CN106158419A - The preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor - Google Patents

The preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor Download PDF

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Publication number
CN106158419A
CN106158419A CN201610598938.7A CN201610598938A CN106158419A CN 106158419 A CN106158419 A CN 106158419A CN 201610598938 A CN201610598938 A CN 201610598938A CN 106158419 A CN106158419 A CN 106158419A
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China
Prior art keywords
nickel
foam
electrode
nitrate
cobalt
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CN201610598938.7A
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Inventor
高志永
陈晨
武大鹏
徐芳
张玲翠
蒋凯
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Henan Normal University
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Henan Normal University
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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
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • H01G11/26Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • 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)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses the preparation method of a kind of cobalt sulfide nickel/nickel foam electrode of super capacitor, with nickel foam, cobalt nitrate, nickel nitrate and thiourea as raw material, with ammonium fluoride as etching agent, with polyvinylpyrrolidone for morphology control agent, in 100 180 DEG C of hydro-thermal reaction 2 8h in hydrothermal reaction kettle, in foam nickel base, the ultra-thin lamella of deposition growing assembles cellular multilevel hierarchy cobalt sulfide nickel and forms active electrode.Cobalt sulfide nickel electrode prepared by the present invention is provided that higher fake capacitance, is provided simultaneously with higher electronics and ionic conductivity and superior fracture toughness, it is thus possible to the ratio electric capacity of comprehensive raising capacitor and high rate performance.

