Revealing dual capacitive mechanism of carbon cathode toward ultrafast quasi-solid-state lithium ion capacitors

High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretical calculations,it is found that the critical pore size of 0.8 nm for PF_6~-ion adsorption decreases strong interactive repulsion of electrons and largely reduces adsorption energy barrier,which greatly improves the charge accommodation capacity in electrical double-layer behavior.Most importantly,the chemical-bond evolution process of C=O group has been firstly revealed by X-ray photoelectron spectroscopy(XPS),indicating that the introduction of C=O group can provide abundant redox active sites for PF_6~-ion adsorption accompanied with enhanced pseudocapacitive capacity.Attributed to the synergistic effect of dual capacitive mechanism,porous carbon sheet(PCS) cathode shows a reversible specific capacity of 53.6 mAh g^(-1) even at a high current density of 50 A g^(-1).Significantly,the quasisolid-state LIC manifests state-of-the-art electrochemical performances with an integrated maximum energy density of 163 Wh kg^(-1) and an outstanding power density of 15,000 W kg^(-1).This elaborate work promotes better fundamental understanding about capacitive mechanism of PF_6~-ion and offers a rational dual-capacitive strategy for the design of advanced carbon cathodes.

Insights into Enhanced Capacitive Behavior of Carbon Cathode for Lithium Ion Capacitors: The Coupling of Pore Size and Graphitization Engineering

The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors,limiting the advancement of lithium ion capacitors(LICs).Here,an orientateddesigned pore size distribution(range from 0.5 to 200 nm)and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed,which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode.Significantly,after the systematical analysis cooperating with experimental result and density functional theory calculation,it is uncovered that the size of solvated PF6-ion is about 1.5 nm.Moreover,the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5-3 nm.Triggered with synergistic effect of graphitization and appropriate pore size distribution,optimized carbon cathode(Zn90Co10-APC)displays excellent capacitive performances with a reversible specific capacity of^50 mAh g-1at a current density of 5 A g-1.Furthermore,the assembly pre-lithiated graphite(PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg-1 and a high power density of 150,000 W kg-1 as well as excellent long-term ability with 10,000 cycles.This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF<sub>6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.

Bifunctional Li6CoO4 serving as prelithiation reagent and pseudocapacitive electrode for lithium ion capacitors

Lithium ion capacitors(LICs)have been widely used as energy storage devices due to their high energy density and high power density.For LICs,pre-lithiation of negative electrode is necessary.In this work,we employ a bifunctional Li6CoO4(LCO)as cathodic pre-lithiation reagent to improve the electrochemical performance of LICs.The synthesized LCO exhibited high first charge specific capacity of 721 mAh g-1and extremely low initial coulombic efficiency of 3.19%,providing sufficient Li+ for the pre-lithiation of negative electrode in the first charge.Simultaneously,Li6–xCoOy is generated from LCO during the first charge process,which exhibits pseudocapacitive property and contributes to capacity in form of surface capacitance during subsequent cycles,increasing the capacity of capacitive positive electrode.With the appropriate amounts of addition to the positive side in LICs,this bifunctional prelithiation reagent LCO shows significantly improved the electrochemical performance with the energy density of 78.5 Wh kg-1after 300 cycles between 2.0 and 4.2 V at 250 mA g-1.

Carbonaceous mesophase spherule/activated carbon composite as anode materials for super lithium ion capacitors

A series of carbonaceous mesophase spherule/activated carbon composites were prepared as anode materials for super lithium ion capacitors using carbonaceous mesophase spherules as the core materials and pitch as the active carbon shell precursor.The structures of the composites were examined by scanning electron microscopy and X-ray diffractometry.The electrochemical performance was investigated in electric double layer capacitor and half-cell.The results show that,the composite exhibits good performance in both capacitor and battery with a high reversible capacity of 306.6 mA·h/g(0.2C) in the half-cell,along with a capacitance of 25.8 F/g in the capacitor when an optimum ratio of carbonaceous mesophase spherules to active carbon is adopted.The composite also shows a favorable rate performance and good cycle ability.A working model of this anode in super lithium ion capacitors was established.

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.

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.

Vanadium Nitride Nanoparticles as Anode Material for Lithium Ion Hybrid Capacitor Applications

A high production efficiency synthesis method was used to produce a stacked vanadium nitride nanoparticle structure with an inexpensive raw material as an anode material and high surface area polystyrene was used the cathode material for lithium ion hybrid capacitors. The Li-HCs cell displayed an excellent specific capacitance of 64.2 F·g^-1 at a current density of 0.25 A·g^-1 and a wide potential window of 0.01 to 3.5 V. Furthermore, the device exhibited a high energy density of 109.3 W·h·kg^-1 at a power density of 512.3 W·kg^-1 and retained an energy density of 69.2 W·h·kg^-1 at a high power density of 3 498.9 W· kg^-1 at 2 A·g^-1. Due to the short synthesis time and simple raw materials, this method is suitable for industrial production.

In situ XRD and electrochemical investigation on a new intercalation-type anode for high-rate lithium ion capacitor

A new intercalation-type anode material is reported herein to improve the lithium storage kinetics for high-rate lithium ion capacitors.The crystal structure of orthorhombic NaNbO3 indicates two possible tunnels for lithium ions insertion into NaNbO3 host along the<101>and<141>directions.Moreover,in situ XRD is conducted to investigate the lithium storage mechanism and structural evolution of the NaNb O_(3) anode,demonstrating its intercalation behavior through(101)and(141)planes.Furthermore,the rGO nanosheets are introduced to facilitate the charge transfer,which also effectively prevent the aggregation of NaNbO3 nanocubes.As expected,the NaNbO_(3)/rGO nanocomposites possess remarkable reversible capacity(465 mA h g^(-1) at 0.1 A g^(-1)),superior rate capability(325 mA h g^(-1) at 1.0 A g^(-1))and cycling stability,attributed to their synergistic effect and high Li+diffusion coefficient DLi[D(NaNbO_(3)/rGO)/D(NaNbO_(3))≈31.54].Remarkably,the NaNbO3/rGO-based LIC delivers a high energy density of 166.7 W h kg^(-1) at 112.4 W kg^(-1) and remains 24.1 W h kg^(-1) at an ultrahigh power density of26621.2 W kg^(-1),with an outstanding cycling durability(90%retention over 3000 cycles at 1.0 A g^(-1)).This study provides new insights on novel intercalation-type anode material to enrich the materials system of LICs.

