CN110223851A - A kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material - Google Patents
A kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material Download PDFInfo
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- CN110223851A CN110223851A CN201910433932.8A CN201910433932A CN110223851A CN 110223851 A CN110223851 A CN 110223851A CN 201910433932 A CN201910433932 A CN 201910433932A CN 110223851 A CN110223851 A CN 110223851A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of methods of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material, comprising the following steps: washes and dries nickel foam, as collector；Using molysite and cobalt salt as nickel source and cobalt source, it is sufficiently stirred with ammonium chloride and being mixed with deionized water, obtains mixed solution；Using mixed solution as electrolyte, under three-electrode system, electrochemical deposition reaction is carried out to collector in electrochemical workstation；After reaction, products therefrom washing is obtained into the flower-shaped Co-Fe double-metal hydroxide electrode material that several two-dimentional lamellars are combined into after dry；Phosphorating treatment is carried out to electrode material, obtains the Co-Fe-P combination electrode material.Method preparation time of the invention is short, high-efficient, laboratory apparatus, easy to operate, when resulting metal phosphide material is used for electrode material for super capacitor, shows specific capacitance height, good rate capability, the characteristic with longer cycle life.
Description
Technical field
The present invention relates to a kind of electrodeposition process to prepare the supercapacitor method of Co-Fe-P combination electrode material, belongs to
Metal sulfide electrode material for super capacitor technical field.
Background technique
Along with the sharp increase of world population and the fast development of social economy, facing mankind energy crisis and ecology
The double challenge of environmental degradation.With the rapid development of science and technology, people require energy storage device that must possess biggish capacitance, tool
Standby good cycle performance, and manufacturing cost is low, manufacturing process green non-pollution.These are that common batteries are unable to satisfy.
Supercapacitor appears in the visual field of people as the new type of energy storage device to emerge.
Supercapacitor is mainly formed by four parts, this four parts are collector, electrolyte, electrode and diaphragm respectively,
In this four part, the effect of electrode material is mostly important, and electrode material is to the storage performance of supercapacitor and is produced into
The influence of this control is most heavy in four parts, is the most critical part for controlling both factors, so developmental research is simultaneously
It has high-performance concurrently and inexpensive electrode material is the most main content of supercapacitor research work.Up to the present,
Most study has electrode material for super capacitor, and electrode material mainly has carbon material, hydroxide or metal oxide.Carbon
Material and metal oxidizing electrode investigation of materials are more, are commercialized gradually, and metal phosphide is studied focus primarily upon control at present
The growth tendency and pattern of prepared material, the Material cladding of exploitation and other advantages, to optimize the electrochemistry of metal phosphide
Can, it is more suitable for electrode material for super capacitor.
When the electrode material prepared possesses biggish specific surface area, the contact area change of electrode material and electrolyte
Greatly, the path of electron-transport is just shorter by, and the efficiency of electronics transfer increases, and improves the chemical property of material.
Summary of the invention
The object of the present invention is to provide a kind of sides of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material
Method, to obtain the metal phosphide electrode material for the surface area for having high.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material, comprising the following steps:
(1) nickel foam is washed and dried, as collector；
(2) it using molysite and cobalt salt as nickel source and cobalt source, is sufficiently stirred, is mixed with ammonium chloride and being mixed with deionized water
Close solution；
(3) mixed solution obtained using step (2) is right in electrochemical workstation under three-electrode system as electrolyte
Collector carries out electrochemical deposition reaction；
(4) after reaction, products therefrom washing is obtained into the flower-shaped Co- that several two-dimentional lamellars are combined into after dry
Fe double-metal hydroxide electrode material；
(5) phosphorating treatment is carried out to step (4) obtained electrode material, specifically: electrode material is loaded in ceramic boat,
NaH is added in bottom2PO2.H2O powder is put in heating and thermal insulation in tube furnace, after cooling, after cleaning-drying, is obtained described
Co-Fe-P combination electrode material.
