CN108878167A - A kind of supercapacitor CoNi2S4/ graphene composite material and preparation method thereof - Google Patents

A kind of supercapacitor CoNi2S4/ graphene composite material and preparation method thereof Download PDF

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CN108878167A
CN108878167A CN201810716251.8A CN201810716251A CN108878167A CN 108878167 A CN108878167 A CN 108878167A CN 201810716251 A CN201810716251 A CN 201810716251A CN 108878167 A CN108878167 A CN 108878167A
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preparation
coni
graphene
supercapacitor
composite material
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卢德力
常哲馨
林静静
韩生
刘玥冉
张小杰
薛原
魏巍
常伟
颜松
姚璐
连俊
赵豆豆
刘业萍
解麦莹
陈凤飞
任析朦
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Shanghai Institute of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of supercapacitor CoNi2S4/ graphene composite material and preparation method thereof.Specific step is as follows:First by Co (NO3)2·6H2O、Ni(NO3)2·6H2O and thioacetamide CH3CSNH2It is mixed in ethyl alcohol, the ethanol solution ultrasonic disperse that graphene oxide GO is added later is uniform, is then transferred in water heating kettle and carries out solvent thermal reaction, after reaction, is filtered, washed, is lyophilized, obtain supercapacitor CoNi2S4/ graphene composite material.Material circulation stability of the present invention is good, and capacity retention ratio is 87.4% after 5000 circulations, and highest energy density is 39.56W hkg‑1, power density 374.8Wkg‑1.The present invention prepares electrode material for super capacitor by controlling the quality of graphene, show strong specific capacitance ability, good cycle and it is environmentally protective the advantages that.