Graphitic nanorings for super-long lifespan lithium-ion capacitors

Porous graphitic carbon nanorings(PGCNs)are proposed by smart catalytic graphitization of nano-sized graphene quantum dots(GQDs).The as-prepared PGCNs show unique ring-like morphology with diameter around 10 nm,and demonstrate extraordinary mesoporous structure,controllable graphitization degree and highly defective nature.The mechanism from GQDs to PGCNs is proven to be a dissolution-precipitation process,undergoing the procedure of amorphous carbon,intermediate phase,graphitic carbon nanorings and graphitic carbon nanosheets.Further,the relationship between particles size of GQDs precursor and graphitization degree of PGCNs products is revealed.The unique microstructure implies PGCNs a broad prospect for energy storage application.When applied as negative electrode materials in dual-carbon lithium-ion capacitors,high energy density(77.6 Wh·kg^(−1))and super long lifespan(89.5%retention after 40,000 cycles at 5.0 A·g^(−1))are obtained.The energy density still maintains at 24.5 Wh·kg^(−1)even at the power density of 14.1 kW·kg^(−1),demonstrating excellent rate capability.The distinct microstructure of PGCNs together with the strategy for catalytic conversion from nanocarbon precursors to carbon nanorings opens a new window for carbon materials in electrochemical energy storage.

Multiple Functional Biomass-Derived Activated Carbon Materials for Aqueous Supercapacitors, Lithium-Ion Capacitors and Lithium-Sulfur Batteries

Biomass-derived activated carbon electrode materials have been synthesized by carbonization and KOH activa- tion processes from an agriculture waste - rice husk, composed of organic compound and silica. The surface area of activated carbon reached 1098.1 m2/g mainly including mesopores and macropores due to the template effect of sil- ica in rice husk. Owing to the existence of mesopores and macropores, the as-obtained activated carbon materials can be used in aqueous supercapacitors, lithium-ion （Li-ion） capacitors and lithium-sulfur （Li-S） batteries. In KOH electrolyte, fast rate performance （as high as 2 V/s） was obtained due to the existence of ideal electrical double layer capacitance. In organic electrolyte, high voltage （2.5 V） was achieved. Activated carbon electrode for Li-ion capac- itor also showed capacity of 17 mAh/g at 100 mA/g with the high voltage range of 2.5 V. The capacities of sul- fur-activated carbon in Li-S batteries were 1230 and 970 mAh/g at the current densities of 0.1 and 0.2 C. The pre- sent results showed that activated carbon materials with mesopores were good host to immobilize polysulfides.

Nitrogen-doped carbon nanotubes by multistep pyrolysis process as a promising anode material for lithium ion hybrid capacitors

Lithium-ion hybrid capacitors(LIHCs) is a promising electrochemical energy storage devices which combines the advantages of lithium-ion batteries and capacitors.Herein,we developed a facile multistep pyrolysis method,prepared an amorphous structure and a high-level N-doping carbon nanotubes(NCNTs),and by removing the Co catalyst,opening the port of NCNTs,and using NCNTs as anode material.It is shows good performance due to the electrolyte ions enter into the electrode materials and facilitate the charge transfer.Furthermore,we employ the porous carbon material(APDC) as the cathode to couple with anodes of NCNTs,building a LIHCs,it shows a high energy density of 173 Wh/kg at 200 W/kg and still retains 53 Wh/kg at a high power density of 10 kW/kg within the voltage window of 0-4.0 V,as well as outstanding cyclic life keep 80% capacity after 5000 cycles.This work provides an opportunity for the preparation of NCNTs,that is as a promising high-performance anode for LIHCs.

Porous carbon spheres anode with the stable output of low delithiation plateau and constant delithiation ratio for lithium ion hybrid capacitor

Porous carbon spheres derived from the facile hydrothermal treatment associated with the calcination process exhibit the good spherical morphology and unique porous structure.For the Li-based half-cell test,porous carbon spheres electrode not only exhibits larger reversible capacities and better compatibility as compared to the widely-used graphite,but also provides stable delithiation plateaus under different current density.Additionally,the delithiation ratio below 1 V almost accounts for a constant value(around 70%)with the increase of current density,evidencing that Li intercalation storage is the dominant model and Li insertion/extraction processes are propitious.The lithium ion hybrid capacitor configured with S-doped mesoporous graphene and porous carbon spheres as cathode and anode,delivers satisfied energy and power densities(up to 177 Wh kg^(−1) and 12,303 W kg^(−1),respectively)as well as long-term cyclability,which is superior to the corresponding S-doped mesoporous graphene//graphite and activated carbon//porous carbon spheres.In addition,the developed synthesis strategy is in favor of the realization of the scalable production of porous carbon spheres.

“Soft” graphene oxide-organopolysulfide nanocomposites for superior pseudocapacitive lithium storage

We report a “soft” graphene oxide-polymeric organosulfide nanocomposite with improved pseudocapacitive performance for high-potential（1–2.8 V vs. Li^0/Li~＋）, high-capacity（278 mAh/g） and stable（500 cycles） lithium storage.