Low-Temperature Carbonized Nitrogen-Doped Hard Carbon Nanofiber Toward High-Performance Sodium-Ion Capacitors

Carbon nanofiber(CNF)was widely utilized in the field of electrochemical energy storage due to its superiority of conductivity and mechanics.However,CNF was generally prepared at relatively high temperature.Herein,nitrogen-doped hard carbon nanofibers(NHCNFs)were prepared by a lowtemperature carbonization treatment assisted with electrospinning technology.Density functional theory analysis elucidates the incorporation of nitrogen heteroatoms with various chemical states into carbon matrix would significantly alter the total electronic configurations,leading to the robust adsorption and efficient diffusion of Na atoms on electrode interface.The obtained material carbonized at 600°C(NHCNF-600)presented a reversible specific capacity of 191.0 mAh g^(−1)and no capacity decay after 200 cycles at 1 A g^(−1).It was found that the sodium-intercalated degree had a correlation with the electrochemical impedance.A sodium-intercalated potential of 0.2 V was adopted to lower the electrochemical impedance.The constructed sodium-ion capacitor with activated carbon cathode and presodiated NHCNF-600 anode can present an energy power density of 82.1 Wh kg^(−1)and a power density of 7.0 kW kg^(−1).

Ordered Macroporous MoS_(2)-Carbon Composite with Fast and Robust Sodium Storage Properties to Solve the Issue of Kinetics Mismatch of Sodium-Ion Capacitors

Metal-ion capacitors(including Li^(+),Na^(+),and K^(+))effectively combine a battery negative electrode capable of reversibly intercalating metal cations,together with an electrical double-layer positive electrode.However,such novel cell design has a birth defect,namely kinetics mismatch between sluggish negative electrode and fast positive electrode,thus limiting the energy-power performance.Herein,we design a MoS_(2)-carbon composite anode with the ordered macroporous architecture and interlayer-expanded feature,exhibiting the fast and reversible Na^(+)redox processes.This kinetically favored anode is coupled with a homemade activated carbon cathode that allows for the excellent electrochemical performance of sodiumion capacitor with respect to large specific capacity,high-rate capability,and robust cycling.Through quantification of the potential swings of anode and cathode via a three-electrode Swagelok cell,we for the first time observe the abnormal variation law of potential swings and thus directly providing the evidence that the kinetics gap has been filled up by this kinetically favored anode.Our results represent a crucial step toward understanding the key issues of kinetics mismatch for hybrid cell,thus propelling the development of design of kinetically favored anode materials for high-performance metalion capacitors.

A safe,low-cost and high-efficiency presodiation strategy for pouch-type sodium-ion capacitors with high energy density

Sodium-ion capacitors(SICs)have attracted appreciable attention in virtue of the higher energy and power densities compared with their rivals,supercapacitors and sodium-ion batteries.Due to the lack of sodium resources in cathode,presodiation is critical for SICs to further augment performances.However,current presodiation strategy utilizes metallic sodium as the presodiation material.In this strategy,assembling/disassembling of half-cells is required,which is dangerous and in creases the time and cost of SIC leading to the restriction of their industrialization and commercialization.Herein we present a safe,low-cost and high-efficiency presodiation strategy by first employing Na_(2)C_(2)O_(4) as the sacrificial salt applied in SICs.Na_(2)C_(2)O_(4) is environmentally friendly and possesses considerably low expenditure.No additional residues remain after sodium extraction ascribed to its"zero dead mass"property.When paired with commercial activated carb on as the cathode and commercial hard carbon as the ano de,the constructed pouch-type SICs exhibit high energy and power densities of 91.7 Wh/kg and 13.1 kW/kg,respectively.This work shows a prospect of realizing the safe and low-cost manufacturing for high-performance SICs commercially.

A Novel Strategy of In Situ Trimerization of Cyano Groups Between the Ti3C2Tx(MXene) Interlayers for High-Energy and High-Power Sodium-Ion Capacitors

2D MXenes are attractive for energy storage applications because of their high electronic conductivity.However,it is still highly challenging for improving the sluggish sodium(Na)-ion transport kinetics within the MXenes interlayers.Herein,a novel nitrogen-doped Ti3C2Tx MXene was synthesized by introducing the in situ polymeric sodium dicyanamide(Na-dca)to tune the complex terminations and then utilized as intercalation-type pseudocapacitive anode of Na-ion capacitors(NICs).The Na-dca can intercalate into the interlayers of Ti3C2 Tx nanosheets and simultaneously form sodium tricyanomelaminate(Na3TCM)by the catalyst-free trimerization.The as-prepared Ti3C2Tx/Na3TCM exhibits a high N-doping of 5.6 at.%in the form of strong Ti-N bonding and stabilized triazine ring structure.Consequently,coupling Ti3C2Tx/Na3 TCM anode with different mass of activated carbon cathodes,the asymmetric MXene//carbon NICs are assembled.It is able to deliver high energy density(97.6 Wh kg-1),high power output(16.5 kW kg-1),and excellent cycling stability(≈82.6%capacitance retention after 8000 cycles).