Description

The preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor
Technical field
The invention belongs to the preparing technical field of electrode of super capacitor, be specifically related to a kind of cobalt sulfide nickel/nickel foam and surpass The preparation method of level electrode for capacitors.
Background technology
Ultracapacitor is the electrochemical energy storing device that a class is important, mainly by porous electrode/electrolyte interface electric charge Assemble (electric double layer capacitance) or surface of active material and internal Reversible redox reaction (fake capacitance) stores electric charge, often compare Rule secondary cell has superior power density, charge-discharge velocity, cycle performance and wider operating temperature range, at higher-wattage There is important DEVELOPMENT PROSPECT in the electricity consumption facility such as field such as portable electronic products and hybrid vehicle of output.But, relatively other Secondary cell, the ratio electric capacity of ultracapacitor and energy density have much room for improvement, and therefore improve specific volume and the energy of ultracapacitor Density is the emphasis that this field researchs and develops at present.Electrode material is the key components of ultracapacitor, its electric conductivity, table Electric capacity and the energy density of device are had a direct impact by the factors such as face characteristic and redox active.Fake capacitance active substance table Face can occur Reversible redox reaction, is provided that relatively high specific capacitance, thus is an efficient electrode material for super capacitor of class.Logical Cross Rational structure design improve the electrolyte diffusion passage of fake capacitance active electrode material and carry with effectively connecting of collector The ion of high electrode, electron conduction, thus it is provided simultaneously with relatively high rate capability, the application of ultracapacitor is extremely closed by this Important.
Cobalt sulfide nickel is the electrode material that a class is important, and the oxidoreduction between metallic element difference oxidation number therein is anti- Higher fake capacitance should be able to be provided, therefore can be used as high-performance super capacitor electrode material.But fake capacitance active electrode material Relatively low electric conductivity can limit its high rate performance, use Rational Path, deposit multilevel structure material, energy on metal collector surface It is effectively improved active material and the conductive contact of collector and electrolyte diffusion passage, the ratio electric capacity of comprehensive raising capacitor And high rate performance.
Summary of the invention
Present invention solves the technical problem that the preparation side that there is provided a kind of cobalt sulfide nickel/nickel foam electrode of super capacitor Method, the method with nickel foam collector as substrate, a kind of multilevel hierarchy cobalt sulfide nickel fake capacitance active material of deposition growing, with Simple technical scheme prepares the electrode of super capacitor of relatively high specific capacitance and high rate performance, cobalt sulfide prepared by the method Nickel electrode in the alkaline electrolyte, is provided that relatively high charge-discharge specific volume, is provided simultaneously with significant high rate performance, demonstrate this electrode Huge potentiality to be exploited at electrochemical energy storage aspect of performance.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, cobalt sulfide nickel/nickel foam super capacitor electrode The preparation method of pole, it is characterised in that: with nickel foam, cobalt nitrate, nickel nitrate and thiourea as raw material, with ammonium fluoride as etching agent, With polyvinylpyrrolidone for morphology control agent, in 100-180 DEG C of hydro-thermal reaction 2-8h in hydrothermal reaction kettle, Ni-based at foam , the ultra-thin lamella of deposition growing assembles cellular multilevel hierarchy cobalt sulfide nickel and forms active electrode at the end.
Further preferably, described cobalt nitrate and the integral molar quantity of nickel nitrate with the molar ratio of thiourea and ammonium fluoride are 1.5:0.25-2:0.25-2, cobalt nitrate and nickel nitrate total amount are 1.5mmol:25-with the ingredient proportion of polyvinylpyrrolidone The mol ratio of 80mg, cobalt nitrate and nickel nitrate is 1:2-2:1, and the size of foam nickel base is 10mm × 10mm × 1mm.
Further preferably, concretely comprising the following steps of the preparation method of described cobalt sulfide nickel/nickel foam electrode of super capacitor: 0.5mmol cobalt nitrate, 1mmol nickel nitrate, 0.5mmol thiourea, 0.25mmol ammonium fluoride and 25mg polyvinylpyrrolidone are existed It is dissolved in 30mL deionized water formation homogeneous mixture solotion under magnetic agitation, then this homogeneous mixture solotion is transferred to hydro-thermal In reactor, simultaneously by molten for the nitric acid that foam nickel base molar concentration is 0.1mol/L of a size of 10mm × 10mm × 1mm Liquid etching processing 5min, washing is immersed in the reaction solution in hydrothermal reaction kettle after drying, in 150 DEG C of hydro-thermal reactions 5h, Grow depositing ultrathin lamella in foam nickel base and assemble cellular multilevel hierarchy cobalt sulfide nickel formation active electrode.
Ultra-thin lamella provided by the present invention assembles cellular multilevel hierarchy cobalt sulfide nickel material and has high specific surface area With wider bore footpath, beneficially electrolyte ion to the quick scattering and permeating of electrode surface and absorption, simultaneously its lamellar primary structure with And the close contact of this material and nickel foam collector is provided that efficent electronic transmission channel, beneficially electrode electrolyte interface Quick Oxidation reduction reaction, therefore this electrode can not only provide relatively Fabrication of High Specific Capacitance and demonstrate good high rate performance, suitableeer Close high current charge-discharge.Additionally, utilize hydrothermal deposition make cobalt sulfide nickel electrode technique simple, it is expected to fairly large making High-performance super capacitor.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the active electrode that the embodiment of the present invention 3 prepares;