Description

A kind of supercapacitor CoNi2S4/ graphene composite material and preparation method thereof
Technical field
The invention belongs to electrode material for super capacitor preparation technical fields, specifically, are related to a kind of supercapacitor Use CoNi2S4/ graphene composite material and preparation method thereof.
Background technique
Supercapacitor is as a kind of novel energy accumulating device, compared with other energy storage devices, function with higher Rate density, fast charging and discharging have extended cycle life, can operating temperature range it is wide, it is environmentally protective the advantages that.Carbon nanotube (CNTs), Graphene, the charge transfer process between electrode surfaces and electrolyte ion such as active carbon are mainly with electric double layer energy storage mechnism It is main, carbon nano-fiber and organic carbon compound.Compared with other carbonaceous materials, graphene has unique structure, and electric conductivity is high, machine The advantages that tool intensity is high, and theoretical surface is high, and thermal stability is good.Ionic charge, graphene are readily adjusted by electrostatic interaction It can be used as a current-collector, provide electronics rapidly from the charge transfer reaction of fixed pseudo-capacitance.Therefore, graphene-based electricity Active material provides huge potentiality in supercapacitor.Although graphene has excellent cyclical stability and highly conductive Performance, but there is lower capacitor and lower energy density than fake capacitance material.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide a kind of supercapacitor CoNi2S4/ stone Black alkene composite material and preparation method, preparation method of the present invention is simple, prepared CoNi2S4/ rGO nanocomposite is made For the electrode material of supercapacitor, there is excellent chemical property, specific capacitance is high, good rate capability, good cycling stability.
In the present invention, CoNi is prepared for by solvent-thermal method2S4/ graphene composite material.In CoNi2S4/ rGO nanometers multiple In condensation material, graphene is as CoNi2S4The substrate of nanoparticle growth can fix fake capacitance nano material, accelerate electrode The electronics and ion of material transmit.Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of supercapacitor CoNi2S4The preparation method of/graphene composite material, specific steps are such as Under:First by Co (NO3)2·6H2O、Ni(NO3)2·6H2O and thioacetamide CH3CSNH2It mixes in ethyl alcohol, is added later The ethanol solution ultrasonic disperse of graphene oxide GO is uniform, is then transferred in water heating kettle and carries out solvent thermal reaction, after reaction, It is filtered, washed, is lyophilized, obtain supercapacitor CoNi2S4/ graphene composite material.
In the present invention, Co (NO3)2·6H2O、Ni(NO3)2·6H2O and CH3CSNH2Molar ratio be (1-20):(1-20): (1-20).Preferably, Co (NO3)2·6H2O、Ni(NO3)2·6H2O and CH3CSNH2Molar ratio be (1-3):(3-6):(6- 15)。
In the present invention, Co (NO3)2·6H2O and the feed ratio of ethyl alcohol are 1:1~1:100mmol/ml.
In the present invention, the concentration of the ethanol solution of graphene oxide GO is 1:10~15:1mg/ml, graphene oxide GO and Co(NO3)2·6H2The feed ratio of O is 10:1~20:1mg/mmol.
In the present invention, the ultrasonic disperse time is 0.5-3h.
In the present invention, solvent heat temperature is 120~200 DEG C, and the solvent thermal reaction time is 8~32h.Preferably, solvent heat Temperature is 150~180 DEG C, and the solvent thermal reaction time is 15~18h.
Compared to the prior art, the beneficial effects of the present invention are:
The synthetic method that the present invention uses is solvent-thermal method, simple and convenient, can large-scale application.The CoNi of preparation2S4/ stone Black alkene nanocomposite effectively improves simple graphene phenomenon easy to reunite, substantially increases the ratio electricity of supercapacitor Appearance ability, specific capacitance ability are up to 1621Fg–1
By CoNi2S4Nano particle is entrained in graphene layer, is conducive to the chemical property for improving material.CoNi2S4/ The chemical property of graphene nano combination electrode has fake capacitance behavior, has high specific capacitance (0.5Ag-1When be 1619F G-1), good high rate performance (reaches 10Ag-1When capacity retention be 76.7% cyclical stability (in 5Ag-1's There is no capacitance loss after 2500 charge and discharge cycles) in addition, anode as asymmetric super-capacitor, the material is in 0.5A g-1When also there is 126.6Fg-1High specific capacitance;Good cycling stability, under the current density condition of 10Ag-1,5000 times Capacity retention ratio is 87.4% after circulation, and highest energy density is 39.56W hkg-1, power density 374.8Wkg-1
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1, the CoNi that embodiment 2 and embodiment 3 are prepared respectively2S4/ graphene nano composite wood Expect the specific capacitance under different current densities.
Fig. 2 is the embodiment of the present invention 1, the CoNi that embodiment 2 and embodiment 3 are prepared respectively2S4/ graphene nano composite wood Material is in 10Ag-1Under the conditions of 2500 circle charge and discharge circulation figure.
Fig. 3 is the embodiment of the present invention 1, the CoNi that embodiment 2 and embodiment 3 are prepared respectively2S4/ graphene nano composite wood Material is in 10mVs-1Under the conditions of cyclic voltammogram.
Fig. 4 is CoNi prepared by the embodiment of the present invention 22S4The electron-microscope scanning figure of/graphene nanocomposite material.
Fig. 5 is CoNi prepared by the embodiment of the present invention 22S4The electron-microscope scanning figure of/graphene nanocomposite material.
Fig. 6 is CoNi prepared by the embodiment of the present invention 22S4/ graphene nanocomposite material is 5000 under the conditions of 10Ag-1 Enclose the circulation figure of charge and discharge.
Fig. 7 is CoNi prepared by the embodiment of the present invention 22S4/ graphene nanocomposite material power density and energy density Corresponding diagram.
Specific embodiment
