Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

An Environment-Friendly High-Performance Aqueous Mg-Na Hybrid-Ion Battery Using an Organic Polymer Anode

Aqueous Mg ion batteries(AMIBs)show great potential in energy storage for their advantages of high capacity,abundant resource,and environmental friendliness.However,the development of AMIBs is limited due to the scarcity of suitable anode materials.In this study,a new polymer anode material(PNTAQ)with flower-like nanosheet structure is synthesized for aqueous Mg-Na hybrid-ion battery(AMNHIB).PNTAQ possess carbonyl functional groups which can be oxidized and reduced reversibly in aqueous solution containing alkaline metal ions.PNTAQ displays a discharge specific capacity of 245 mAh g^(−1)at 50 mA g^(−1)in 1 M MgCl_(2)+0.5 M NaCl electrolyte,which is much higher than that in single 1 M MgCl_(2)or 0.5 M NaCl electrolyte.Even cycling at 1000 mA g^(−1)for 1000 times,the capacity retention can still maintain at 87.2%.A full Mg-Na hybrid-ion cell is assembled by employingβ-MnO_(2)as cathode and PNTAQ as anode material,it exhibits a specific capacity of 91.6 mAh g^(−1)at 100 mA g^(−1).The polymer electrode material well maintains its framework structure during the discharge/charge cycling process of the hybrid-ion battery.

Nitrogen and Phosphorus Dual-Doped Multilayer Graphene as Universal Anode for Full Carbon-Based Lithium and Potassium Ion Capacitors

Lithium/potassium ion capacitors(LICs/PICs) have been proposed to bridge the performance gap between high-energy batteries and high-power capacitors.However,their development is hindered by the choice,electrochemical performance,and preparation technique of the battery-type anode materials.Herein,a nitrogen and phosphorus dual-doped multilayer graphene(NPG) material is designed and synthesized through an arc discharge process,using low-cost graphite and solid nitrogen and phosphorus sources.When employed as the anode material,NPG exhibits high capacity,remarkable rate capability,and stable cycling performance in both lithium and potassium ion batteries.This excellent electrochemical performance is ascribed to the synergistic effect of nitrogen and phosphorus doping,which enhances the electrochemical conductivity,provides a higher number of ion storage sites,and leads to increased interlayer spacing.Full carbon-based NPG‖LiPF6‖active carbon(AC) LICs and NPG‖KPF6‖AC PICs are assembled and show excellent electrochemical performance,with competitive energy and power densities.This work provides a route for the large-scale production of dual-doped graphene as a universal anode material for high-performance alkali ion batteries and capacitors.

Electrostatic self-assembly of MXene and edge-rich CoAl layered double hydroxide on molecular-scale with superhigh volumetric performances

It is highly desirable to design and synthesize two-dimensional nanostructured electrode materials with high electrical conductivity,large electrolyte-accessible surface area and more exposed active sites for energy storage applications.Herein,MXene/Co Al-LDH heterostructure has been prepared through electrostatic ordered hetero-assembly of monolayer MXene and edge-rich Co Al-LDH nanosheets in a faceto-face manner on molecular-scale for supercapacitor applications.Benefiting from the unique structure,strong interfacial interaction and synergistic effects between MXene and Co Al-LDH nanosheets,the electrical conductivity and exposed electrolyte-accessible active sites are significantly enhanced.The asprepared MXene/Co Al-LDH-80%(ML-80)film exhibits high volumetric capacity of 2472 C cm-3 in 3 M KOH electrolyte with high rate capability of 70.6%at 20 A g-1.Notably,to the best of our knowledge,the high volumetric capacity is the highest among other previously reported values for supercapacitors in aqueous electrolytes.Furthermore,our asymmetric supercapacitor device fabricated with ML-80 and MXene/graphene composite as cathode and anode,respectively,exhibits impressive volumetric energy density of 85.4 Wh L-1 with impressive cycling stability of 94.4%retention ratio after 30,000 continuous charge/discharge cycles.