Fig. 2 is the embodiment of the present invention 3 prepared active electrode charging and discharging curve under different electric current densities;
Fig. 3 is the embodiment of the present invention 3 prepared active electrode curve of double curvature under different electric current densities.
Detailed description of the invention
By the following examples the foregoing of the present invention is described in further details, but this should be interpreted as this The scope inventing above-mentioned theme is only limitted to below example, and all technology realized based on foregoing of the present invention belong to this Bright scope.
Embodiment 1
By 1mmol cobalt nitrate, 0.5mmol nickel nitrate, 0.25mmol thiourea, 0.25mmol ammonium fluoride and 25mg polyvinylpyrrolidine Ketone is dissolved in 30mL deionized water formation homogeneous mixture solotion under magnetic stirring, is then transferred to by this homogeneous mixture solotion In hydrothermal reaction kettle, it is the salpeter solution of 0.1mol/L by foam nickel base (10mm × 10mm × 1mm) by molar concentration simultaneously Etching processing 5min, washing is immersed in the reaction solution in hydrothermal reaction kettle after drying, in 100 DEG C of hydro-thermal reactions 5h, at bubble Grow depositing ultrathin lamella in foam nickel substrate and assemble cellular multilevel hierarchy cobalt sulfide nickel formation active electrode.By prepared work Property electrode as working electrode, platinized platinum is as auxiliary electrode, and HgO/Hg electrode, as reference electrode, immerses 2mol/L KOH electrolysis Matter forms three-electrode system, carries out electrochemical energy storage performance test at 0-0.5 potential window.In 1A/g constant current charge-discharge condition Under ratio electric capacity be 1892F/g.
Embodiment 2
By 0.75mmol cobalt nitrate, 0.75mmol nickel nitrate, 0.5mmol thiourea, 0.5mmol ammonium fluoride and 50mg polyvinyl pyrrole Alkanone is dissolved in 30mL deionized water formation homogeneous mixture solotion under magnetic stirring, is then shifted by this homogeneous mixture solotion To hydrothermal reaction kettle, simultaneously that foam nickel base (10mm × 10mm × 1mm) is molten with the nitric acid that molar concentration is 0.1mol/L Liquid etching processing 5min, washing is immersed in the reaction solution in hydrothermal reaction kettle after drying, in 130 DEG C of hydro-thermal reactions 2h, Grow depositing ultrathin lamella in foam nickel base and assemble cellular multilevel hierarchy cobalt sulfide nickel formation active electrode.By prepared Active electrode, as working electrode, assembles three-electrode system test chemical property according to embodiment 1, and electrode fills in 1A/g constant current Ratio electric capacity under discharging condition is up to 1536F/g.
Embodiment 3
By 0.5mmol cobalt nitrate, 1mmol nickel nitrate, 0.5mmol thiourea, 0.25mmol ammonium fluoride and 25mg polyvinylpyrrolidine Ketone is dissolved in 30mL deionized water formation homogeneous mixture solotion under magnetic stirring, is then transferred to by this homogeneous mixture solotion In hydrothermal reaction kettle, it is the salpeter solution of 0.1mol/L by foam nickel base (10mm × 10mm × 1mm) by molar concentration simultaneously Etching processing 5min, washing is immersed in the reaction solution in hydrothermal reaction kettle after drying, in 150 DEG C of hydro-thermal reactions 5h, at bubble Grow depositing ultrathin lamella in foam nickel substrate and assemble cellular multilevel hierarchy cobalt sulfide nickel (as shown in Figure 1) formation active electrode. This kind of electrode material has abundant hole, is suitable for the quick diffusion of electrolyte, is conducive to obtaining relatively high rate capability.By made Standby electrode, as working electrode, assembles three-electrode system test chemical property according to embodiment 1, at 1A/g constant current charge-discharge Under the conditions of specific volume up to 2844F/g(as shown in Figures 2 and 3);In 1-50A/g current density range, its specific volume conservation rate (multiplying power) be 76%(as shown in Figure 3).
Embodiment 4
By 0.5mmol cobalt nitrate, 1mmol nickel nitrate, 2mmol thiourea, 2mmol ammonium fluoride and 80mg polyvinylpyrrolidone at magnetic It is dissolved in 30mL deionized water formation homogeneous mixture solotion under power stirring, then this homogeneous mixture solotion is transferred to hydro-thermal anti- Answer in still, simultaneously by foam nickel base (10mm × 10mm × 1mm) with at the salpeter solution etching that molar concentration is 0.1mol/L Reason 5min, washing is immersed in the reaction solution in hydrothermal reaction kettle after drying, in 180 DEG C of hydro-thermal reactions 8h, Ni-based at foam Grow depositing ultrathin lamella at the end and assemble cellular multilevel hierarchy cobalt sulfide nickel formation active electrode.By prepared active electrode As working electrode, assembling three-electrode system test chemical property according to embodiment 1, electrode is in 1A/g constant current charge-discharge condition Under ratio electric capacity up to 2176F/g.
By embodiment it can be seen that by the regulation and control consumption of cobalt nickel salt and ratio, thiourea, ammonium fluoride and polyvinyl pyrrole The preparation conditions such as the consumption of alkanone and hydrothermal treatment consists temperature, time, energy Effective Regulation electrode is than electric capacity and high rate performance.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage, the technical staff of the industry should Understanding, the present invention is not restricted to the described embodiments, and the simply explanation present invention's described in above-described embodiment and description is former Reason, under the scope without departing from the principle of the invention, the present invention also has various changes and modifications, and these changes and improvements each fall within In the scope of protection of the invention.

