CN109267047A - A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide - Google Patents

A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide Download PDF

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CN109267047A
CN109267047A CN201811278008.9A CN201811278008A CN109267047A CN 109267047 A CN109267047 A CN 109267047A CN 201811278008 A CN201811278008 A CN 201811278008A CN 109267047 A CN109267047 A CN 109267047A
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cotton
electrode
nickel
preparation
deposition
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CN109267047B (en
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李乾
戚继球
赵宇龙
隋艳伟
委福祥
何业增
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China University of Mining and Technology CUMT
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China University of Mining and Technology CUMT
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
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    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
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    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/32Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
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    • C25D9/00Electrolytic coating other than with metals
    • C25D9/04Electrolytic coating other than with metals with inorganic materials
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    • 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
    • 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
    • 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
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Abstract

A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, comprising the following steps: (1) by cotton sensitized treatment;(2) cotton is activated;(3) cotton after activation is subjected to chemical deposit processing;(4) constant pressure electro-deposition is carried out to nickel plating conduction cotton on electrochemical workstation;(5) nickel nitrate and protochloride manganese, ammonium chloride and deionized water are mixed, obtain mixed solution;(6) electrochemical deposition is carried out to it using chronoptentiometry to collector nickel plating conductive fabric, the flower-shaped Ni-Mn double-metal hydroxide electrode material that several two-dimentional lamellars are combined into is obtained after washing, drying.Preparation method synthesis path of the present invention is simple, raw material are easy to get, are at low cost, when electric deposition nickel manganese hydroxide is used for electrode material for super capacitor on nickel plating conductive fabric, specific capacitance height, good rate capability.

Description

A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide
Technical field
The present invention relates to a kind of preparation method of flexible cloth electrode, specifically a kind of double-metal hydroxide flexible electrode Preparation method belongs to electrode material field.
Background technique
With the sharp increase of world population and the fast development of social economy, facing mankind energy crisis and ecological ring The double challenge that border deteriorates.With the rapid development of science and technology, people require energy storage device that must possess biggish capacitance, have Good cycle performance, and manufacturing cost is low, manufacturing process green non-pollution.These are that common batteries are unable to satisfy.It is super Grade capacitor appears in the visual field of people as the new type of energy storage device to emerge.
It is electrode material that the most important factor of its chemical property is influenced in supercapacitor, its performance directly determines The performance quality of supercapacitor, according to the physics and chemical property of active material on electrode material, electrode material can divide It is three kinds: carbon-based material, transistion metal compound and conducting polymer.Layered double-hydroxide (Layered Double Hydroxides, LDHs) also known as houghite compound or Layered compound, it is by two or more metal The stratified material that hydroxides are constituted.Ionic species sum number purpose adjustability allows it between its layer structure and controllable synusia Important position is seized of in the electrode material field of supercapacitor.In scientific research, the group of optimal metal cation is studied It closes, in the different anion of Intercalation reaction, controls the growth tendency and pattern of material, develop the Material cladding with other advantages, To optimize the chemical property of layered double-hydroxide, it is more suitable for electrode material for super capacitor.
Since pseudocapacitors come out, metal oxide, hydroxide is exactly the optimal selection of pseudocapacitors electrode material, The valuableness of selection and there is the ruthenium-oxide (RuO of certain toxicity since most2) start to deliver develop to nowadays common nickel oxide, Cobalt oxide, manganese oxide, manganese dioxide, nickel hydroxide, cobalt hydroxide.In addition, portable intelligent electronic device development is fast in recent years Suddenly, the too busy to get away corresponding efficient flexible energy storage device of the development of electronic device, so, with carbon fiber, conductive gold layer category fabric Cotton fabric/paper with CNT coating is that flexible capacitor made of substrate is come into being.But these matrixes involve great expense, market Economic competition ability is weak, it is difficult to which invested in plant metaplasia produces.
It is one of the approach of chemical property for improving electrode material, lamella that preparing, which has the electrode material of high-specific surface area, The electrode material of shape possesses biggish specific surface area, this means that the contact area of electrode material and electrolyte becomes larger, thus The path for shortening electron-transport increases the efficiency of electronics transfer, improves the chemical property of material.But leading in the market The manufacturing process flow of electric cloth material is complicated, and cost is relatively high, and the deposition liquid of physics silence is uneven, leads to last lead It is electrically also inhomogenous.
