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.

Furfural residues derived nitrogen-sulfur co-doped sheet-like carbon: An excellent electrode for dual carbon lithium-ion capacitors

The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.

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)).

Insights into Formation and Li-Storage Mechanisms of Hierarchical Accordion-Shape Orthorhombic CuNb_(2)O_(6) toward Lithium-Ion Capacitors as an Anode-Active Material

The orthorhombic CuNb_(2)O_(6)(O-CNO)is established as a competitive anode for lithium-ion capacitors(LICs)owing to its attractive compositional/structural merits.However,the high-temperature synthesis(>900℃)and controversial charge-storage mechanism always limit its applications.Herein,we develop a low-temperature strategy to fabricate a nano-blocks-constructed hierarchical accordional O-CNO framework by employing multilayered Nb_(2)CT_(x)as the niobium source.The intrinsic stress-induced formation/transformation mechanism of the monoclinic CuNb_(2)O_(6)to O-CNO is tentatively put forward.Furthermore,the integrated phase conversion and solid solution lithium-storage mechanism is reasonably unveiled with comprehensive in(ex)situ characterizations.Thanks to its unique structural merits and lithium-storage process,the resulted O-CNO anode is endowed with a large capacity of 150.3 mAh g^(-1)at 2.0 A g^(-1),along with long-duration cycling behaviors.Furthermore,the constructed O-CNO-based LICs exhibit a high energy(138.9 Wh kg^(-1))and power(4.0 kW kg^(-1))densities with a modest cycling stability(15.8%capacity degradation after 3000 consecutive cycles).More meaningfully,the in-depth insights into the formation and charge-storage process here can promote the extensive development of binary metal Nb-based oxides for advanced LICs.

Dendrite-structured FeF_(2) consisting of closely linked nanoparticles as cathode for high-performance lithium-ion capacitors

Lithium-ion capacitors(LICs)are regarded as a good choice for next-generation energy storage devices,which are expected to exhibit high energy densities,high power densities,and ultra-long cycling stability.Nevertheless,only a few battery-type cathode materials with limited kinetic properties can be employed in LICs,and their electrochemical properties need to be optimized urgently.Here,we exploit a new dendrite-structured FeF_(2) consisting of closely linked primary nanoparticles using a facile solvothermal method combined with the subsequent annealing treatment.This particular architecture has favorable transport pathways for both lithium ions and electrons and exhibits an ultrafast chargedischarge capability with high reversible capacities.Furthermore,a well-designed LIC employing the prepared dendrite-structured FeF_(2) as the battery-type cathode and commercialized activated carbon(AC)as supercapacitor-type anode was constructed in an organic electrolyte containing Li ions.The LIC operates at an optimal voltage range of 1.1-3.8 V and shows a maximum high energy density of 152 W h kg^(-1) and a high power density of 4900 W kg^(-1) based on the total mass of cathode and anode.Long-term cycling stability(85%capacity retention after 2000 cycles)was achieved at 1 A g^(-1).This work suggests that the dendrite-structured FeF_(2) is a prime candidate for high-performance LICs and accelerates the development of hybrid ion capacitor devices.

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.

Mechanically flexible reduced graphene oxide/carbon composite films for high-performance quasi-solid-state lithium-ion capacitors

Practical applications of diverse flexible wearable electronics require electrochemical energy storage(EES)devices with multiple configurations.Moreover,to fabricate flexible EES devices with high energy density and stability,organic integration from electrode design to device assembly is required.To address these challenges,a free-standing reduced graphene oxide(rGO)/carbon film with a unique sandwich structure has been designed via the assistance of vacuum-assistant filtration for lithium-ion capacitors(LICs).The graphene acts as not only a binder to construct a three-dimensional conductive network but also an active material to provide additional capacitive lithium storage sites,thus enabling fast ion/electron transport and improving the capacity.The designed rGO/hard carbon(rGO/HC)and rGO/activated carbon(rGO/AC)free-standing films exhibit enhanced specific capacities(513.7 mA h g^(-1)for rGO/HC and 102.8 mA h g^(-1)for rGO/AC)and excellent stability.Moreover,the integrated flexible quasi-solid-state rGO/AC//rGO/HC LIC devices possess a maximum energy density of 138.3 Wh kg^(-1),a high power density of 11 kW kg^(-1),and improved cycling performance(84.4%capacitance maintained after 10,000 cycles),superior to the AC//HC LIC(43.5%retention).Such a strategy enlightens the development of portable flexible LICs.