A new catalyst for urea oxidation: NiCo2S4 nanowires modified 3D carbon sponge

Urea oxidation is a significant reaction for utilizing urea-rich wastewater or human urine as sustainable power sources which can ease the water eutrophication while generate electricity. A direct urea-hydrogen peroxide fuel cell is a new kind of fuel cell employing urea as fuel and hydrogen peroxide as oxidant which possesses a larger cell voltage. Herein, this work tries to promote the kinetics process of urea oxidation by preparing low-cost and high-efficient NiCo2S4 nanowires modified carbon sponge electrode. The carbon sponge used in this work with a similar three-dimensional multi-channel structure to Ni foam, is prepared by carbonizing recycled polyurethane sponge which is also a process of recycling waste. The performance of the prepared catalyst in an alkaline solution is investigated in a three-electrode system.With the introduction of Co element to the catalyst, a reduced initial urea oxidation potential and a high performance are obtained. Furthermore, a direct urea-hydrogen peroxide fuel cell is assembled using the NiCo2S4 nanowires modified carbon sponge anode. Results indicate that the prepared catalyst provides a chance to solve the current problems that hinder the development of urea electrooxidation(high initial urea oxidation potential, low performance, and high electrode costs).

MXene-Derived Defect-Rich TiO2@rGO as High-Rate Anodes for Full Na Ion Batteries and Capacitors

Sodium ion batteries and capacitors have demonstrated their potential applications for next-generation low-cost energy storage devices.These devices’s rate ability is determined by the fast sodium ion storage behavior in electrode materials.Herein,a defective TiO2@reduced graphene oxide(M-TiO2@rGO)self-supporting foam electrode is constructed via a facile MXene decomposition and graphene oxide self-assembling process.The employment of the MXene parent phase exhibits distinctive advantages,enabling defect engineering,nanoengineering,and fluorine-doped metal oxides.As a result,the M-TiO2@rGO electrode shows a pseudocapacitance-dominated hybrid sodium storage mechanism.The pseudocapacitance-dominated process leads to high capacity,remarkable rate ability,and superior cycling performance.Significantly,an M-TiO2@rGO//Na3 V2(PO4)3 sodium full cell and an M-TiO2@rGO//HPAC sodium ion capacitor are fabricated to demonstrate the promising application of M-TiO2@rGO.The sodium ion battery presents a capacity of 177.1 mAh g-1 at 500 mA g-1 and capacity retention of 74%after 200 cycles.The sodium ion capacitor delivers a maximum energy density of 101.2 Wh kg-1 and a maximum power density of 10,103.7 W kg-1.At 1.0 A g-1,it displays an energy retention of 84.7%after 10,000 cycles.

Organic 3D interconnected graphene aerogel as cathode materials for high-performance aqueous zinc ion battery

Aqueous rechargeable zinc ion batteries are very attractive in large-scale storage applications,because they have high safety,low cost and good durability.Nonetheless,their advancements are hindered by a dearth of positive host materials(cathode)due to sluggish diffusion of Zn2+in the solid inorganic frameworks.Here,we report a novel organic electrode material of poly 3,4,9,10-perylentetracarboxylic dianhydride(PPTCDA)/graphene aerogel(GA).The 3D interconnected porous architecture synthesized through a simple solvothermal reaction,where the PPTCDA is homogenously embedded in the GA nanosheets.The self-assembly of PPTCDA/GA coin-type cell will not only significantly improve the durability and extend lifetime of the devices,but also reduce the electronic waste and economic cost.The self-assembled structure does not require the auxiliary electrode and conductive agent to prepare the electrode material,which is a simple method for preparing the coin-type cell and a foundation for the next large-scale production.The PPTCDA/GA delivers a high capacity of≥200 m Ah g^–1 with the voltage of 0.0~1.5 V.After 300 cycles,the capacity retention rate still close to 100%.The discussion on the mechanism of Zn2+intercalation/deintercalation in the PPTCDA/GA electrode is explored by Fourier transform infrared spectrometer(FT-IR),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)characterizations.The morphology and structure of PPTCDA/GA are examined by scanning electron microscopy(SEM)and transmission electron microscopy(TEM).