Summary of the invention
In view of the above-mentioned problems of the prior art, the purpose of the present invention is to propose to a kind of based on the soft of nickel manganese hydroxide Property cloth electrode preparation method to improve the preparation method of the electrode material of flexible electrode optimize cost so that electrode material Pattern is optimised, meanwhile, the chemical property and electro-chemical activity of flexible cloth electrode material are improved, and simplify production stream Journey improves preparation efficiency.
To achieve the above object, the technical solution adopted by the present invention is that: it is a kind of based on nickel manganese hydroxide flexible cloth electricity The preparation method of pole, comprising the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, cotton is immersed in sensitizing solution and carries out sensitized treatment;
(2) cotton at least three times, is then immersed in activating solution and is carried out by the cotton after cleaning sensitization with deionized water, cleaning It is activated;
(3) then the cotton after activation is carried out chemical deposit processing, coating by the cotton after being washed with deionized water activation Use ammonium hydroxide by the pH value adjustment of solution to 9-10 before processing;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, using the Pt plate of 2*2cm as anode, NiSO4、NH4Cl is electricity Electrolyte solution carries out constant pressure electro-deposition, deposition voltage 2V to nickel plating conduction cotton on electrochemical workstation, and sedimentation time is 8-10min;Nickel plating conductive fabric is just obtained after cleaning-drying processing;
(5) nickel nitrate and protochloride manganese, ammonium chloride and deionized water are mixed and are stirred by deposition liquid needed for preparing electro-deposition It mixes, obtains mixed solution;
(6) mixed solution obtained by step (5) is placed in a beaker by starting electrochemical workstation, using collector as work electricity Pole, platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under collector nickel plating conductive fabric is used Chronoptentiometry carries out electrochemical deposition to it, after reaction, Ni-Mn double-metal hydroxide electricity is obtained after washing, drying Pole material.
Preferably, the sensitizing solution in step (1) includes SnCl2And a little Sn particle, wherein SnCl2With the substance of HCl Amount is than being 1:10, and sensitization time is 10min.
Preferably, the activating solution in step (2) includes PdCl2And HCl, and activation time is 10min.
It preferably, include NiSO in the coating liquid that the chemical deposit in step (3) uses4、NH4Cl, sodium citrate and NaH2PO2, and the chemical deposit time is 2h.
Preferably, nickel nitrate and protochloride manganese mass ratio are 0.9:1~1.5:1 in the mixed solution in step (5).
Preferably, the condition of the electrochemical deposition in step (6) are as follows: current density 8mA cm-2, sedimentation time 900S.
It is compared with existing technology, the preparation method of flexible cloth electrode provided by the invention is by a series of chemistry sides The cotton of insulation is just processed to be nickel coating cotton by method.A kind of collection of the nickel plating conductive fabric as novel chemical mode synthesis Fluid both has the satisfactory electrical conductivity of collector such as nickel screen, iron net nowadays generally used etc., also possesses bigger active matter Matter loaded area, and the synthesis path of nickel coating cotton is simple, raw material are easy to get, are at low cost.Electrodeposition process preparation It is short, high-efficient that sample possesses preparation time, laboratory apparatus, simple operation and other advantages, and the sedimentary that electro-deposition is formed is equal It is even and smooth, it is often more important that the thickness of sedimentary is controllable.Electric deposition nickel manganese hydroxide is used on nickel plating conductive fabric When electrode material for super capacitor, specific capacitance height, good rate capability.
Detailed description of the invention
Fig. 1 is nickel manganese double-metal hydroxide scanning electron microscope (SEM) photograph, wherein (a), (b), (c) are respectively to be in Ni:Mn ratio The SEM for the nickel manganese double-metal hydroxide being prepared under conditions of 1:1,1:2,2:3 schemes;
Fig. 2 is obtained nickel manganese double-metal hydroxide electrochemical property test figure, wherein (a) figure is different proportion The CV curve of nickel manganese double-metal hydroxide, (b) figure is the GCD curve of the nickel manganese double-metal hydroxide of different proportion.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment 1:
A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, comprising the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, it includes 0.01Mol SnCl that cotton, which is immersed,2、0.1Mol Sensitized treatment, sensitization time 10min are carried out in the sensitizing solution of HCl and a little Sn particle;
(2) cotton after cleaning sensitization with deionized water, then immersing cotton includes 10 μ g/mL PdCl2With It is activated in the activating solution of 0.018Mol HCl, activation time 10min;
(3) then the cotton after activation is carried out chemical deposit processing, coating by the cotton after being washed with deionized water activation Liquid includes 0.0712Mol NiSO4、0.561Mol NH4Cl, 0.034Mol sodium citrate and 0.0283Mol NaH2PO2, coating The processing time is 2h;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, the Pt plate of 2*2cm is anode, with 0.15Mol NiSO4、 0.12Mol NH4Cl is that electrolyte solution carries out constant pressure electro-deposition to nickel plating conduction cotton on CHI660E electrochemical workstation, Deposition voltage is 2V, sedimentation time 8-10min;
(5) 0.58g Ni (NO is weighed3)2With 0.38g MnCl2It is added in the deionized water of 100mL, carries out magnetic agitation 5min obtains mixed solution.