Further, in the step (1), nickel foam is cut into 1*2cm2Bulk；Then successively with dilute hydrochloric acid, go
It is cleaned by ultrasonic in ionized water and dehydrated alcohol, wherein the mass concentration of dilute hydrochloric acid is 1/8；Be placed in vacuum oven with
Temperature 70 C dries 9~12h.
Further, in the step (2), molysite is Fe (NO3)3·9H2O, cobalt salt are Co (NO3)2·6H2O。
Further, in the mixed solution of the step (2), Fe3+With Co2+Molar ratio be 1:2~2:1；Ammonium chloride
Molar concentration is 0.2mmol/mL.
Further, in the step (3), three-electrode system refers to: the collector obtained using step (1) is work electricity
Pole, platinum electrode are to electrode, and saturated calomel electrode is reference electrode.
Further, in the step (3), when electrochemical deposition reacts, holding current density is that holding current density is 5
~8mA/cm2, sedimentation time is 800~900S.
Further, in the step (4), deionized water and dehydrated alcohol is successively used respectively to clean 2~3 electrode material
It is secondary, be placed on 70~90 DEG C of dry 5~9h in vacuum oven.
Further, in the step (5), NaH2PO2.H2The dosage of O powder be every piece of electrode material need 0.1~
0.4g。
Further, in the step (5), when heating and thermal insulation, using argon gas as protective gas, added with the speed of 2 DEG C/min
Heat is to 300 DEG C；And 2~3 hours are kept the temperature at this temperature, after being cooled to room temperature, take out product.
Further, in the step (5), the step of cleaning-drying are as follows: replace product deionized water and anhydrous second
It rinses 2~3 times, is then placed in 70 DEG C of vacuum ovens dry 10~12h.
The utility model has the advantages that method of the invention can be obtained using the nickel screen cleaned up as collector by electrodeposit reaction
Sheet double-metal hydroxide electrode material, then metal sulfide can be obtained by a phosphorating treatment.Side of the invention
Method preparation time is short, high-efficient, laboratory apparatus, easy to operate, deposits the sedimentary uniform ground of formation and thickness is controllable.Preparation
Resulting metal phosphide material be used for electrode material for super capacitor when, show specific capacitance height, good rate capability, with compared with
The characteristic of long cycle life, application prospect are very wide.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the resulting phosphide electrode material of the embodiment of the present invention；
Fig. 2 a- Fig. 2 d is the electrochemical property test figure of the resulting phosphide electrode material of the embodiment of the present invention, wherein
Fig. 2 a, 2b, 2c, 2d are CV curve, GCD curve, AC impedance spectroscopy and the cycle life figure of composite material respectively.
Specific embodiment
In order to more specifically illustrate the present invention, below by the present invention will be further elaborated in conjunction with the embodiments,
But do not limit the scope of the invention,
Embodiment 1
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 3 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed in vacuum oven
In the dry 9h of temperature 70 C, collector is obtained；
(2) 2mmolCo (NO is weighed3)2·6H2O, 2mmol Fe (NO3)3·9H2O and 20mmolNH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 10min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out in electrochemical workstation
Density is 8mA/cm2, electrodeposition time 900S；
(4) deionized water and dehydrated alcohol is successively used respectively to clean 2 times electrodeposit reaction obtained electrode material, later
70 DEG C of dry 8h in vacuum oven are placed in, the flower-shaped Co-Fe bimetal hydroxide that several two-dimentional lamellars are combined into is obtained
Object electrode material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.2g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, product is taken out, alternately rinses 3 with deionized water and anhydrous second
It is secondary, after dry 12h is then placed in 70 DEG C of vacuum ovens obtain iron cobalt metal phosphide.
