CN109994715A - A kind of self-supporting electrode and its preparation method and application - Google Patents
A kind of self-supporting electrode and its preparation method and application Download PDFInfo
- Publication number
- CN109994715A CN109994715A CN201810005771.8A CN201810005771A CN109994715A CN 109994715 A CN109994715 A CN 109994715A CN 201810005771 A CN201810005771 A CN 201810005771A CN 109994715 A CN109994715 A CN 109994715A
- Authority
- CN
- China
- Prior art keywords
- electrode
- self
- solution
- conductive substrates
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention provides a kind of self-supporting electrodes and its preparation method and application.The self-supporting electrode includes conductive substrates and the metal carbonitride chemical combination object electrode material being supported in the conductive substrates.The preparation method includes: that (1) grows polypyrrole film in conductive substrates, obtains the conductive substrates of polypyrrole cladding；(2) metal precursor is grown in the conductive substrates of step (1) the polypyrrole cladding, obtains electrode precursor；(3) step (2) the electrode precursor calcining carbonization is obtained into the self-supporting electrode.The self-supporting electrode is used for electrocatalytic decomposition water, electro-catalysis oxygen reduction or lithium ion battery.The stability of self-supporting electrode provided by the invention is high, and electron-transport is high-efficient, high catalytic efficiency；Preparation method provided by the invention simplifies the preparation method of synthesis self-supporting electrode, and improves the catalytic efficiency of self-supporting electrode, ensure that the performance of product fine.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of self-supporting electrode and preparation method thereof.
Background technique
Metal carbonitride chemical combination object is urged with advantages such as electric conductivity in catalytic field, especially electricity due to having excellent stability
Change the fields such as decomposition water, electro-catalysis oxygen reduction and lithium ion battery and all obtains extensive concern.But metal carbonitride chemical combination
The synthesis of object, the method being especially prepared in situ on the electrode are also considerably less.Currently, most metals carboritride electrode
Preparation is that fine catalyst is attached to electrode surface by spin-coating method.Conductive polymer is usually introduced in electrode production process
Adhesive of the polymer as catalyst and electrode basement.This traditional electrode preparation method is primarily present following drawback: 1)
The microscopic appearance of catalyst is not easy to control；2) presence of adhesive limits the exposure in catalyst surface active site；3) it is catalyzed
It is obstructed to inhibit electron transfer process in the interface of agent and electrode basement；4) gas that electrode surface generates is easy to make catalyst
It falls off from electrode basement, reduces electrode efficiency and service life.Develop self-supporting catalyst electrode (self-supported
It electrocatalyst) is the effective way for solving traditional electrode drawback.Compared with traditional electrode, the advantages of self-supporting electrode
Mainly the following aspects: 1) catalyst is directly grown in electrode basement, effectively increases the steady of electrode surface catalyst
Qualitative and electron-transport efficiency；2) microstructure of catalyst, the more conducively exposure of active site are easy to control；3) conductive polymer
Sub- adhesive it is expensive, self-supporting preparation method greatly reduces cost, is more suitable for industrial application.
However the preparation method of self-supporting electrode is generally relatively complicated at present, long flow path is at high cost, is unfavorable for industry metaplasia
It produces.CN105655153A provides a kind of preparation method of self-supporting capacitor electrode material, and this method first impregnates nickel foam
In polyacrylonitrile/polyvinylpyrrolidone N-N dimethyl formamide solution of various concentration, then further take out be put into from
In sub- water, the porous polypropylene nitrile precursor thin-film of nickel foam support is formed.Before the porous polypropylene nitrile that the nickel foam is supported
It drives body to be placed in inert atmosphere, 800 degrees Celsius of -1000 degrees Celsius of carbonization treatments and 750 degrees Celsius of potassium hydroxide activation processing,
The nickel foam porous carbon nano-electrode material of the self-supporting of high-specific surface area can be obtained.The disadvantage of this method is that process
Long, at high cost, industrialization prospect is bad.
Therefore, develop it is a kind of more simplify, the lower self-supporting electrode preparation method of cost has this field important
Meaning.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of self-supporting electrode and its systems
Preparation Method and purposes.In the present invention, the self-supporting electrode refers to that material prepared itself can be used as electrode material, is not necessarily to
It is carried on other electrodes.Self-supporting electrode stability provided by the invention is good, high catalytic efficiency.Preparation side provided by the invention
Method simplifies the method for preparing metal carbonitride chemical combination object electrode, saves the preparation cost.Self-supporting electrode provided by the invention is suitable
For a variety of electrocatalytic reactions.
In order to achieve the above object, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of self-supporting electrode, the self-supporting electrode includes conductive substrates and load
Metal carbonitride chemical combination object electrode material in the conductive substrates.