(6) 1.07gNH is weighed4Above-mentioned mixed solution is added in Cl, and magnetic agitation 5min obtains electrolyte.
(7) mixed solution obtained using step (6) is electrolyte, using clean nickel plating conductive fabric as working electrode, platinum electrode For to electrode, saturated calomel electrode is reference electrode, constant current electrodeposit reaction is carried out under electrochemical workstation, conductive fabric Area is 1*2cm2, current density is 8mA cm-2, electrodeposition time 900S.
After reaction, the three-dimensional flower-shaped nickel manganese being composed of many sheets pair is just obtained after supersound washing, drying Metal hydroxides electrode material.
The nickel manganese double-metal hydroxide being prepared through this embodiment, shows the three-dimensional being combined by two-dimensional slice Style shape space structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
Electrochemical property test method: simultaneously using the three-dimensional style Ni-Mn double-metal hydroxide material of preparation as electrode Its chemical property is tested, the chemical property of working electrode tests completion in three-electrode system, and electrolyte is that 1M KOH is molten Liquid is to electrode with platinized platinum, and with saturated calomel electrode (SCE) for reference electrode, this three-electrode system is connected to electrochemical operation Stand upper (Shanghai Chen Hua, CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) The chemical property of technical testing electrode, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in 1A/g, than electricity Holding is 554F/g;Cycle charge-discharge 2000 encloses, and quality specific capacitance is 470F/g, cycle efficieny 80%.
Embodiment 2:
A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, comprising the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, it includes 0.01Mol SnCl that cotton, which is immersed,2、0.1Mol Sensitized treatment, sensitization time 10min are carried out in the sensitizing solution of HCl and a little Sn particle;
(2) cotton after cleaning sensitization with deionized water, then immersing cotton includes 10 μ g/mL PdCl2With It is activated in the activating solution of 0.018Mol HCl, activation time 10min;
(3) then the cotton after activation is carried out chemical deposit processing, coating by the cotton after being washed with deionized water activation Liquid includes 0.0712Mol NiSO4、0.561Mol NH4Cl, 0.034Mol sodium citrate and 0.0283Mol NaH2PO2, coating The processing time is 2h;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, the Pt plate of 2*2cm is anode, with 0.15Mol NiSO4、 0.12Mol NH4Cl is that electrolyte solution carries out constant pressure electro-deposition to nickel plating conduction cotton on CHI660E electrochemical workstation, Deposition voltage is 2V, sedimentation time 8-10min;
(5) 1.16g Ni (NO is weighed3)2With 1.14g MnCl2It is added in the deionized water of 100mL, carries out magnetic agitation 5min obtains mixed solution.
(6) 1.07gNH is weighed4Above-mentioned mixed solution is added in Cl, and magnetic agitation 5min obtains electrolyte.
(7) mixed solution obtained using step (6) is electrolyte, and using clean conductive fabric as working electrode, platinum electrode is pair Electrode, saturated calomel electrode are reference electrode, and the reaction of constant current spot deposition, the area of conductive fabric are carried out under electrochemical workstation For 1*2cm2, current density is 8mA cm-2, electrodeposition time 900S.
After reaction, the three-dimensional flower-shaped nickel manganese being composed of many sheets pair is just obtained after supersound washing, drying Metal hydroxides electrode material.
The nickel manganese double-metal hydroxide being prepared through this embodiment, shows the three-dimensional being combined by two-dimensional slice Style shape space structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
Electrochemical property test method: simultaneously using the three-dimensional style Ni-Mn double-metal hydroxide material of preparation as electrode Its chemical property is tested, the chemical property of working electrode tests completion in three-electrode system, and electrolyte is that 1M KOH is molten Liquid is to electrode with platinized platinum, and with saturated calomel electrode (SCE) for reference electrode, this three-electrode system is connected to electrochemical operation Stand upper (Shanghai Chen Hua, CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) The chemical property of technical testing electrode, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in 1A/g, than electricity Holding is 955F/g;Cycle charge-discharge 2000 encloses, and quality specific capacitance is 764F/g, cycle efficieny 85%.