The ferro-cobalt phosphide being prepared through this embodiment shows the three-dimensional knot built by a kind of nanoscale twins
Structure, there are biggish holes, and the phosphide of some areas bulk is assembled, the large specific surface area of the electrode material, style
Shape structure can be observed by scanning electron microscope (SEM) photograph, such as Fig. 1.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is the KOH solution that concentration is 1M, is to electricity with platinized platinum
Pole, with saturated calomel electrode (SCE) be reference electrode, this three-electrode system be connected on electrochemical workstation (Shanghai Chen Hua,
CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Chemical property, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 1493.75F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 1195F/g, cycle efficieny is
80%.
Embodiment 2
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 2 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed in vacuum oven
In the dry 9h of temperature 70 C, collector is obtained；
(2) 2mmol Co (NO is weighed3)2·6H2O、4mmol Fe(NO3)3·9H2O and 20mmol NH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 5min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out under electrochemical workstation
Density is 8mA/cm2, electrodeposition time 800S；
(4) electrodeposit reaction obtained electrode material is used into deionized water and washes of absolute alcohol 2 times, be placed on it is true
70 DEG C of dry 5h in empty drying box obtain the flower-shaped Co-Fe double-metal hydroxide electrode that several two-dimentional lamellars are combined into
Material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.2g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, sample products are taken out, are replaced with deionized water and anhydrous second
It rinses 2 times, obtains iron cobalt metal phosphide after being then placed in 70 DEG C of vacuum ovens dry 12h.
It is empty to show the three-dimensional style shape being combined by two-dimensional slice for the ferro-cobalt phosphide being prepared through this embodiment
Between structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is the KOH solution that concentration is 1M, is to electricity with platinized platinum
Pole, with saturated calomel electrode (SCE) be reference electrode, this three-electrode system be connected on electrochemical workstation (Shanghai Chen Hua,
CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Chemical property, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 302F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 241F/g, cycle efficieny 82%.
Embodiment 3
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 3 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed in vacuum oven
In the dry 10h of temperature 70 C, collector is obtained；
(2) 4mmolCo (NO is weighed3)2·6H2O, 2mmol Fe (NO3)3·9H2O and 20mmolNH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 10min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out in electrochemical workstation
Density is 8mA/cm2, electrodeposition time 900S；
(4) deionized water and dehydrated alcohol is successively used respectively to clean 3 times electrodeposit reaction obtained electrode material, later
80 DEG C of dry 5h in vacuum oven are placed in, the flower-shaped Co-Fe bimetal hydroxide that several two-dimentional lamellars are combined into is obtained
Object electrode material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.2g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, product is taken out, alternately rinses 3 with deionized water and anhydrous second
It is secondary, after dry 10h is then placed in 70 DEG C of vacuum ovens obtain iron cobalt metal phosphide.
It is empty to show the three-dimensional style shape being combined by two-dimensional slice for the ferro-cobalt phosphide being prepared through this embodiment
Between structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is 1M KOH solution, is to electrode, with full with platinized platinum
It is reference electrode with calomel electrode (SCE), this three-electrode system is connected on electrochemical workstation (Shanghai Chen Hua, CHI660E),
Using cyclic voltammetry (CV), the electrochemistry of constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Can, cyclical stability test carries out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 570F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 416F/g, cycle efficieny 73%.
Embodiment 4
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 2 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed in vacuum oven
In the dry 12h of temperature 70 C, collector is obtained；
(2) 2mmolCo (NO is weighed3)2·6H2O, 2mmol Fe (NO3)3·9H2O and 20mmolNH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 8min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out in electrochemical workstation
Density is 8mA/cm2, electrodeposition time 800S；
(4) deionized water and dehydrated alcohol is successively used respectively to clean 3 times electrodeposit reaction obtained electrode material, later
90 DEG C of dry 9h in vacuum oven are placed in, the flower-shaped Co-Fe bimetal hydroxide that several two-dimentional lamellars are combined into is obtained
Object electrode material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.1g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, product is taken out, alternately rinses 2 with deionized water and anhydrous second
~3 times, obtain iron cobalt metal phosphide after dry 12h is then placed in 70 DEG C of vacuum ovens.