In this self-supporting electrode provided by the invention, metal carbonitride chemical combination object electrode material is also used as catalyst, so that
The self-supporting electrode has catalytic action.In self-supporting electrode provided by the invention, metal carbonitride chemical combination object growth in situ
In forming self-supporting electrode in conductive substrates, this structure has organically combined metal carbonitride chemical combination object with conductive substrates
Come, significantly reduce the interface resistance between metal carbonitride chemical combination object and conductive substrates, improve metal carbonitride chemical combination object and
Electron-transport efficiency between conductive substrates, improves catalytic efficiency, is suitable for a variety of electrocatalytic reactions, and this structure makes
Metal carbonitride chemical combination object is not easily to fall off, excellent in stability.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the self-supporting electrode is conductive substrates and is supported on the conductive base
Metal carbonitride chemical combination object electrode material on bottom.Self-supporting electrode provided by the invention only by conductive substrates and is being supported on institute
The metal carbonitride chemical combination object electrode material composition in conductive substrates is stated, when being free of other materials, the performance of product is more excellent.
Preferably, in the metal carbonitride chemical combination object, metallic element include in iron, cobalt, nickel, copper or molybdenum any one or
At least two combination, it is typical but be non-limiting combination and have: the group of the combination of the combination of iron and cobalt, nickel and copper, copper and molybdenum
Close etc..
Preferably, the conductive substrates are carbon cloth.
Preferably, the metal carbonitride chemical combination object with a thickness of 2nm-20nm, such as 2nm, 4nm, 6nm, 8nm, 10nm,
12nm, 14nm, 16nm, 18nm or 20nm etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable.
Second aspect, the present invention provides the preparation method of self-supporting electrode as described in relation to the first aspect, the method packets
Include following steps:
(1) polypyrrole film is grown in conductive substrates, obtains the conductive substrates of polypyrrole cladding；
(2) metal precursor is grown in the conductive substrates of step (1) the polypyrrole cladding, obtains electrode precursor；
(3) step (2) the electrode precursor calcining carbonization is obtained into the self-supporting electrode.
In preparation method provided by the invention, using polypyrrole film coated with conductive substrate, polypyrrole film is used as carbon source simultaneously
And nitrogen source, the method for preparing metal carbonitride chemical combination object electrode is greatly simplified, is saved the preparation cost.Furthermore the present invention provides
Preparation method made metal carbonitride chemical combination object growth in situ in conductive substrates surface, ensure that finally obtained self-supporting electricity
The excellent performance of pole.
As currently preferred technical solution, in step (1), the growth polypyrrole film is galavanic growth polypyrrole
Film.
Preferably, the galavanic growth polypyrrole film the following steps are included:
Using the conductive substrates as working electrode, and to electrode, reference electrode and electrolyte group containing pyrrole monomer
At plating system, it is electroplated to obtain the conductive substrates of polypyrrole cladding in the plating system.
As currently preferred technical solution, the conductive substrates are carbon cloth.
Preferably, described is platinum electrode and/or carbon-point, preferably platinum electrode to electrode.In the present invention, the platinum electrode
And/or carbon-point refers to can be platinum electrode, or carbon-point can also be the combination of platinum electrode and carbon-point.
Preferably, the reference electrode is silver/silver chloride electrode and/or saturated calomel electrode, preferably silver/silver chlorate electricity
Pole.In the present invention, the silver/silver chloride electrode and/or saturated calomel electrode, which refer to, to be silver/silver chloride electrode, can also be with
It can also be the combination of silver/silver chloride electrode and saturated calomel electrode for saturated calomel electrode.
Preferably, the electrolyte is the sodium perchlorate aqueous solution containing pyrrole monomer.
Preferably, the concentration of the sodium perchlorate aqueous solution be 0.01mol/L-2.0mol/L, such as 0.01mol/L,
0.02mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1.0mol/L, 1.5mol/L or 2.0mol/L etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 0.5mol/L.
Preferably, in the electrolyte, the ratio between volume and the volume of sodium perchlorate aqueous solution of pyrrole monomer are 1:1-1:
20, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, such as 1:1,1:2,
1:4,1:6,1:8,1:10,1:12,1:14,1:16,1:18 or 1:20 etc., preferably 1:10.
Preferably, the volume of the electrolyte be 10mL-200mL, such as 10mL, 20mL, 50mL, 100mL, 150mL or
200mL etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably
50mL。
Preferably, the voltage of the plating be 0.1V-2V, such as 0.1V, 0.2V, 0.5V, 1.0V, 1.5V or 2.0V etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 1.0V.
Preferably, the time of the plating be 50s-1000s, such as 50s, 100s, 150s, 200s, 250s, 500s,
550s, 600s, 650s, 700s, 750s, 800s, 850s, 900s, 950s or 1000s etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 500s.