Embodiment 3:
A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, comprising the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, it includes 0.01Mol SnCl that cotton, which is immersed,2、0.1Mol Sensitized treatment, sensitization time 10min are carried out in the sensitizing solution of HCl and a little Sn particle;
(2) cotton after cleaning sensitization with deionized water, then immersing cotton includes 10 μ g/mL PdCl2With It is activated in the activating solution of 0.018Mol HCl, activation time 10min;
(3) then the cotton after activation is carried out chemical deposit processing, coating by the cotton after being washed with deionized water activation Liquid includes 0.0712Mol NiSO4、0.561Mol NH4Cl, 0.034Mol sodium citrate and 0.0283Mol NaH2PO2, coating The processing time is 2h;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, the Pt plate of 2*2cm is anode, with 0.15Mol NiSO4、 0.12Mol NH4Cl is that electrolyte solution carries out constant pressure electro-deposition to nickel plating conduction cotton on CHI660E electrochemical workstation, Deposition voltage is 2V, sedimentation time 8-10min;
(5) 0.58g Ni (NO is weighed3)2With 0.76g MnCl2It is added in the deionized water of 100mL, carries out magnetic agitation 5min obtains mixed solution.
(6) 1.07gNH is weighed4Above-mentioned mixed solution is added in Cl, and magnetic agitation 5min obtains electrolyte.
(7) mixed solution obtained using step (6) is electrolyte, and using clean conductive fabric as working electrode, platinum electrode is pair Electrode, saturated calomel electrode are reference electrode, and the reaction of constant current spot deposition, the area of conductive fabric are carried out under electrochemical workstation For 1*2cm2, current density is 8mA cm-2, electrodeposition time 900S.
After reaction, the three-dimensional flower-shaped nickel manganese being composed of many sheets pair is just obtained after supersound washing, drying Metal hydroxides electrode material.
The nickel manganese double-metal hydroxide being prepared through this embodiment, shows the three-dimensional being combined by two-dimensional slice Style shape space structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
Electrochemical property test method: simultaneously using the three-dimensional style Ni-Mn double-metal hydroxide material of preparation as electrode Its chemical property is tested, the chemical property of working electrode tests completion in three-electrode system, and electrolyte is that 1M KOH is molten Liquid is to electrode with platinized platinum, and with saturated calomel electrode (SCE) for reference electrode, this three-electrode system is connected to electrochemical operation Stand upper (Shanghai Chen Hua, CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) The chemical property of technical testing electrode, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in 1A/g, than electricity Holding is 447F/g;Cycle charge-discharge 2000 encloses, and quality specific capacitance is 366F/g, cycle efficieny 82%.
Embodiment 4:
A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, comprising the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, it includes 0.01Mol SnCl that cotton, which is immersed,2、0.1Mol Sensitized treatment, sensitization time 10min are carried out in the sensitizing solution of HCl and a little Sn particle;
(2) cotton after cleaning sensitization with deionized water, then immersing cotton includes 10 μ g/mL PdCl2With It is activated in the activating solution of 0.018Mol HCl, activation time 10min;
(3) then the cotton after activation is carried out chemical deposit processing, coating by the cotton after being washed with deionized water activation Liquid includes 0.0712Mol NiSO4、0.561Mol NH4Cl, 0.034Mol sodium citrate and 0.0283Mol NaH2PO2, coating The processing time is 2h;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, the Pt plate of 2*2cm is anode, with 0.15Mol NiSO4、 0.12Mol NH4Cl is that electrolyte solution carries out constant pressure electro-deposition to nickel plating conduction cotton on CHI660E electrochemical workstation, Deposition voltage is 2V, sedimentation time 8-10min;
(5) 0.58g Ni (NO is weighed3)2With 0.38g MnCl2It is added in the deionized water of 100mL, carries out magnetic agitation 5min obtains mixed solution.
(6) 1.07gNH is weighed4Above-mentioned mixed solution is added in Cl, and magnetic agitation 5min obtains electrolyte.