A Review:Pre-lithiation Strategies Based on Cathode Sacrificial Lithium Salts for Lithium-Ion Capacitors

Similar to lithium-ion batteries(LIBs),during the first charge/discharge process of lithium-ion capacitors(LICs),lithium-intercalated anodes(e.g.,silicon,graphite,and hard carbon)also exhibit irreversible lithium intercalation behaviors,such as the formation of a solid electrolyte interface(SEI),which will consume Li^(+)in the electrolyte and significantly reduce the electrochemical performance of the system.Therefore,pre-lithiation is an indispensable procedure for LICs.At present,commercial LICs mostly use lithium metal as the lithium source to compensate for the irreversible capacity loss,which has the demerits of operational complexity and danger.However,the pre-lithiation strategy based on cathode sacrificial lithium salts(CSLSs)has been proposed,which has the advantages of low cost,simple operation,environmental protection,and safety.Therefore,there is an urgent need for a timely and comprehensive summary of the application of CSLSs to LICs.In this review,the important roles of pre-lithiation in LICs are detailed,and different pre-lithiation methods are reviewed and compared systematically and comprehensively.After that,we systematically discuss the pre-lithiation strategies based on CSLSs and mainly introduce the lithium extraction mechanism of CSLSs and the influence of intrinsic characteristics and doping amount of CSLSs on LICs performance.In addition,a summary and outlook are conducted,aiming to provide the essential basic knowledge and guidance for developing a new pre-lithiation technology.

Observations on Arrhenius Degradation of Lithium-Ion Capacitors

Earlier research determined that lithium-ion capacitor (LIC) cycle life degradation can be accelerated by elevated temperature. LIC cycle life degradation can be described by an Arrhenius equation. This study performed cycle life testing at a constant temperature but varied cycle current. The results were described by an Arrhenius equation relying upon the number of cycles and a constant, which was determined by cycle current. Using mathematical derivations and experimental results, the researchers quantified the effects of activation energy and temperature upon this constant. Because cell temperature is nearly constant during cycles, it was deduced that elevated cycle current decreases activation energy. This lower activation energy then accelerates degradation. Thus this research demonstrates that cycle current ages LICs through its effects on their activation energies.

Improvements to Temperature, Warburg Impedance, and Voltage Computations for a Design-Based Predictive Model for Lithium-Ion Capacitors

An earlier study manipulated the Butler-Volmer equation to effectively model a lithium-ion capacitor’s (LIC) energy storage as a function of its constituent components and charge current. However, this model had several shortcomings: computed temperature values were too low, voltage was inaccurate, and the model required Warburg impedance values that were two orders of magnitude higher than experimental results. This study began by analyzing the model’s temperature and voltage computations in order to justify output values. Ultimately, these justifications failed. Therefore, in situ temperature rise was measured during charge cycles. Experimental results indicated that temperature increases minimally during a charge cycle (<1%). At high current densities (≥150 A·kg-1) temperature increase is negligible. After it was found that LIC temperature change is minimal during a charge cycle, the model accurately computed LIC voltage during the charge cycle and computed Warburg impedance that agreed with values derived from earlier experimental studies, even falling within the measurements’ precision error.