Encapsulation of MnS Nanocrystals into N,S-Co-doped Carbon as Anode Material for Full Cell Sodium-Ion Capacitors

Sodium-ion capacitors(SICs)have received increasing interest for grid stationary energy storage application due to their affordability,high power,and energy densities.The major challenge for SICs is to overcome the kinetics imbalance between faradaic anode and nonfaradaic cathode.To boost the Na+reaction kinetics,the present work demonstrated a high-rate MnS-based anode by embedding the MnS nanocrystals into the N,S-co-doped carbon matrix(MnS@NSC).Benefiting from the fast pseudocapacitive Na+storage behavior,the resulting composite exhibits extraordinary rate capability(205.6 mAh g−1 at 10 A g−1)and outstanding cycling stability without notable degradation after 2000 cycles.A prototype SIC was demonstrated using MnS@NSC anode and N-doped porous carbon(NC)cathode;the obtained hybrid SIC device can display a high energy density of 139.8 Wh kg−1 and high power density of 11,500 W kg−1,as well as excellent cyclability with 84.5%capacitance retention after 3000 cycles.The superior electrochemical performance is contributed to downsizing of MnS and encapsulation of conductive N,S-co-doped carbon matrix,which not only promote the Na+and electrons transport,but also buffer the volume variations and maintain the structure integrity during Na+insertion/extraction,enabling its comparable fast reaction kinetics and cyclability with NC cathode.

Gas free oxidation of NaCN for presodiating and stabilizing the anodic host of sodium-ion capacitors

Sodium-ion capacitors(NICs)trigger considerable attention due to their higher specific energy than electrical double-layer capacitors(EDLCs)at comparable specific power.However,the presodiation process of the anodic host is extremely crucial for the construction of high-performance NICs.Herein,a positive EDL electrode containing activated carbon(AC)mixed with sodium cyanide(NaCN)as a sacrificial material was electrochemically oxidized to presodiate a Sn_(4)P_(3) anodic host buffered by hard carbon(HC).The oxidation of CN-occurred ca.2.9 V vs.Na/Na+and finished by a short region of linearly increasing potential with a total capacity close to the theoretical value of 547 mAh g^(-1).The operando electrochemical mass spectrometry(EMS)analysis of the atmosphere in the cell together with the internal pressure measurements realized during the galvanostatic oxidation of a YP80F-NaCN electrode demonstrate that the process occurs without any gas evolution.A precursor cell of an NIC was constructed in a pouch with YP80FNaCN and HC/Sn_(4)P_(3) electrodes.After the oxidative sodium transfer from NaCN to HC/Sn_(4)P_(3),the realized YP80F//Nax(HC/Sn_(4)P_(3))NIC demonstrated a discharge capacitance retention higher than 80%for 8900 cycles in the voltage range from 2.0 to 3.8 V.The infrared analysis of the anode obtained by the herein described transfer process detected polycyanogen,which stabilizes the electrode structure during cycling,and thereof is at the origin of the enhanced life span of the NIC.

Revisiting N,S co-doped carbon materials with boosted electrochemical performance in sodium-ion capacitors:The manipulation of internal electric field