(7) mixed solution obtained using step (6) is electrolyte, and using clean conductive fabric as working electrode, platinum electrode is pair Electrode, saturated calomel electrode are reference electrode, and the reaction of constant current spot deposition, the area of conductive fabric are carried out under electrochemical workstation For 1*2cm2, current density is 4mA cm-2, electrodeposition time 900S.
After reaction, the three-dimensional flower-shaped nickel manganese being composed of many sheets pair is just obtained after supersound washing, drying Metal hydroxides electrode material.
The nickel manganese double-metal hydroxide being prepared through this embodiment, shows the three-dimensional being combined by two-dimensional slice Style shape space structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
Electrochemical property test method: simultaneously using the three-dimensional style Ni-Mn double-metal hydroxide material of preparation as electrode Its chemical property is tested, the chemical property of working electrode tests completion in three-electrode system, and electrolyte is that 1M KOH is molten Liquid is to electrode with platinized platinum, and with saturated calomel electrode (SCE) for reference electrode, this three-electrode system is connected to electrochemical operation Stand upper (Shanghai Chen Hua, CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) The chemical property of technical testing electrode, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in 1A/g, than electricity Holding is 540F/g;Cycle charge-discharge 2000 encloses, and quality specific capacitance is 426F/g, cycle efficieny 79%.
Embodiment 5:
A kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, comprising the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, it includes 0.01Mol SnCl that cotton, which is immersed,2、0.1Mol Sensitized treatment, sensitization time 10min are carried out in the sensitizing solution of HCl and a little Sn particle;
(2) cotton after cleaning sensitization with deionized water, then immersing cotton includes 10 μ g/mL PdCl2With It is activated in the activating solution of 0.018Mol HCl, activation time 10min;
(3) then the cotton after activation is carried out chemical deposit processing, coating by the cotton after being washed with deionized water activation Liquid includes 0.0712Mol NiSO4、0.561Mol NH4Cl, 0.034Mol sodium citrate and 0.0283Mol NaH2PO2, coating The processing time is 2h;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, the Pt plate of 2*2cm is anode, with 0.15Mol NiSO4、 0.12Mol NH4Cl is that electrolyte solution carries out constant pressure electro-deposition to nickel plating conduction cotton on CHI660E electrochemical workstation, Deposition voltage is 2V, sedimentation time 8-10min;
(5) 0.58g Ni (NO is weighed3)2With 0.38g MnCl2It is added in the deionized water of 100mL, carries out magnetic agitation 5min obtains mixed solution.
(6) 1.07gNH is weighed4Above-mentioned mixed solution is added in Cl, and magnetic agitation 5min obtains electrolyte.
(7) mixed solution obtained using step (6) is electrolyte, and using clean conductive fabric as working electrode, platinum electrode is pair Electrode, saturated calomel electrode are reference electrode, and the reaction of constant current spot deposition, the area of conductive fabric are carried out under electrochemical workstation For 1*2cm2, current density is 8mA cm-2, electrodeposition time 1800S.
After reaction, the three-dimensional flower-shaped nickel manganese being composed of many sheets pair is just obtained after supersound washing, drying Metal hydroxides electrode material.
The nickel manganese double-metal hydroxide being prepared through this embodiment, shows the three-dimensional being combined by two-dimensional slice Style shape space structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
Electrochemical property test method: simultaneously using the three-dimensional style Ni-Mn double-metal hydroxide material of preparation as electrode Its chemical property is tested, the chemical property of working electrode tests completion in three-electrode system, and electrolyte is that 1M KOH is molten Liquid is to electrode with platinized platinum, and with saturated calomel electrode (SCE) for reference electrode, this three-electrode system is connected to electrochemical operation Stand upper (Shanghai Chen Hua, CHI660e), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) The chemical property of technical testing electrode, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, material manufactured in the present embodiment is in 1A/g, than electricity Holding is 500F/g;Cycle charge-discharge 2000 encloses, and quality specific capacitance is 350F/g, cycle efficieny 70%.
In conclusion the pattern of prepared electrode material is as shown in Figure 1, wherein (a) figure is the SEM that Ni:Mn ratio is 1:1 Figure, the round-like structure that structure as shown in the figure is made of two-dimensional nano piece layered double hydroxide;(b) figure is Ni:Mn The SEM that ratio is 1:2 schemes, and frame sheet shape double-metal hydroxide as shown in the figure forms the biggish frustum cone structure in gap;(c) figure The SEM figure for being 2:3 for Ni:Mn ratio, the flower that structure as shown in the figure is made of two-dimensional nano piece layered double hydroxide Shape structure.Compare and obtain by analysis: the specific surface area of the resulting electrode material of (c) figure is bigger, so there is superior electricity Chemical property.