As currently preferred technical solution, in step (2), the growth metal precursor the following steps are included:
The conductive substrates of step (1) the polypyrrole cladding are mixed with source metal solution, are reacted, before obtaining electrode
Body.
The step in, metal reacts with polypyrrole, obtains polypyrrole metal precursor, i.e. electrode precursor.
As currently preferred technical solution, the source metal solution is source metal aqueous solution.
Preferably, the source metal solution is transition metal source solution.
Preferably, the transition metal source solution includes source of iron solution, cobalt source solution, nickel source solution, copper source solution or molybdenum
In the solution of source any one or at least two combination, typical but be non-limiting combination and have: source of iron solution and cobalt source are molten
The combination of liquid, the combination of nickel source solution and copper source solution, copper source solution and the combination of molybdenum source solution etc..
Preferably, the cobalt source solution includes in cobalt chloride solution, cobalt nitrate solution, cobalt sulfate solution or acetic acid cobalt liquor
Any one or at least two combination, it is typical but be non-limiting combination and have: cobalt chloride solution and cobalt nitrate solution
Combination, the combination of cobalt sulfate solution and acetic acid cobalt liquor, cobalt nitrate solution and the combination of cobalt sulfate solution etc..
Preferably, the source metal solution is transition metal source aqueous solution.
Preferably, the concentration of the source metal solution be 0.5mol/L-2.5mol/L, such as 0.5mol/L, 1mol/L,
1.5mol/L, 2mol/L or 2.5mol/L etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable, preferably 1mol/L.
Preferably, the temperature of the reaction be 80 DEG C -200 DEG C, such as 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C,
180 DEG C or 200 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable,
Preferably 160 DEG C.
Preferably, the time of the reaction be 5h-72h, such as 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h,
50h, 55h, 60h, 65h, 70h or 72h etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable, preferably for 24 hours.
As currently preferred technical solution, in step (3), the temperature of the calcining carbonization is 800 DEG C -1200 DEG C,
Such as 800 DEG C, 900 DEG C, 1000 DEG C, 1100 DEG C or 1200 DEG C etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable, and preferably 900 DEG C.
Preferably, in step (3), it is described calcining carbonization time be 0.5h-5h, such as 0.5h, 1h, 1.5h, 2h,
2.5h, 3h, 3.5h, 4h, 4.5h or 5h etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value is equally applicable, preferably 2h.
Preferably, in step (3), the atmosphere of the calcining carbonization is the mixed gas of hydrogen and argon gas.
Preferably, in the mixed gas of the hydrogen and argon gas, the volume fraction of hydrogen is 5%.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
(1) using the conductive substrates as working electrode, and to electrode, reference electrode and contain pyrrole monomer
0.5mol/L sodium perchlorate aqueous solution forms plating system, is gathered in the plating system with the voltage plating 500s of 1.0V
The conductive substrates of pyrroles's cladding；Described is platinum electrode to electrode, and the reference electrode is silver/silver chloride electrode, and the pyrroles is single
The ratio between volume and the volume of sodium perchlorate aqueous solution of body are 1:10；
(2) conductive substrates of step (1) the polypyrrole cladding are mixed with the transition metal source aqueous solution of 1mol/L,
It is reacted at 160 DEG C for 24 hours, obtains electrode precursor；
(3) by step (2) electrode precursor, 900 DEG C of calcining carbonization 2h obtain institute under the mixed gas of hydrogen and argon gas
State self-supporting electrode, in the mixed gas of the hydrogen and argon gas, the volume fraction of hydrogen is 5%.
The third aspect, the present invention provides the purposes of self-supporting electrode as described in relation to the first aspect, the self-supporting electrode
For electrocatalytic decomposition water, electro-catalysis oxygen reduction or lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) in self-supporting electrode provided by the invention, metal carbonitride chemical combination object is grown on conductive base as catalyst in situ
Bottom surface, not easily to fall off, the stability of this self-supporting metal carbonitride chemical combination object electrode is high, and electron-transport is high-efficient, catalysis effect
Rate is high, these excellent performances make self-supporting electrode applications provided by the invention extensive；
(2) polypyrrole film of growth in situ is introduced in preparation method provided by the invention as carbon source and nitrogen source, is carbonized
Metal carbonitride chemical combination object growth in situ simplifies synthesis self-supporting metal carbonitride chemical combination object electrode in conductive substrates surface in journey
Preparation method, and the catalytic efficiency of self-supporting metal carbonitride chemical combination object electrode is improved, it ensure that the performance of product fine.