Claims (3)

1. the preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor, it is characterised in that: with nickel foam, cobalt nitrate, nitric acid Nickel and thiourea are raw material, with ammonium fluoride as etching agent, with polyvinylpyrrolidone for morphology control agent, in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 2-8h, in foam nickel base, the ultra-thin lamella of deposition growing assembles cellular multilevel hierarchy cobalt sulfide Nickel forms active electrode.
The preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor the most according to claim 1, it is characterised in that: The molar ratio of described cobalt nitrate and the integral molar quantity of nickel nitrate and thiourea and ammonium fluoride is 1.5:0.25-2:0.25-2, The ingredient proportion of cobalt nitrate and nickel nitrate total amount and polyvinylpyrrolidone is 1.5mmol:25-80mg, cobalt nitrate and nickel nitrate Mol ratio be 1:2-2:1, the size of foam nickel base is 10mm × 10mm × 1mm.
The preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor the most according to claim 1 and 2, its feature exists In concretely comprising the following steps: by 0.5mmol cobalt nitrate, 1mmol nickel nitrate, 0.5mmol thiourea, 0.25mmol ammonium fluoride and the poly-second of 25mg Alkene pyrrolidone is dissolved in 30mL deionized water formation homogeneous mixture solotion under magnetic stirring, then this is uniformly mixed molten Liquid is transferred in hydrothermal reaction kettle, by the foam nickel base molar concentration of a size of 10mm × 10mm × 1mm is simultaneously Salpeter solution etching processing 5min of 0.1mol/L, washing is immersed in the reaction solution in hydrothermal reaction kettle, after drying in 150 DEG C hydro-thermal reaction 5h, grows depositing ultrathin lamella in foam nickel base and assembles cellular multilevel hierarchy cobalt sulfide nickel and form activity Electrode.
CN201610598938.7A 2016-07-27 2016-07-27 The preparation method of cobalt sulfide nickel/nickel foam electrode of super capacitor Pending CN106158419A (en)

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Cited By (13)

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Publication number Priority date Publication date Assignee Title
CN106783227A (en) * 2016-12-09 2017-05-31 广东工业大学 A kind of preparation method and application of electrode material
CN106898501A (en) * 2017-02-21 2017-06-27 华侨大学 A kind of NiCo2S4/XS(X=Ni、Co)Composite nano materials and its preparation method and application
CN107265521A (en) * 2017-08-08 2017-10-20 卢荣红 A kind of preparation method of the CoxNiyS nano materials as the empty battery of lithium
CN107316758A (en) * 2017-08-02 2017-11-03 河南师范大学 The preparation method of multilevel hierarchy cobalt sulfide nickel carbon quantum dot composite/nickel foam electrode of super capacitor
CN107492657A (en) * 2017-07-12 2017-12-19 三峡大学 A kind of preparation method of cobalt sulfide nickel both positive and negative polarity battery and its application on the recyclable battery of alkalescence
TWI631080B (en) * 2017-03-23 2018-08-01 國立臺北科技大學 Nickel cobalt sulfide synthesizing method and electrode
CN109280938A (en) * 2018-09-30 2019-01-29 陕西科技大学 A kind of Ni of the V doping of flower ball-shaped3S2/ NF self-supporting electrode material and preparation method thereof
CN109524247A (en) * 2017-09-18 2019-03-26 天津大学 3D- graphene/nickel foam and its preparation method and application
CN110098068A (en) * 2019-04-03 2019-08-06 中南大学 A kind of preparation method of ternary nickel cobalt manganese sulfide fake capacitance super capacitor material
CN110724220A (en) * 2019-10-15 2020-01-24 江苏科技大学 Needle-shaped control agent and preparation method and application thereof
CN110808172A (en) * 2019-10-31 2020-02-18 上海应用技术大学 Fe-Co-S nanosheet material and preparation method and application thereof
CN111276340A (en) * 2020-01-23 2020-06-12 上海应用技术大学 Ce-Co-S composite material and preparation method and application thereof
CN111986929A (en) * 2020-07-31 2020-11-24 江苏大学 Preparation method of cobalt manganate/nickel sulfide core-shell array structure electrode material