More preferably to illustrate the contents of the present invention, following further clarification is made to the present invention combined with specific embodiments below, but The present invention is not limited by following implementation, other any made without departing from the spirit and principles of the present invention Changes, modifications, substitutions, combinations, simplifications should be equivalent substitute mode, be included within the scope of the present invention.
Fig. 1 is the embodiment of the present invention 1, the CoNi that embodiment 2 and embodiment 3 are prepared respectively2S4/ graphene nano composite wood Expect the specific capacitance under different current densities.Fig. 2 is the embodiment of the present invention 1, what embodiment 2 and embodiment 3 were prepared respectively CoNi2S4/ graphene nanocomposite material is in 10Ag-1Under the conditions of 2500 circle charge and discharge circulation figure.Fig. 3 is implementation of the present invention The CoNi that example 1, embodiment 2 and embodiment 3 are prepared respectively2S4/ graphene nanocomposite material is in 10mVs-1Under the conditions of follow Ring voltammogram.
Embodiment 1
1) Co (NO is taken3)2·6H2O is 1mmol, Ni (NO3)2·6H2O is 3mmol, CH3CSNH2It is dissolved in for 6mmol In 40ml ethyl alcohol.
2) 10mgGO of preparation is dissolved in ultrasound 1.5h in 20ml ethyl alcohol, then the CoNi2S4 solution of 1) preparation is added, It is transferred in the reaction kettle of 100ml liner tetrafluoroethene and is reacted, the hydro-thermal reaction time 16h, hydrothermal temperature is 180 DEG C.
3) it is washed with deionized several times, freeze-drying, freeze temperature is -70 DEG C, time 72h, and composite material is made CoNi2S4/rGO-1;
4) by composite material CoNiS4/ rGO-1 is finely ground, is according to mass ratio by composite material, acetylene black, polytetrafluoroethylene (PTFE) 8:1:1 mixing, is added a small amount of ethyl alcohol as solvent, magnetic agitation is dried in grume, is taken and is applied in nickel foam and dries in right amount It is dry;5) using 3M KOH solution as electrolyte, three-electrode system is selected to measure its chemical property, three-electrode system reference electrode For Ag/AgCl reference electrode.
By electrochemical property test, charge-discharge test is carried out under constant current, can be obtained from Fig. 1, the electrode material of embodiment 1 Material is in 0.5Ag-1Under current density, specific capacitance 1308Fg-1.In 1Ag-1Current density under, specific capacitance is 1190F·g-1.In 2Ag-1Current density under, specific capacitance 930Fg-1.In 5Ag-1Current density under, specific capacitance For 865Fg-1.In 10Ag-1Current density under, specific capacitance 733Fg-1.As shown in Fig. 2, electrode material 10Ag-1 Under the conditions of by 2500 circle charge and discharge, specific capacitance is almost unchanged, have excellent cycle performance.
Embodiment 2
1) Co (NO is taken3)2·6H2O is 3mmol, Ni (NO3)2·6H2O is 5mmol, CH3CSNH2It is dissolved in for 10mmol In 50ml ethyl alcohol.
2) 60mgGO of preparation is dissolved in ultrasound 1.5h in 40ml ethyl alcohol, then the CoNi that will 1) prepare2S4Solution is added, It is transferred in the reaction kettle of 100ml liner tetrafluoroethene and is reacted, the hydro-thermal reaction time 16h, hydrothermal temperature is 180 DEG C.
Explanation:Remaining is 3)~5) step is identical as example 1, and it repeats no more, CoNi is made2S4/ rGO-2 composite material, and make Make electrode for electrochemical property test.
Fig. 4, Fig. 5 are CoNi prepared by the embodiment of the present invention 22S4The electron-microscope scanning figure of/graphene nanocomposite material, Show composite material in flower-shaped.Fig. 6 is CoNi prepared by the embodiment of the present invention 22S4/ graphene nanocomposite material is in 10Ag- The circulation figure of 5000 circle charge and discharge under the conditions of 1.
By electrochemical property test, charge-discharge test is carried out under constant current, can be obtained in Fig. 1, and embodiment 2 exists 0.5A·g-1Under current density, specific capacitance 1619Fg-1.In 1Ag-1Current density under, specific capacitance 1539Fg-1。 In 2Ag-1Current density under, specific capacitance 1466Fg-1.In 5Ag-1Current density under, specific capacitance 1321F g-1.In 10Ag-1Current density under, specific capacitance 1243Fg-1.Fig. 2 is cycle performance figure, when current density is 10A g-1, after circulation 2500 is enclosed, specific capacitance is not reduced substantially.For embodiment 2, additionally provide when current density is followed for 10Ag-1 (Fig. 6) that ring 5000 encloses, specific capacitance capacity retention ratio are 87.4%.Fig. 7 is CoNi prepared by the embodiment of the present invention 22S4/ graphite The corresponding diagram of alkene nanocomposite power density and energy density, highest energy density are 39.56W hkg-1, power is close Degree is 374.8Wkg-1
Embodiment 3
1) Co (NO is taken3)2·6H2O is 3mmol, Ni (NO3)2·6H2O is 5mmol, CH3CSNH2It is dissolved in for 10mmol In 50ml ethyl alcohol.
2) 80mgGO of preparation is dissolved in ultrasound 1.5h in 40ml ethyl alcohol, then the CoNi that will 1) prepare2S4Solution is added, It is transferred in the reaction kettle of 100ml liner tetrafluoroethene and is reacted, the hydro-thermal reaction time 16h, hydrothermal temperature is 180 DEG C.
Explanation:Remaining is 3)~5) step is identical as example 1, and it repeats no more, CoNi is made2S4/ rGO-3 composite material, and make Make electrode for electrochemical property test.
By electrochemical property test, charge-discharge test is carried out under constant current, can be obtained from Fig. 1, and embodiment 3 exists 0.5A·g-1Under current density, specific capacitance 1216Fg-1.In 1Ag-1Current density under, specific capacitance 1133Fg-1。 In 2Ag-1Current density under, specific capacitance 1001Fg-1.In 5Ag-1Current density under, specific capacitance 895Fg-1.In 10Ag-1Current density under, specific capacitance 762Fg-1.As shown in Fig. 2, electrode material 10Ag-1Under the conditions of pass through 2500 circle charge and discharge, specific capacitance is almost unchanged, has excellent cycle performance.