It is empty to show the three-dimensional style shape being combined by two-dimensional slice for the ferro-cobalt phosphide being prepared through this embodiment
Between structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is the KOH solution that concentration is 1M, is to electricity with platinized platinum
Pole, with saturated calomel electrode (SCE) be reference electrode, this three-electrode system be connected on electrochemical workstation (Shanghai Chen Hua,
CHI660e), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Chemical property, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 693F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 519.7F/g, cycle efficieny 75%.
Embodiment 5
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 3 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed in vacuum oven
In the dry 12h of temperature 70 C, collector is obtained；
(2) 2mmolCo (NO is weighed3)2·6H2O, 2mmol Fe (NO3)3·9H2O and 20mmolNH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 5~10min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out in electrochemical workstation
Density is 5mA/cm2, electrodeposition time 900S；
(4) deionized water and dehydrated alcohol is successively used respectively to clean 2~3 times electrodeposit reaction obtained electrode material,
Be placed on 70 DEG C of dry 9h in vacuum oven, obtain the flower-shaped Co-Fe bimetallic hydrogen that several two-dimentional lamellars are combined into
Oxide electrode material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.4g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, product is taken out, alternately rinses 3 with deionized water and anhydrous second
It is secondary, after dry 10h is then placed in 70 DEG C of vacuum ovens obtain iron cobalt metal phosphide.
It is empty to show the three-dimensional style shape being combined by two-dimensional slice for the ferro-cobalt phosphide being prepared through this embodiment
Between structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is 1M KOH solution, is to electrode, with full with platinized platinum
It is reference electrode with calomel electrode (SCE), this three-electrode system is connected on electrochemical workstation (Shanghai Chen Hua, CHI660E),
Using cyclic voltammetry (CV), the electrochemistry of constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Can, cyclical stability test carries out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 1477F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 1152.06F/g, cycle efficieny is
78%.
Embodiment 6
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 2~3 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed on vacuum oven
It is interior to dry 9h in temperature 70 C, obtain collector；
(2) 2mmolCo (NO is weighed3)2·6H2O, 2mmol Fe (NO3)3·9H2O and 20mmolNH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 10min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out in electrochemical workstation
Density is 7mA/cm2, electrodeposition time 850S；
(4) deionized water and dehydrated alcohol is successively used respectively to clean 3 times electrodeposit reaction obtained electrode material, later
80 DEG C of dry 9h in vacuum oven are placed in, the flower-shaped Co-Fe bimetal hydroxide that several two-dimentional lamellars are combined into is obtained
Object electrode material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.2g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, product is taken out, alternately rinses 3 with deionized water and anhydrous second
It is secondary, after dry 12h is then placed in 70 DEG C of vacuum ovens obtain iron cobalt metal phosphide.
It is empty to show the three-dimensional style shape being combined by two-dimensional slice for the ferro-cobalt phosphide being prepared through this embodiment
Between structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is the KOH solution that concentration is 1M, is to electricity with platinized platinum
Pole, with saturated calomel electrode (SCE) be reference electrode, this three-electrode system be connected on electrochemical workstation (Shanghai Chen Hua,
CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Chemical property, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 279F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 139F/g, cycle efficieny 50%.