Stable and dendrite-free Zn anode with artificial desolvation interface layer toward high-performance Zn-ion capacitor

Aqueous Zn-based energy storage devices possess tremendous advantages, such as low cost, high safety,and competitive energy density, due to employing a Zn metal anode and aqueous electrolyte. However,the cycling stability and rate ability of a Zn anode are hindered by Zn dendrite growth and sluggish ion transfer in the electrode/electrolyte interface. Herein, the interfacial properties of Zn anodes are improved through the introduction of a silver(Ag) protective layer, which facilitates uniform Zn deposition and regulates Zn ion transport. As a result, Ag-coated Zn anodes display stable cycling performance(600 h at 1 m A cm^(-2)) and low overpotential(150 mV at 50 mA cm^(-2)after 2000 cycles). The Ag layer in situ electrochemically converts into an AgZn_(3) layer and promotes Zn ion desolvation and threedimensional diffusion processes. Moreover, a Zn-ion capacitor assembled with an Ag-coated Zn anode and active carbon cathode shows a capable cycling lifespan and rate performance. This study provides a feasible strategy for constructing a stabilized and dendrite-free Zn anode for the development of high-performance Zn-based energy storage devices.

Designandconstructionof athree-dimensionalelectrodewith biomass-derived carbon current collector andwater-soluble binder for high-sulfur-loading lithium-sulfur batteries

Lithium-sulfur batteries attract lots of attention due to their high specific capacity,low cost,and environmental friendliness.However,the low sulfur utilization and short cycle life extremely hinder their application.Herein,we design and fabricate a three-dimensional electrode by a simple filtration method to achieve a high-sulfur loading.Biomass porous carbon is employed as a current collector,which not only enhances the electronic transport but also effectively limits the volume expansion of the active material.Meanwhile,an optimized carboxymethyl cellulose binder is chosen.The chemical bonding restricts the shuttle effect,leading to improved electrochemical performance.Under the ultrahigh sulfur load of 28mg/cm2,the high capacity of 18mAh/cm2 is still maintained,and stable cycling performance is obtained.This study demonstrates a viable strategy to develop promising lithium-sulfur batteries with a three-dimensional electrode,which promotes sulfur loading and electrochemical performance.

A Facile Synthesis of ZnCo2O4 Nanocluster Particles and the Performance as Anode Materials for Lithium Ion Batteries

ZnCo_2O_4 nanocluster particles(NCPs) were prepared through a designed hydrothermal method, with the assistance of a surfactant, sodium dodecyl benzene sulfonate. The crystalline structure and surface morphology of ZnCo_2O_4 were investigated by XRD, XPS, SEM, TEM, and BET analyses. The results of SEM and TEM suggest a clear nanocluster particle structure of cubic ZnCo_2O_4(*100 nm in diameter), which consists of aggregated primary nanoparticles(*10 nm in diameter), is achieved. The electrochemical behavior of synthesized ZnCo_2O_4 NCPs was investigated by galvanostatic discharge/charge measurements and cyclic voltammetry. The ZnCo_2O_4 NCPs exhibit a high reversible capacity of 700 mAh g^(-1) over 100 cycles under a current density of 100 mA g^(-1) with an excellent coulombic efficiency of 98.9% and a considerable cycling stability. This work demonstrates a facile technique designed to synthesize ZnCo_2O_4 NCPs which show great potential as anode materials for lithium ion batteries.

Plastic supported platinum modified nickel electrode and its high electrocatalytic activity for sodium borohydride electrooxidation

A novel plastic/multi-walled carbon nanotube（MWNTs）-nickel（Ni）-platinum（Pt） electrode（PMNP） is prepared by chemical-reducing Pt onto the surface of Ni film covered plastic/MWNTs（PM） substrate. The MWNTs are adhered by a piece of commercial double faced adhesive tape on the surface of plastic paper and the Ni film is prepared by a simple electrodeposition method. The morphology and phase structure of the PMNP electrode are characterized by scanning electron microscopy,transmission electron microscope and X-ray diffractometer. The catalytic activity of the PMNP electrode for Na BH4 electrooxidation is investigated by means of cyclic voltammetry and chronoamperometry. The catalyst combines tightly with the plastic paper and exhibits a good stability. MWNTs serve as both conductive material and hydrogen storage material and the Ni film and Pt are employed as electrochemical catalysts. The PMNP electrode exhibits a high electrocatalytic performance and the oxidation current density reaches to 10.76 A/（mg·cm） in 0.1 mol/dm3 Na BH4at0 V,which is much higher than those in the previous reports. The using of waste plastic reduces the discarding of white pollution and consumption of metal resources.