Claims (9)

1. a kind of supercapacitor CoNi2S4The preparation method of/graphene composite material, which is characterized in that specific steps are such as Under:First by Co (NO3)2·6H2O、Ni(NO3)2·6H2O and thioacetamide CH3CSNH2It mixes in ethyl alcohol, is added later The ethanol solution ultrasonic disperse of graphene oxide GO is uniform, is then transferred in water heating kettle and carries out solvent thermal reaction, after reaction, It is filtered, washed, is lyophilized, obtain supercapacitor CoNi2S4/ graphene composite material.
2. preparation method according to claim 1, which is characterized in that Co (NO3)2·6H2O、Ni(NO3)2·6H2O and CH3CSNH2Molar ratio be (1-20):(1-20):(1-20).
3. preparation method according to claim 1, which is characterized in that Co (NO3)2·6H2O、Ni(NO3)2·6H2O and CH3CSNH2Molar ratio be (1-3):(3-6):(6-15).
4. preparation method according to claim 1, which is characterized in that Co (NO3)2·6H2O and the feed ratio of ethyl alcohol are 1:1 ~1:100mmol/ml.
5. preparation method according to claim 1, which is characterized in that the concentration of the ethanol solution of graphene oxide GO is 1: 10~15:1mg/ml;Graphene oxide GO and Co (NO3)2·6H2The feed ratio of O is 10:1~20:1mg/mmol.
6. preparation method according to claim 1, which is characterized in that the ultrasonic disperse time is 0.5-3h.
7. preparation method according to claim 1, which is characterized in that solvent heat temperature is 120~200 DEG C, and solvent heat is anti- It is 8~32h between seasonable.
8. preparation method according to claim 1 or claim 7, which is characterized in that solvent heat temperature is 150~180 DEG C, solvent heat Reaction time is 15~18h.
9. supercapacitor CoNi made from a kind of preparation method according to claim 12S4/ graphene composite material.
CN201810716251.8A 2018-07-03 2018-07-03 A kind of supercapacitor CoNi2S4/ graphene composite material and preparation method thereof Pending CN108878167A (en)

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CN109741962A (en) * 2019-01-09 2019-05-10 上海应用技术大学 A kind of FeNi-S@N-RGO nanometer sheet electrode material for super capacitor and preparation method thereof
CN111129494A (en) * 2019-12-28 2020-05-08 常州大学 Preparation method of sulfo-spinel/graphene electrode material and electrode material thereof
CN111383848A (en) * 2018-12-27 2020-07-07 郑州轻工业学院 graphene-CoNi for super capacitor2S4Nanocomposite and method for preparing same
CN111415823A (en) * 2020-03-06 2020-07-14 上海应用技术大学 Ni-Sn-S composite material and preparation method and application thereof
CN114620780A (en) * 2022-03-31 2022-06-14 哈尔滨工业大学(威海) Heterostructure composite material and preparation method and application thereof

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CN111383848A (en) * 2018-12-27 2020-07-07 郑州轻工业学院 graphene-CoNi for super capacitor2S4Nanocomposite and method for preparing same
CN109741962A (en) * 2019-01-09 2019-05-10 上海应用技术大学 A kind of FeNi-S@N-RGO nanometer sheet electrode material for super capacitor and preparation method thereof
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CN111415823B (en) * 2020-03-06 2021-12-07 上海应用技术大学 Ni-Sn-S composite material and preparation method and application thereof
CN114620780A (en) * 2022-03-31 2022-06-14 哈尔滨工业大学(威海) Heterostructure composite material and preparation method and application thereof
CN114620780B (en) * 2022-03-31 2023-07-14 哈尔滨工业大学(威海) Heterostructure composite material and preparation method and application thereof

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