Embodiment 7
(1) nickel foam is cut into 1*2cm first2Bulk, the nickel foam sheared then is sequentially placed into dilute hydrochloric acid
Respectively cleaned 2 times in (wherein the mass ratio of HCl and water be 1:8), deionized water, dehydrated alcohol, be placed in vacuum oven
In the dry 10h of temperature 70 C, collector is obtained；
(2) 2mmolCo (NO is weighed3)2·6H2O, 2mmol Fe (NO3)3·9H2O and 20mmolNH4Cl, which is dissolved in, to be filled
In the beaker of 100mL deionized water, ultrasonic vibration stirs 6min, obtains mixed solution；
(3) mixed solution obtained using step (2) is electrolyte, and the collector obtained using step (1) is working electrode, platinum
Electrode is to electrode, and saturated calomel electrode is reference electrode, and constant current electrodeposit reaction, electric current are carried out in electrochemical workstation
Density is 6mA/cm2, electrodeposition time 880S；
(4) deionized water and dehydrated alcohol is successively used respectively to clean 3 times electrodeposit reaction obtained electrode material, later
90 DEG C of dry 6h in vacuum oven are placed in, the flower-shaped Co-Fe bimetal hydroxide that several two-dimentional lamellars are combined into is obtained
Object electrode material；
(5) step (4) obtained electrode material is subjected to phosphorating treatment, specifically: by electrode material in ceramic boat,
Bottom adds 0.3g NaH2PO2.H2O powder, puts it into tube furnace, under an argon atmosphere, is heated to the speed of 2 DEG C/min
300 DEG C, and 2 hours are kept the temperature at this temperature, after being cooled to room temperature, product is taken out, alternately rinses 3 with deionized water and anhydrous second
It is secondary, after dry 11h is then placed in 70 DEG C of vacuum ovens obtain iron cobalt metal phosphide.
It is empty to show the three-dimensional style shape being combined by two-dimensional slice for the ferro-cobalt phosphide being prepared through this embodiment
Between structure, the large specific surface area of the electrode material, style shape structure can be observed by scanning electron microscope (SEM) photograph.
The three-dimensional style ferro-cobalt phosphide prepared through this embodiment as electrode and is tested into its chemical property, is worked
The chemical property of electrode tests completion in three-electrode system, and electrolyte is the KOH solution that concentration is 1M, is to electricity with platinized platinum
Pole, with saturated calomel electrode (SCE) be reference electrode, this three-electrode system be connected on electrochemical workstation (Shanghai Chen Hua,
CHI660E), using cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance (EIS) technical testing electrode
Chemical property, cyclical stability test carry out on blue electric battery test system.
It can be obtained by above-mentioned Series Electrochemical performance test methods, electrode material manufactured in the present embodiment is in current density
Specific capacitance is 440F/g when for 1A/g；After cycle charge-discharge 2000 encloses, specific capacitance 272.8F/g, cycle efficieny 62%.
Fig. 1 is the scanning electron microscope (SEM) photograph of the resulting phosphide electrode material of the embodiment of the present invention, it can be seen that iron cobalt phosphatization
Object shows a kind of three-dimensional structure that nanoscale twins are built, there are biggish hole, and the phosphatization of some areas bulk
Object aggregation.
Fig. 2 a- Fig. 2 d is the electrochemical property test figure of the resulting phosphide electrode material of the embodiment of the present invention, in which:
Fig. 2 a describes cyclic voltammetry (cv) figure in the electrode material of different scanning speed, electrode material electricity
Position window is in 0~0.5V or so, it is shown that the wider potential window of electrode material.Every CV curve can be observed a pair of bright
Aobvious redox peaks, this illustrates that the capacitor main source of electrode material is produced from the oxidation-reduction process of nickel manganese double-hydroxide
Raw fake capacitance.Oxidation peak and reduction peak are all symmetrical about 0.3V, illustrate that electrode material has good invertibity.With scanning
Rate is continuously increased, and CV curve still has obvious redox peaks, illustrates that material has preferable high rate performance.
Fig. 2 b is the constant current charge-discharge test chart of the electrode material under different current densities, charging curve and discharge curve
All there is certain symmetry, this illustrates that electrode material has good stability and high reversible.Each charging and discharging curve
There is a pair of of platform, this corresponds to the position where the redox reaction peak in CV curve, because electrode surface aoxidizes
Along with the consumption of a large amount of electric energy when reduction reaction, being significantly detained can occur as time increases in the current potential of charge and discharge.?
In the case that current density is as potential window, GCD curve to put the time longer, then this material has higher than electricity
Capacity.
