demonstrate our rational design of a porous-fiber network based electrode for quasi-solid-state flexible Na-ion hybrid capacitors. A SiO2-etching approach is deployed to synthesize the freestanding porous carbon nanofiber (PCNF) membrane that is both mechanically robust and light (~1 mg cm−2). The PCNF serves as a 3D scaffold for the uniform growth of MoS2@poly(3,4-ethylenedioxythiophene) (PEDOT) core/shell nanosheets. The resultant PCNF@MoS2@PEDOT double core/shell nanofiber electrode not only maintains the intrinsic high-capacity of MoS2 for Na-ion storage, but also renders long-term cyclability and high rate performance. The constructed quasi-solid-state Na-ion hybrid capacitors can tolerate arbitrary bending and folding, and has a much lower self-discharge rate (15 mV h-1) compared to symmetric capacitors.

MoSe2 nanoplatelets with enriched active edge sites for superior sodium-ion storage and enhanced alkaline hydrogen evolution activity

The development of MoSe2 with largely exposed active sites have recently been studied as promising high-performance active materials for sodium ion batteries (SIBs) and hydrogen evolution reactions (HER) due to their excellent energy storage and conversion capabilities. In the present study, nanostructured MoSe2 platelets with defective edge-sites (denoted as defect-rich, DR-MoSe2) have been synthesized with a nonstoichiometric ratio of precursors. The resulting DR-MoSe2 consists of highly defective ultrasmall MoSe2 nanoplatelets, showing ample pore distribution and highly exposed active edge sites. When testified as SIBs anodes, it reveals enhanced sodium-ion storage capacity and improved rate capability based on a pseudocapacitive charge storage mechanism. Density functional theory (DFT) calculations disclosed that sodium-ions trend to adsorb on the edge sites with a high binding energy and then diffuse along the basal planes with a low transport energy barrier. A hybrid sodium-ion capacitor based on DR-MoSe2 anode has further displayed a maximum energy density of 89 Wh kg−1 at a power output of 5436 W kg−1. In addition, the Tafel slope of 68 mV dec−1 for HER is also achieved in 1 M KOH. This work shed lights on design of two-dimensional materials through edge defect engineering for high-performance energy storage and catalysis.