Heteroatom doping has emerged as a prevailing strategy to enhance the storage of sodium ions in carbon materials.However,the underlying mechanism governing the performance enhancement remains undisclosed.Herein,we fabricated N/S co-doped carbon beaded fibers(S-N-CBFs),which exhibited glorious rate performance and durableness in Na+storage,showcasing no obvious capacity decay even after 3500 cycles.Furthermore,when used as anodes in sodium-ion capacitors,the S-N-CBFs delivered exceptional results,boasting a high energy density of 225 Wh·kg^(-1),superior power output of 22500 W·kg^(-1),and outstanding cycling stability with a capacity attenuation of merely 0.014%per cycle after 4000 cycles at 2 A·g^(-1).Mechanistic investigations revealed that the incorporation of both pyridinic N and pyrrolic N into the carbon matrix of S-N-CBFs induced internal electric fields(IEFs),with the former IEF being stronger than the latter,in conjunction with the doped S atom.Density functional theory calculations further unveiled that the intensity of the IEF directly influenced the adsorption of Na+,thereby resulting in the exceptional performances of S-N-CBFs as sodium-ion storage materials.This work uncovers the pivotal role of IEF in regulating the electronic structure of carbon materials and enhancing their Na^(+)storage capabilities,providing valuable insights for the development of more advanced electrode materials.

Flexible sodium-ion capacitors boosted by high electrochemicallyreactive and structurally-stable Sb_(2)S_(3)nanowire/Ti_(3)C_(2)Tx MXene film anodes

The rapid development of portable,foldable,and wearable electronic devices requires flexible energy storage systems.Sodiumion capacitors(SICs)combining the high energy of batteries and the high power of supercapacitors are promising solutions.However,the lack of flexible and durable electrode materials that allow fast and reversible Na+storage hinders the development of flexible SICs.Herein,we report a high-capacity,free-standing and flexible Sb2S3/Ti_(3)C_(2)Tx composite film for fast and stable sodium storage.In this hybrid nano-architecture,the Sb_(2)S_(3)nanowires uniformly anchored between Ti_(3)C_(2)Tx nanosheets not only act as sodium storage reservoirs but also pillar the two-dimensional(2D)Ti_(3)C_(2)Tx to form three-dimensional(3D)channels benefiting for electrolyte penetration.Meanwhile,the highly conductive Ti_(3)C_(2)Tx nanosheets provide rapid electron transport pathways,confine the volume expansion of Sb_(2)S_(3)during sodiation,and restrain the dissolution of discharged sodium polysulfides through physical constraint and chemical absorption.Owing to the synergistic effects of the one-dimensional(1D)Sb_(2)S_(3)nanowires and 2D MXenes,the resultant composite anodes exhibit outstanding rate performance(553 mAh·g−1 at 2 A·g−1)and cycle stability in sodium-ion batteries.Moreover,the flexible SICs using Sb2S3/Ti_(3)C_(2)Tx anodes and active carbon/reduced graphene oxide(AC/rGO)paper cathodes deliver a superior energy and power density in comparison with previously reported devices,as well as an excellent cycling performance with a high capacity retention of 82.78%after 5,000 cycles.This work sheds light on the design of next-generation low-cost,flexible and fast-charging energy storage devices.

Vacancy defect MoSeTe embedded in N and F co-doped carbon skeleton for high performance sodium ion batteries and hybrid capacitors

Sodium-ion batteries(SIBs) and hybrid capacitors(SIHCs) have garnered significant attention in energy storage due to their inherent advantages,including high energy density,cost-effectiveness,and enhanced safety.However,developing high-performance anode materials to improve sodium storage performa nce still remains a major challenge.Here,a facile one-pot method has been developed to fabricate a hybrid of MoSeTe nanosheets implanted within the N,F co-doped honeycomb carbon skeleton(MoSeTe/N,F@C).Experimental results demonstrate that the incorporation of large-sized Te atoms into MoSeTe nanosheets enlarges the layer spacing and creates abundant anion vacancies,which effectively facilitate the insertion/extraction of Na^(+) and provide numerous ion adsorption sites for rapid surface capacitive behavior.Additionally,the heteroatoms N,F co-doped honeycomb carbon skeleton with a highly conductive network can restrain the volume expansion and boost reaction kinetics within the electrode.As anticipated,the MoSeTe/N,F@C anode exhibits high reversible capacities along with exceptional cycle stability.When coupled with Na_(3)V_(2)(PO_(4))_(3)@C(NVPF@C) to form SIB full cells,the anode delivers a reversible specific capacity of 126 mA h g^(-1) after 100 cycles at 0.1 A g^(-1).Furthermore,when combined with AC to form SIHC full cells,the anode demonstrates excellent cycling stability with a reversible specific capacity of50 mA h g^(-1) keeping over 3700 cycles at 1.0 A g^(-1).In situ XRD,ex situ TEM characterization,and theoretical calculations(DFT) further confirm the reversibility of sodium storage in MoSeTe/N,F@C anode materials during electrochemical reactions,highlighting their potential for widespread practical application.This work provides new insights into the promising utilization of advanced transition metal dichalcogenides as anode materials for Na^(+)-based energy storage devices.