In Fig. 2, (a) figure describes cyclic voltammetry (cv) figure of the electrode material under different nickel manganese ratios, The electrode material potential window is in 0~0.7V or so, it is shown that the wider potential window of electrode material.Every CV curve is ok Observe a pair of apparent redox peaks, this illustrates the capacitor main source of electrode material from the oxidation of nickel manganese double-hydroxide The fake capacitance generated in reduction process.Oxidation peak and reduction peak are all symmetrical about 0.4V, illustrate that electrode material has and well may be used Inverse property.As sweep speed is continuously increased, CV curve still has obvious redox peaks, and it is preferable to illustrate that material has High rate performance.The area of CV curve represents the size of the specific capacitance of this kind of material, can be clearly seen that come from (a) figure When Ni-Mn ratio is 2:3, specific capacitance is the largest in three kinds of ratios;(b) figure is the electrode material under different nickel manganese ratios Constant current charge-discharge test chart, charging curve and discharge curve all have certain symmetry, this illustrates that electrode material has very well Stability and high reversible.Each charging and discharging curve has a pair of of platform, this corresponds to the redox in CV curve React the position where peak.In the case where current density is as potential window, the discharge time of GCD curve is longer, then this A material has higher specific capacitance.When from (b) figure it is also seen that carry out Ni-Mn ratio be 2:3, when the electric discharge of GCD curve Between longest, specific capacitance is the largest in three kinds of ratios.

Claims (6)

1. a kind of preparation method of the flexible cloth electrode based on nickel manganese hydroxide, which comprises the following steps:
(1) pure cotton cloth is cut to several small pieces of 1*2cm, cotton is immersed in sensitizing solution and carries out sensitized treatment;
(2) cotton at least three times, is then immersed in activating solution and is activated by the cotton after cleaning sensitization with deionized water, cleaning Processing;
(3) then the cotton after activation is carried out chemical deposit processing, coating processing by the cotton after being washed with deionized water activation It is preceding using ammonium hydroxide by the pH value adjustment of solution to 9-10;
(4) using nickel plating conduction cotton obtained by step (3) as cathode, using the Pt plate of 2*2cm as anode, NiSO4、NH4Cl is electrolyte Solution carries out constant pressure electro-deposition, deposition voltage 2V, sedimentation time 8- to nickel plating conduction cotton on electrochemical workstation 10min;Nickel plating conductive fabric is just obtained after cleaning-drying processing;
(5) nickel nitrate and protochloride manganese, ammonium chloride and deionized water are mixed, obtain by deposition liquid needed for preparing electro-deposition To mixed solution;
(6) mixed solution obtained by step (5) is placed in a beaker by starting electrochemical workstation, using collector as working electrode, Platinum electrode be to electrode, saturated calomel electrode be reference electrode three-electrode system under timing is used to collector nickel plating conductive fabric Potentiometry carries out electrochemical deposition to it, after reaction, obtains Ni-Mn double-metal hydroxide electrode material after washing, drying Material.
2. a kind of preparation method of flexible cloth electrode based on nickel manganese hydroxide according to claim 1, feature exist In the sensitizing solution in step (1) includes SnCl2And a little Sn particle, wherein SnCl2The mass ratio of the material with HCl is 1:10, and And sensitization time is 10min.
3. a kind of preparation method of flexible cloth electrode based on nickel manganese hydroxide according to claim 2, feature exist In the activating solution in step (2) includes PdCl2And HCl, and activation time is 10min.
4. a kind of preparation method of flexible cloth electrode based on nickel manganese hydroxide according to claim 1 or 2, feature It is, includes NiSO in the coating liquid that the chemical deposit in step (3) uses4、NH4Cl, sodium citrate and NaH2PO2, and chemistry Plating time is 2h.
5. a kind of preparation method of flexible cloth electrode based on nickel manganese hydroxide according to claim 1 or 2, feature It is, nickel nitrate and protochloride manganese mass ratio are 0.9:1~1.5:1 in the mixed solution in step (5).
6. a kind of preparation method of flexible cloth electrode based on nickel manganese hydroxide according to claim 1 or 2, feature It is, the condition of the electrochemical deposition in step (6) are as follows: current density 8mA cm-2, sedimentation time 900S.
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