Lithiophilic Cu-Li_(2)O matrix on a Cu Collector to Stabilize Lithium Deposition for Lithium Metal Batteries

Lithium metal anode is the most ideal candidate for next-generation energy storage system.However,the uncontrolled dendrite growth,infinite volume expansion,and undesired side reactions lead to serious safety issues and hinder their potential application.Herein,a pre-lithiation strategy is proposed to construct a high-lithiophilic Cu-Li_(2)O matrix on commercial Cu foil.The in situ-generated Li_(2)O promises adequate nucleation sites and strengthens solid electrolyte interphase and lateral lithium deposition.Meanwhile,the existence of 3D matrix reduces the local current density.The synergy effect of Li_(2)O and Cu suppresses the growth of lithium dendrites.As a result,Cu-Li_(2)O matrix reveals an enhanced lithium plating/stripping behavior with Coulombic efficiency of 98.46%after 270 cycles.The symmetrical cell assembled by Li-plated electrodes displays a prolonged lifespan of 1400 h.The work demonstrates a scalable and effective approach for modified current collectors toward stable Li metal anode.

Petroleum pitch derived hard carbon via NaCl-template as anode materials with high rate performance for sodium ion battery

Sodium-ion batteries(SIBs)have garnered significant interest in energy storage due to their similar working mechanism to lithium ion batteries and abundant reserves of sodium resource.Exploring facile synthesis of a carbon-based anode materials with capable electrochemical performance is key to promoting the practical application of SIBs.In this work,a combination of petroleum pitch and recyclable sodium chloride is selected as the carbon source and template to obtain hard carbon(HC)anode for SIBs.Carbonization times and temperatures are optimized by assessing the sodium ion storage behavior of different HC materials.The optimized HC exhibits a remarkable capacity of over 430 mAh·g^(-1) after undergoing full activation through 500 cycles at a density of current of 0.1 A·g^(-1).Furthermore,it demonstrates an initial discharge capacity of 276 mAh·g^(-1) at a density of current of 0.5 A·g^(-1).Meanwhile,the optimized HC shows a good capacity retention(170 mAh·g^(-1) after 750 cycles)and a remarkable rate ability(166 mAh·g^(-1) at 2 A·g^(-1)).The enhanced capacity is attributed to the suitable degree of graphitization and surface area,which improve the sodium ion transport and storage.

Conductive Framework-Stabilized Zn-Metal Anodes for High-Performance Zn-Ion Batteries and Capacitors

Aqueous zinc(Zn)-based energy storage devices possess promising applications for large-scale energy storage systems due to the advantage of high safety,low price,and environment-friendliness.However,their development is restricted by dendrite growth and hydrogen evolution issues from the Zn-metal anode.Herein,a facile stress-pressing method is reported for constructing a grid zinc anode(GZn)with a conductive framework.The highly conductive copper(Cu)-mesh framework reduces electrode hydrogen evolution and increases electrode conductivity.Meanwhile,the in situ-formed Cu-Zn nano-alloy stabilizes the Zn deposition interface.As a result,the GZn symmetrical cell presents a low overpotential of 49 mV after cycling for 1,200 h(0.2 mA∙cm^(-2)).In addition,GZn displays its potential application as a universal anode for Zn-ion capacitors and batteries.An activated carbon||GZn Zn-ion capacitor delivers a stable cycling performance after 10,000 cycles at 5 A∙g^(−1) and MnO2||GZn Zn-ion batteries exhibit satisfactory cycle stability and excellent rate performance.This demonstrates that GZn appears to be a promising universal anode for Zn-ion capacitors and batteries.

Uniformly grown PtCo-modified C03O4 nanosheets as a highly efficient catalyst for sodium borohydride electrooxidation

A facile hydrothermal synthetic method, followed by in situ reduction and galvanic replacement processes, is used to prepare PtCo-modified Co304 nanosheets （PtCo/C0304 NSs） supported on Ni foam. The prepared nanomaterial is used as an electrocatalyst for NaBH4 oxidation in alkaline solution. The morphology and phase composition of PtCo/C0304 NSs are characterized by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD）, and X-ray photoelectron spectroscopy （XPS）. The catalytic performance of PtCo/Co3O4 NSs is investigated by cyclic voltammetry （CV） and chronoamperometry （CA） in a standard three-electrode system. Current densities of 70 and 850 mA·cm^-2 were obtained at -0.4 V for Co/Co3O4 and PtCo/Co3O4 NSs, respectively, in a solution containing 2 mol·L^-1 NaOH and 0.2 mol·L^-1 NaBH4. The use of a noble metal （Pt） greatly enhances the catalytic activity of the transition metal （Co） and Co3O4. Besides, both Co and Co3O4 exhibit good B-H bond breaking ability （in NaBH4）, which leads to better electrocatalytic activity and stability of PtCo/Co3O4 NSs in NaBH4 electrooxidation compared to pure Pt. The results demonstrate that the as-prepared PtCo/Co3O4 NSs can be a promising electrocatalyst for borohydride oxidation.