Carbon nanocages bridged with graphene enable fast kinetics for dual-carbon lithium-ion capacitors

Lithium-ion capacitors(LICs) combining the advantages of lithium-ion batteries and supercapacitors are considered a promising nextgeneration energy storage device. However, the sluggish kinetics of battery-type anode cannot match the capacitor-type cathode, restricting the development of LICs. Herein, hierarchical carbon framework(HCF) anode material composed of 0D carbon nanocage bridged with 2D graphene network are developed via a template-confined synthesis process. The HCF with nanocage structure reduces the Li^(+) transport path and benefits the rapid Li^(+) migration, while 2D graphene network can promote the electron interconnecting of carbon nanocages. In addition, the doped N atoms in HCF facilitate to the adsorption of ions and enhance the pseudo contribution, thus accelerate the kinetics of the anode. The HCF anode delivers high specific capacity, remarkable rate capability. The LIC pouch-cell based on HCF anode and active HCF(a-HCF) cathode can provide a high energy density of 162 Wh kg^(-1) and a superior power density of 15.8 kW kg^(-1), as well as a long cycling life exceeding 15,000cycles. This study demonstrates that the well-defined design of hierarchical carbon framework by incorporating 0D carbon nanocages and 2D graphene network is an effective strategy to promote LIC anode kinetics and hence boost the LIC electrochemical performance.

Coupling of Adhesion and Anti‑Freezing Properties in Hydrogel Electrolytes for Low‑Temperature Aqueous‑Based Hybrid Capacitors

Solid-state zinc-ion capacitors are emerging as promising candidates for large-scale energy storage owing to improved safety,mechanical and thermal stability and easy-to-direct stacking.Hydrogel electrolytes are appealing solid-state electrolytes because of eco-friendliness,high conductivity and intrinsic flexibility.However,the electrolyte/electrode interfacial contact and anti-freezing properties of current hydrogel electrolytes are still challenging for practical applications of zinc-ion capacitors.Here,we report a class of hydrogel electrolytes that couple high interfacial adhesion and anti-freezing performance.The synergy of tough hydrogel matrix and chemical anchorage enables a well-adhered interface between hydrogel electrolyte and electrode.Meanwhile,the cooperative solvation of ZnCl2 and LiCl hybrid salts renders the hydrogel electrolyte high ionic conductivity and mechanical elasticity simultaneously at low temperatures.More significantly,the Zn||carbon nanotubes hybrid capacitor based on this hydrogel electrolyte exhibits low-temperature capacitive performance,delivering high-energy density of 39 Wh kg^(-1)at-60°C with capacity retention of 98.7%over 10,000 cycles.With the benefits of the well-adhered electrolyte/electrode interface and the anti-freezing hydrogel electrolyte,the Zn/Li hybrid capacitor is able to accommodate dynamic deformations and function well under 1000 tension cycles even at-60°C.This work provides a powerful strategy for enabling stable operation of low-temperature zinc-ion capacitors.

Defect engineering on BiFeO_(3) through Na and V codoping for aqueous Na-ion capacitors

Sodium with low cost and high abundance is considered as a substitute element of lithium for batteries and supercapacitors,which need the appropriate host materials to accommodate the relatively large Na^(+) ions.Compared to Li^(+) storage,Na^(+) storage makes higher demands on the structural optimization of perovskite bismuth ferrite(BiFeO_(3)).We propose a novel strategy of defect engineering on BiFeO_(3) through Na and V codoping for high-efficiency Na^(+) storage,to reveal the roles of oxygen vacancies and V ions played in the enhanced electrochemical energy storage performances of Na-ion capacitors.The formation of the oxygen vacancies in the Na and V codoped BiFeO_(3)(denoted as NV-BFO),is promoted by Na doping and suppressed by V doping,which can be demonstrated by XPS and EPR spectra.By the first-principles calculations,the oxygen vacancies and V ions in NV-BFO are confirmed to substantially lower the Na^(+)migration energy barriers through the space and electric field effects,to effectively promote the Na^(+) transport in the crystals.Electrochemical kinetic analysis of the NV-BFO//NV-BFO capacitors indicates the dominant capacitive-controlled capacity,which depends on fast Na^(+) deintercalation-intercalation process in the NV-BFO electrode.The NV-BFO//NV-BFO capacitors open up a new avenue for developing highperformance Na-ion capacitors.