Fig. 2 c is the ac impedance spectroscopy of combination electrode.Impedance spectrum is by the high frequency region of semi arch and the low frequency range structure of oblique line
At the intersection point of curve and reference axis is the contact impedance of electrode.Half circular diameter of electrode high frequency region represent electrode and electrolyte it
Between charge transfer resistance, diameter is smaller to illustrate that the resistance of electrode electro Chemical reaction is smaller.The straight line of low frequency range represents electrolyte
In diffusion impedance (Warburg impedance) of the ion in electrode active material, what is mainly reflected is the attribute of electrochemical capacitor,
The bigger diffusion resistance for representing electrolyte in electrode material of slope is smaller.The contact impedance and diffusion impedance of combination electrode material
It is all smaller.
Fig. 2 d is the cycle life figure of prepared combination electrode.After 2000 circle charge and discharge cycles, the circulation of combination electrode is protected
Holdup is respectively 80%, and the combination electrode material possesses certain advantage on cyclical stability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material, it is characterised in that: including with
Lower step:
(1) nickel foam is washed and dried, as collector；
(2) it using molysite and cobalt salt as nickel source and cobalt source, is sufficiently stirred with ammonium chloride and being mixed with deionized water, obtains mixing molten
Liquid；
(3) mixed solution obtained using step (2) is electrolyte, under three-electrode system, to afflux in electrochemical workstation
Body carries out electrochemical deposition reaction；
(4) after reaction, it is bis- that the flower-shaped Co-Fe that several two dimension lamellars are combined into is obtained after products therefrom washing being dried
Metal hydroxides electrode material；
(5) phosphorating treatment is carried out to step (4) obtained electrode material, specifically: electrode material is loaded in ceramic boat, bottom
NaH is added2PO2.H2O powder is put in heating and thermal insulation in tube furnace, after cooling, after cleaning-drying, obtains the Co-
Fe-P combination electrode material.
2. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
It is characterized in that: in the step (1), nickel foam being cut into 1*2cm2Bulk；Then successively with dilute hydrochloric acid, deionized water and
It is cleaned by ultrasonic in dehydrated alcohol, wherein the mass concentration of dilute hydrochloric acid is 1/8；Be placed in vacuum oven with temperature 70 C
Dry 9~12h.
3. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
Be characterized in that: in the step (2), molysite is Fe (NO3)3·9H2O, cobalt salt are Co (NO3)2·6H2O。
4. the side of electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1 or 3
Method, it is characterised in that: in the mixed solution of the step (2), Fe3+With Co2+Molar ratio be 1:2~2:1；Ammonium chloride rubs
Your concentration is 0.2mmol/mL.
5. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
Be characterized in that: in the step (3), three-electrode system refers to: the collector obtained using step (1) is working electrode, platinum electrode
For to electrode, saturated calomel electrode is reference electrode.
6. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
Be characterized in that: in the step (3), when electrochemical deposition reacts, holding current density is that holding current density is 5~8mA/
cm2, sedimentation time is 800~900S.
7. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
It is characterized in that: in the step (4), electrode material successively being used deionized water and dehydrated alcohol respectively clean 2~3 times, later
It is placed in 70~90 DEG C of dry 5~9h in vacuum oven.
8. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
It is characterized in that: in the step (5), NaH2PO2.H2The dosage of O powder is that every piece of electrode material needs 0.1~0.4g.
9. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
It is characterized in that: in the step (5), when heating and thermal insulation, using argon gas as protective gas, being heated to 300 with the speed of 2 DEG C/min
℃；And 2~3 hours are kept the temperature at this temperature, after being cooled to room temperature, take out product.
10. the method for electrodeposition process preparation supercapacitor Co-Fe-P combination electrode material according to claim 1,
It is characterized by: in the step (5), the step of cleaning-drying are as follows: product deionized water and anhydrous second are alternately rinsed 2~
3 times, dry 10~12h is then placed in 70 DEG C of vacuum ovens.
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