Free-standing ternary metallic sulphides/Ni/C-nanofiber anodes for high-performance lithium-ion capacitors

As a promising energy-storage device,the hybrid lithium-ion capacitor coupling with both a large energy density battery-type anode and a high power density capacitor-type cathode is attracting great attention.For the sake of improving the energy density of hybrid lithium-ion capacitor,the free-standing anodes with good electrochemical performance are essential.Herein,we design an effective electrospinning strategy to prepare free-standing MnS/Co4S3/Ni3S2/Ni/C-nanofibers(TMSs/Ni/C-NFs)film and firstly use it as a binder-free anode for hybrid lithium-ion capacitor.We find that the carbon nanofibers can availably prevent MnS/Co4S3/Ni3S2/Ni nanoparticles from aggregation as well as significantly improve the electrochemical performance.Therefore,the binder-free TMSs/Ni/C-NFs membrane displays an ultrahigh reversible capacity of 1246.9 m Ah g-1at 100 m A g-1,excellent rate capability(398 mAh g-1 at2000 mA g-1),and long-term cyclic endurance.Besides,we further assemble the hybrid lithium-ion capacitor,which exhibits a high energy density of 182.0 Wh kg-1at 121.1 W kg-1(19.0 Wh kg-1 at 3512.5 W kg-1)and remarkable cycle life.

Fabrication of porous lithium titanate self-supporting anode for high performance lithium-ion capacitor

Lithium titanate has unique "zero-strain" characteristics, which makes it promising for rapid energy storage lithium-ion capacitors. However, extremely low electronic conductivity and lithium ion diffusion coefficient severely limit its performance at high rate. Herein, we have constructed in situ clusters of porous lithium titanate nanoparticles on self-supporting carbon nanotube film by combining iron oxide hard template method and F127 soft template method. Due to the nano-structured particle size and the penetrating lithium ion transmission channel, a greatly improved lithium ion diffusion coefficient has been achieved, which brings significantly better electrochemical performance than dense lithium titanate. By assembling with a durable graphene foam cathode, a lithium-ion capacitor with an energy density of up to 101.8 Wh kg-1 was realized(at a power density of 436.1 W kg-1). And its capacitance retention reaches 84.8% after 5000 cycles. With such an alluring result, our work presents a novel lithium-ion capacitor system with practical application prospects.

Intercalation-pseudocapacitance hybrid anode for high rate and energy lithium-ion capacitors

Existing rechargeable batteries not only fail to meet the demand for high power applications but also cause heavy metal pollution.Li-ion capacitors(LICs),which can achieve higher charging speeds and energy densities than supercapacitors,have attracted extensive attention.Nevertheless,sluggish Li-ion diffusion of the battery-type anode results in limited rate performance of LICs.Herein,highperformance LICs using both battery and capacitor type Mn_(2)V_(2)O_(7)-graphene(MVO-G)anodes and hempstem-derivated activated carbon(HSAC)cathodes with a large surface area are first reported.In addition to high pseudocapacitance,the MVO-G possesses the advantage of fast Li^(+)storage performance making it a suitable choice for advanced LIC anodes.Graphene is employed to enhance overall conductivity and cycling stability leading to enhanced energy storage.The MVO-G//HSAC LICs exhibit a high energy density of 148.1 Wh kg^(-1) at a power density of 150 W kg^(-1) and 25 Wh kg^(-1) even at15 k W kg^(-1).More importantly,the MVO-G//HSAC LICs also show excellent cycling stability of 90%after15,000 cycles,which is expected for high performance energy storage systems.

Sustainable Lignin-Derived Carbon as Capacity-Kinetics Matched Cathode and Anode towards 4.5 V High-Performance Lithium-Ion Capacitors

The Li-ion capacitors(LICs)develop rapidly due to their double-high features of high-energy density and high-power density.However,the relative low capacity of cathode and sluggish kinetics of anode seriously impede the development of LICs.Herein,the precisely pore-engineered and heteroatomtailored defective hierarchical porous carbons(DHPCs)as large-capacity cathode and high-rate anode to construct high-performance dual-carbon LICs have been developed.The DHPCs are prepared based on triple-activation mechanisms by direct pyrolysis of sustainable lignin with urea to generate the interconnected hierarchical porous structure and plentiful heteroatominduced defects.Benefiting from these advanced merits,DHPCs show the well-matched high capacity and fast kinetics of both cathode and anode,exhibiting large capacities,superior rate capability and long-term lifespan.Both experimental and computational results demonstrate the strong synergistic effect of pore and dopants for Li storage.Consequently,the assembled dual-carbon LIC exhibits high voltage of 4.5 V,high-energy density of 208 Wh kg^(−1),ultrahigh power density of 53.4 kW kg^(−1)and almost zerodecrement cycling lifetime.Impressively,the full device with high mass loading of 9.4 mg cm^(−2)on cathode still outputs high-energy density of 187 Wh kg^(−1),demonstrative of their potential as electrode materials for high-performance electrochemical devices.