Mechanically flexible V_(3)S_(4)@carbon composite fiber as a high-capacity and fast-charging anode for sodium-ion capacitors

Hybrid Na-ion capacitors(NICs)have received considerable interests owing to their low-cost,high-safety,and rapidly charging energy-storage characteristics.The NICs are composed of a capacitor-type cathode and a battery-type anode.The major challenge for NICs is to search for suitable electrode materials to overcome the sluggish diffusion of Na^(+)in the anode.Herein,ultrafine vanadium sulfide is encapsulated in carbon fiber(V_(3)S_(4)@CNF)as a self-supported electrode by electrospinning and in situ sulfurization.The carbon cladding and one-dimensional(ID)nanofiber network-like structure could alleviate the volume expansion of V_(3)S_(4)during Na^(+)de-/intercalation process.Consequently,the V_(3)S_(4)@CNF anode exhibited a pseudocapacitive sodium storage in terms of large Na^(+)-storage capacity(476 mAh·g^(-1)at 0.1A·g^(-1)),high-rate capability(290 mAh·g^(-1)at 20.0 A·g^(-1))and excellent cycling stability(95%capacity retention for1500 cycles at 2.0 A·g^(-1))in Na half-cells.By employing V_(3)S_(4)@CNF as the anode and the activated carbon(AC)cathode,the as-assembled NICs could deliver a high energy density of 110 Wh·kg^(-1)at a power density of200 W·kg^(-1).Even at a high power of 10,000 W·kg^(-1),the specific energy is still up to 42 Wh·kg^(-1).

MOF-derived porous graphitic carbon with optimized plateau capacity and rate capability for high performance lithium-ion capacitors

The development of anode materials with high rate capability and long charge-discharge plateau is the key to improve per-formance of lithium-ion capacitors(LICs).Herein,the porous graphitic carbon(PGC-1300)derived from a new triply interpenetrated co-balt metal-organic framework(Co-MOF)was prepared through the facile and robust carbonization at 1300°C and washing by HCl solu-tion.The as-prepared PGC-1300 featured an optimized graphitization degree and porous framework,which not only contributes to high plateau capacity(105.0 mAh·g^(−1)below 0.2 V at 0.05 A·g^(−1)),but also supplies more convenient pathways for ions and increases the rate capability(128.5 mAh·g^(−1)at 3.2 A·g^(−1)).According to the kinetics analyses,it can be found that diffusion regulated surface induced capa-citive process and Li-ions intercalation process are coexisted for lithium-ion storage.Additionally,LIC PGC-1300//AC constructed with pre-lithiated PGC-1300 anode and activated carbon(AC)cathode exhibited an increased energy density of 102.8 Wh·kg^(−1),a power dens-ity of 6017.1 W·kg^(−1),together with the excellent cyclic stability(91.6%retention after 10000 cycles at 1.0 A·g^(−1)).

Defect-induced electron rich nanodomains in CoSe_(0.5)S_(1.5)/GA realize fast ion migration kinetics as sodium-ion capacitor anode

Optimizing charge migration and alleviating volume expansion in anode materials are the key to improve the electrochemical performance for sodium-ion storage devices.Herein,a hierarchical porous conducting matrix confining defect-rich selenium doped cobalt dichalcogenide(CoSe_(0.5)S_(1.5)/GA)is constructed as a promising SICs anode based on the guidance of theoretical calculation analysis.The increased defect concentration significantly enhanced the disorder degree of the compound and presented electron aggregation around the S atoms,which effectively modulated the electronic structure,further enabling high rate and ultra-capacity sodium storage.Moreover,strong interfacial coupling could construct spatial constraint to alleviate volume expansion as well as maintain electrode integrity and stability.The CoSe_(0.5)S_(1.5)/GA electrode can deliver a high capacity of 310.1 mA h g^(-1)after 2000 cycles at 1 A g^(-1),and the CoSe_(0.5)S_(1.5)/GA//AC sodium ion capacitor can exhibit an outstanding energy density of 237.5 W h kg^(-1).A series of characterization and theoretical calculation convincingly reveal that the defect moieties can regulate the Na^(+)storage and diffusion kinetics,which prove that our defect manufacture coupling with space-confined strategy can provide deep insights into the development of high-performance Na^(+)storage devices.

Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

Boosting High-Voltage Dynamics Towards High-Energy-Density Lithium-Ion Capacitors

Lithium-ion capacitors(LICs)are becoming important electrochemical energy storage systems due to their great potential to bridge the gap between supercapacitors and lithium-ion batteries.However,capacity lopsidedness and low output voltage greatly hinder the realization of high-energy-density LICs.Herein,a strategy of balancing capacity towards fastest dynamics is proposed to enable high-voltage LICs.Through electrochemical prelithiation of Nb_(2)C to be 1.1 V with 165 mAh g^(-1),Nb_(2)C//LiFePO_(4) LICs show a broadened potential window from 3.0 to 4.2 V and an according high energy density of 420 Wh kg^(-1).Moreover,the underlying mechanism between prelithiation and high voltage is disclosed by electrochemical dynamic analysis.Prelithiation declines the Nb_(2)C anode potential that facilitates electron transmission in the interlayer of two-dimensional Nb_(2)C MXene.This effect induces small drive force for Li^(+)ions deposition and hence weakens the repulsive force from adsorbed ions on the electrode surface.Benefiting from even more Li^(+)ions deposition,a higher voltage is eventually delivered.In addition,prelithiation significantly increases Coulomb efficiency of the 1st cycle from 74%to 90%,which is crucial to commercial application of LICs.

Nitrogen-doped porous carbon nanosheets as both anode and cathode for advanced potassium-ion hybrid capacitors

Potassium-ion hybrid capacitors(PIHCs)as a burgeoning research hotspot are an ideal replacement for lithium-ion hybrid capacitors(LIHCs).Here,we report nitrogen-doped porous carbon nanosheets(NPCNs)with enlarged interlayer spacing,abundant defects,and favorable mesoporous structures.The structural changes of NPCNs in potassiation and depotassiation processes are analyzed by using Raman spectroscopy and transmission electron microscopy.Due to the unique structure of NPCNs,the PIHC device assembled using NPCNs as both the anode and cathode material(double-functional self-matching material)exhibits a superior energy density of 128 Wh kg^(-1)with a capacity retention of 90.8%after 9000 cycles.This research can promote the development of double-functional self-matching materials for hybrid energy storage devices with ultra-high performance.

High-energy sodium-ion hybrid capacitors through nanograin-boundary-induced pseudocapacitance of Co_(3)O_(4) nanorods

Sodium-ion hybrid capacitors (SICs) have been proposed to bridge performance gaps between batteries and supercapacitors,and thus realize both high energy density and power density in a single configuration.Nevertheless,applications of SICs are severely restricted by their insufficient energy densities (<100Wh/kg) resulted from the kinetics imbalance between cathodes and anodes.Herein,we report a nanograin-boundary-rich hierarchical Co_(3)O_(4) nanorod anode composed of~20 nm nanocrystallites.Extreme pseudocapacitance (up to 72%@1.0 mV/s) is achieved through nanograin-boundary-induced pseudocapacitive-type Na^(+) storage process.Co_(3)O_(4) nanorod anode delivers in this case highly reversible capacity (810 mAh/g@0.025 A/g),excellent rate capability (335 mAh/g@5.0 A/g),and improved cycle stability (100 cycles@1.0 A/g with negligible capacity degradation).The outstanding performance can be credited to the hierarchical morphology of Co_(3)O_(4) nanorods and the well-designed nanograinboundaries between nanocrystallites that avoid particle agglomeration,induce pseudocapacitive-type Na^(+) storage,and accommodate volume variation during sodiation-desodiation processes.Nitrogendoping of the Co_(3)O_(4) nanorods not only generates defects for extra surficial Na^(+) storage but also increases the electronic conductivity for efficient charge separation and lowers energy barrier for Na^(+) intercalation.Synergy of conventional reaction mechanism and pseudocapacitive-type Na^(+) storage enables high specific capacity,rapid Na^(+) diffusion,and improved structural stability of the Co_(3)O_(4) nanorod electrode.The SIC integrating this highly pseudocapacitive anode and activated carbon cathode delivers exceptional energy density (175 Wh/kg@40 W/kg),power density (6632 W/kg@37 Wh/kg),cycle life (6000 cycles@1.0 A/g with a capacity retention of 81%),and coulombic efficiency (~100%).

The key challenges and future opportunities of electrochemical capacitors

Electrochemical capacitors(ECs)with unique merits of fast charge/discharge rate and long cyclability are one of the representative electrochemical energy storage systems,possessing wide applications in power electronics and automotive transportation,etc.[1,2].Furthermore.