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106783227A (en) * 2016-12-09 2017-05-31 广东工业大学 A kind of preparation method and application of electrode material
CN106783227B (en) * 2016-12-09 2019-02-22 广东工业大学 A kind of preparation method and application of electrode material
CN106898501A (en) * 2017-02-21 2017-06-27 华侨大学 A kind of NiCo2S4/XS(X=Ni、Co)Composite nano materials and its preparation method and application
TWI631080B (en) * 2017-03-23 2018-08-01 國立臺北科技大學 Nickel cobalt sulfide synthesizing method and electrode
CN107492657A (en) * 2017-07-12 2017-12-19 三峡大学 A kind of preparation method of cobalt sulfide nickel both positive and negative polarity battery and its application on the recyclable battery of alkalescence
CN107492657B (en) * 2017-07-12 2019-12-10 三峡大学 preparation method of cobalt-nickel sulfide positive and negative electrode batteries and application of cobalt-nickel sulfide positive and negative electrode batteries in alkaline recyclable batteries
CN107316758A (en) * 2017-08-02 2017-11-03 河南师范大学 The preparation method of multilevel hierarchy cobalt sulfide nickel carbon quantum dot composite/nickel foam electrode of super capacitor
CN107265521A (en) * 2017-08-08 2017-10-20 卢荣红 A kind of preparation method of the CoxNiyS nano materials as the empty battery of lithium
CN109524247A (en) * 2017-09-18 2019-03-26 天津大学 3D- graphene/nickel foam and its preparation method and application
CN109280938A (en) * 2018-09-30 2019-01-29 陕西科技大学 A kind of Ni of the V doping of flower ball-shaped3S2/ NF self-supporting electrode material and preparation method thereof
CN110098068A (en) * 2019-04-03 2019-08-06 中南大学 A kind of preparation method of ternary nickel cobalt manganese sulfide fake capacitance super capacitor material
CN110098068B (en) * 2019-04-03 2021-06-15 中南大学 Preparation method of ternary nickel-cobalt-manganese sulfide pseudocapacitance supercapacitor material
CN110724220A (en) * 2019-10-15 2020-01-24 江苏科技大学 Needle-shaped control agent and preparation method and application thereof
CN110808172A (en) * 2019-10-31 2020-02-18 上海应用技术大学 Fe-Co-S nanosheet material and preparation method and application thereof
CN110808172B (en) * 2019-10-31 2022-04-05 上海应用技术大学 Fe-Co-S nanosheet material and preparation method and application thereof
CN111276340A (en) * 2020-01-23 2020-06-12 上海应用技术大学 Ce-Co-S composite material and preparation method and application thereof
CN111276340B (en) * 2020-01-23 2022-05-17 上海应用技术大学 Ce-Co-S composite material and preparation method and application thereof
CN111986929A (en) * 2020-07-31 2020-11-24 江苏大学 Preparation method of cobalt manganate/nickel sulfide core-shell array structure electrode material

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Application publication date: 20161123