Modeling of a Lithium-Ion Capacitor and Its Charging and Discharging Circuit in a Model-Based Design

For several years now, electric vehicles (EVs) have been expected to become widely available in the micro-mobility field. However, the insufficiency of such vehicles’ battery-charging and discharging performance has limited their practical use. A hybrid energy storage system, which comprises a capacitor and battery, is a promising solution to this problem;however, to apply model-based designs, which are indispensable to embedded systems, such as the electronic control units used in EVs, a simple and accurate capacitor model is required. Within this framework, a lithium-ion capacitor (LIC) model is proposed, and its charging and discharging performances are evaluated against an actual LIC. The model corresponds accurately to the actual LIC, and the results indicate that the proposed LIC model will work well when used with Model-Based Design (MBD).

The application of metal-organic frameworks and their derivatives for lithium-ion capacitors

There is an urgent need for lithium-ion capacitors(LICs)that have both high energy and high power densities to meet the continuously growing energy storage demands.LICs effectively balance the high energy density of traditional rechargeable batteries with the superior power density and long life of supercapacitors(SCs).Nevertheless,the development of LICs is still hampered by limited kinetic processes and capacity mismatch between the cathode and anode.Metal-organic frameworks(MOFs)and their derivatives have received significant attention because of their extensive specific surface area,different pore structures and topologies,and customizable functional sites,making them compelling candidate materials for achieving high-performance LICs.MOF-derived carbons,known for their exceptional electronic conductivity and large surface area,provide improved charge storage and rapid ion transport.MOF-derived transition metal oxides contribute to high specific capacities and improved electrochemical stability.Additionally,MOF-derived metal compounds/carbons provide combined effects that increase both the capacitive and Faradaic reactions,leading to a superior overall performance.The review begins with an overview of the fundamental principles of LICs,followed by an exploration of synthesis strategies and ligand selection for MOF-based composite materials.It then analyzes the advantages of original MOFs and their derived materials,such as carbon materials and metal compounds,in enhancing LIC performance.Finally,the review discusses the major challenges faced by MOFs and their derivatives in LIC applications and offers future research directions and recommendations.

Interfacial/bulk synergetic effects accelerating charge transferring for advanced lithium-ion capacitors

The exploration of advanced materials through rational structure/phase design is the key to develop highperformance lithium-ion capacitors(LICs).However,high complexity of material preparation and difficulty in quantity production largely hinder the further development.Herein,Cu_(5)FeS_(4-x)/C(CFS@C)heterojunction with rich sulfur vacancies has successfully achieved from natural bornite,presenting low costeffective and bulk-production prospect.Density functional theory(DFT)calculations indicate that rich vacancies in bulk phase can decrease band gap of bornite and thus improve its intrinsic electron conductivity,as well as the heterojunction spontaneously evokes a built-in electric field between its interfacial region,largely reducing the migration barrier from 1.27 e V to 0.75 e V.Benefited from these merits,the CFS@C electrodes deliver outperformed lithium storage performance,e.g.,high reversible capacity(822.4m Ah/g at 0.1 A/g),excellent cycling stability(up to 820 cycles at 2 A/g and 540 cycles at 5 A/g with respective capacity retention of over or nearly 100%).With CFS@C as anode and porous carbon nanosheets(PCS)as cathode,the assembled CFS@C//PCS LIC full cells exhibit high energy/power density characteristics of 139.2 Wh/kg at 2500 W/kg.This work is expected to offer significant insights into structure modifications/devising toward natural minerals for advanced energy-storage systems.