Ultrahigh energy density battery-type asymmetric supercapacitors： NiMoO4 nanorod-decorated graphene and graphene/Fe2O3 quantum dots

NiMoO4 has attracted intensive attention as one of the promising ternary metal oxides because of its high specific capacitance and electrical conductivity compared to traditional transition-metal oxides. In this study, NiMoO4 nanorods uniformly decorated on graphene nanosheets （G-NiMoO4） are synthesized through a facile hydrothermal method. The prepared G-NiMoO4 composite exhibits a high specific capacitance of 714 C·g^-1 at 1 A·g^-1 and an excellent rate capability, with a retention ratio of 57.7% even at 100 A·g^-1. An asymmetric supercapacitor （ASC） fabricated with the G-NiMoO4 composite as the positive electrode and Fe2O3 quantum dot-decorated graphene （G-Fe2O3-QDs） as the negative electrode delivers an ultrahigh energy density of 130 Wh.kg^-1, which is comparable to those of previously reported aqueous NiMoO4-based ASCs. Even when the power density reaches 33.6 kW·kg^-1, an energy density of 56 Wh·kg^-1 can be maintained. The ASC device exhibits outstanding cycling stability, with a capacitance retention of 113% after 40,000 cycles. These results indicate that the G-NiMoO4 composite is a promising candidate for ASCs with ultrahigh energy density and excellent cycling stability. Moreover, the present work provides an exciting guideline for the future design of high-performance supercapacitors for industrial and consumer applications via the simultaneous use of various pseudocapacitive materials with suitable potential windows as the positive and negative electrodes.

Porous and free-standing Ti3C2Tx-RGO film with ultrahigh gravimetric capacitance for supercapacitors

MXene-based electrode materials exhibit favorable supercapacitor performance in sulfuric acid due to praised pseudocapacitance charge storage mechanism.However,self-stacking of conventional MXene electrodes severely restricts their electrochemical performance,especially at high loading.Herein,a flexible cross-linked porous Ti3C2Tx-MXene-reduced graphene oxide(Ti3C2Tx-RGO)film is skillfully designed and synthesized by microscopic explosion of graphene oxide(GO)at sudden high te mperature.The generated chamber structure between layers could hold a few of electrolyte,leading to a close-fitting reaction at interlayer and avoiding complex ions transmission paths.The Ti3C2Tx-RGO film displayed a preferable rate performance than that of pure Ti3C2Tx film and a high capacitance of 505 F/g at 2 mV/s.Furthermore,the uniform intralayer structure and unique energy storage process lead to thicknessindependenct electrochemical performances.This work provides a simple and feasible improvement approach for the design of MXene-based electrodes,which can be spread other electrochemical systems limited by ions transport,such as metal ions batteries and catalysis.

Dendrite-free and anti-corrosion Zn metal anode enabled by an artificial layer for high-performance Zn ion capacitor

Aqueous zinc energy storage devices,holding various merits such as high specific capacity and low costs,have attracted extensive attention in recent years.Nevertheless,Zn metal anodes still suffer from a short lifespan and low Coulombic efficiency due to corrosion and side reactions in aqueous electrolytes.In this paper,we construct an artificial Sn inorganic layer on Zn metal anode through a facile strategy of atom exchange.The Sn layer suppresses Zn dendrite growth by facilitating homogeneous Zn plating and stripping during charge and discharge processes.Meanwhile,the Sn protective layer also serves as a physical barrier to decrease Zn corrosion and hydrogen generation.As a result,The Sn-coated anode(Sn|Zn)exhibits a low polarization voltage(~34 mV at 0.5 mAh/cm^(2))after 800 testing hours and displays a smooth and an even surface without corrosion.Moreover,the zinc ion capacitor(Sn|Zn‖activated carbon)is assembled with an enhanced capacity of 42 mAh/g and a capacity retention of 95%after 10,000 cycles at 5 A/g.This work demonstrates a feasible approach for the commercialization of aqueous Zn-based energy storage devices.