Metal-organic framework-derived CoSe_(2)@N-doped carbon nanocubes for high-performance lithium-ion capacitors

Cobalt selenide(CoSe_(2))has garnered considerable attention as a prospective anode candidate for advanced lithium-ion storage,prompting comprehensive investigations.However,CoSe_(2)-based anodes usually suffer from significant volume variation upon lithiation leading to unsatisfactory cycling stability.Herein,a versatile synthesis route is proposed for the in-situ fabrication of CoSe2nanoparticles embedded in N-dope carbon skeleton(CoSe_(2)@NC)through annealing treatment and selenization of a metal–organic framework-derived(MOF)precursor.The N-doped carbon derived from the MOF serves not only as an excellent conductive substrate but also as a confined reactor,effectively inhibiting the structural instability and alleviating the inevitable volume change of CoSe_(2).Owing to their unique nanostructure,the as-prepared CoSe_(2)@NC exhibits a high capacity of 745.9mAh·g^(-1)at 0.1 A·g^(-1),while maintaining excellent rate capability and an impressive lifespan.Furthermore,the assembled lithium-ion capacitor(LIC)based on CoSe_(2)@NC demonstrates an energy density of 130Wh·kg^(-1),a power density of 24.6 kW·kg^(-1),and remarkable capacity retention of 90.8%after 8000 cycles.These results highlight the great potential of CoSe_(2)@NC for practical applications.

Improving anode performances of lithium-ion capacitors employing carbon-Si composites

The lithium-ion capacitor is a promising energy storage system with a higher energy density than traditional supercapacitors.However,its cycling and rate performances,which depend on the electrochemical properties of the anode,are still required to be improved.In this work,soft carbon anodes reinforced using carbon-Si composites of various compositions were fabricated to investigate their beneficial influences on the performance of lithium-ion capacitors.The results showed that the specific capacities of the anodes increased significantly by 16.6 mAh g^(-1) with 1.0 wt% carbon-Si composite,while the initial discharge efficiency barely changed.The specific capacity of the anode with a 10.0 wt% carbon-Si composite reached 513.1 mAh g^(-1),and the initial discharge efficiency was 83.79%.Furthermore,the anodes with 7.5 wt% or lower amounts of carbon-Si composite demonstrated reduced charge transfer resistances,which caused an improvement in the rate performance of the lithium-ion capacitors.Moreover,the use of the optimized amount(7.5 wt%) of carbon-Si composite in the anode could significantly improve the cycling performance of the lithium-ion capacitor by compensating the consumption of active lithium.The capacity retention of the lithium-ion capacitor reached 95.14% at 20 C after 10,000 cycles,while the anode potential remained below 0.412 V,which is much lower than that of a soft carbon anode.

Ultrathin porous graphitic carbon nanosheets activated by alkali metal salts for high power density lithium-ion capacitors

Graphitic carbons with reasonable pore volume and appropriate graphitization degree can provide efficient Li+/electrolyte-transfer channels and ameliorate the sluggish dynamic behavior of battery-type carbon negative electrode in lithium-ion capacitors(LICs).In this work,onion-like graphitic carbon materials are obtained by using carbon quantum dots as precursors after sintering,and the effects of alkali metal salts on the structure,morphology and performance of the samples are focused.The results show that alkali metal salts as activator can etch graphitic carbons,and the specific surface area and pore size distribution are intimately related to the description of the alkali metal salt.Moreover,it also affects the graphitization degree of the materials.The porous graphitic carbons(SGCs)obtained by NaCl activation exhibit high specific surface area(77.14 m^(2)·g^(-1))and appropriate graphitization degree.It is expectable that the electrochemical performance for lithium-ions storage can be largely promoted by the smart combination of catalytic graphitization and pores-creating strategy.High-performance LICs(S-GCs//AC LICs)are achieved with high energy density of 92 Wh·kg^(-1)and superior rate capability(66.3 Wh·kg^(-1)at10 A·g^(-1))together with the power density as high as10020.2 W·kg^(-1).