Detailed description of the invention
Shape appearance figure of the Fig. 1 for carbon cloth used in 1 step of embodiment (1) at scanning electron microscope (SEM)；
Fig. 2 is the obtained polypyrrole film for being coated on carbon cloth of 1 step of embodiment (1) at scanning electron microscope (SEM)
Shape appearance figure；
Fig. 3 is that the original position that 1 step of embodiment (3) obtains is carried on the cobalt carboritride of carbon cloth in scanning electron microscope
(SEM) shape appearance figure under.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 3.0g anhydrous sodium perchlorate is dissolved in 200mL deionized water, obtains sodium perchlorate aqueous solution；
(B) 10mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) being placed in electrolytic cell, carbon cloth is used as working electrode, silver-colored/
Silver chloride electrode is used as to electrode as reference electrode, platinum plate electrode, is electrolysed 500s under 0.5V voltage, obtains being coated on carbon cloth
Polypyrrole film；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 2.0g cobalt chloride is dissolved in 20mL water, obtains cobalt chloride solution, be placed in 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film that carbon cloth is coated on obtained in step (1) is placed in cobalt chloride solution, at 160 DEG C
Heat 12h.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
Cobalt precursors-polypyrrole film-carbon cloth material obtained in step (2) is placed in tube furnace, it is mixed in hydrogen and argon gas
Close atmosphere (in the mixed atmosphere, the volume fraction of hydrogen be 5%) under, 900 DEG C of heating 2h are to get to the metal for being carried on carbon cloth
Cobalt carboritride self-supporting electrode.
In the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metallic cobalt carbon nitrification
The thickness of object is about 5nm.
The stability of the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 310mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.
The metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Shape appearance figure of the Fig. 1 for carbon cloth used in 1 step of embodiment (1) at scanning electron microscope (SEM), can by the figure
To find out that carbon cloth is made of the fiber line that diameter is about 10 microns.
Fig. 2 is the obtained polypyrrole film for being coated on carbon cloth of 1 step of embodiment (1) at scanning electron microscope (SEM)
Shape appearance figure, can be seen that polypyrrole film uniform load in carbon cloth surfaces, forms shell/nuclear structure by the figure.
Fig. 3 is that the original position that 1 step of embodiment (3) obtains is carried on the cobalt carboritride of carbon cloth in scanning electron microscope
(SEM) shape appearance figure under can be seen that cobalt carboritride forms evenly dispersed nano particle on carbon cloth surface layer by the figure.
Embodiment 2
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 5.0g anhydrous sodium perchlorate is dissolved in 100mL deionized water, obtains sodium perchlorate aqueous solution；
(B) 6mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) being placed in electrolytic cell, carbon cloth is used as working electrode, silver-colored/
Silver chloride electrode is used as to electrode as reference electrode, platinum plate electrode, is electrolysed 50s under 1.0V voltage, obtains being coated on carbon cloth
Polypyrrole film；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 2.0g nickel chloride is dissolved in 20mL water, obtains nickel chloride aqueous solution, be placed in 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film that carbon cloth is coated on obtained in step (1) is placed in nickel chloride aqueous solution, at 100 DEG C
Heat 12h.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
The precursor of nickel obtained in step (2)-polypyrrole film-carbon cloth material is placed in tube furnace, it is mixed in hydrogen and argon gas
It closes under atmosphere, 800 DEG C of heating 3h are to get to the metallic nickel carboritride self-supporting electrode for being carried on carbon cloth.
In the metallic nickel carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metallic nickel carbon nitrification
The thickness of object is about 10nm.
The stability of the metallic nickel carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 300mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.Its electrocatalytic decomposition aquatic products hydrogen, catalytic efficiency can also be stablized holding 10 hours or more.
The metallic nickel carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Embodiment 3
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 1.0g anhydrous sodium perchlorate is dissolved in 20mL deionized water, obtains sodium perchlorate aqueous solution；
(B) 10mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) is placed in electrolytic cell, carbon cloth is as working electrode, saturation
Calomel electrode is used as to electrode as reference electrode, carbon-point, is electrolysed 500s under 0.5V voltage, obtains the poly- pyrrole for being coated on carbon cloth
Cough up film；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 5.0g ammonium molybdate is dissolved in 20mL water, obtains ammonium molybdate aqueous solution, be placed in 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film for being coated on carbon cloth obtained in step (1) is placed in ammonium molybdate aqueous solution, is added at 80 DEG C
Heat is for 24 hours.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
The precursor of molybdenum obtained in step (2)-polypyrrole film-carbon cloth material is placed in tube furnace, it is mixed in hydrogen and argon gas
Close atmosphere (in the mixed atmosphere, the volume fraction of hydrogen be 5%) under, 1000 DEG C of heating 3h are to get to the gold for being carried on carbon cloth
Belong to molybdenum carboritride self-supporting electrode.
In the metal molybdenum carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metal molybdenum carbon nitrification
The thickness of object is about 8nm.
The stability of the metal molybdenum carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 360mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.
The metal molybdenum carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Embodiment 4
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 10.0g anhydrous sodium perchlorate is dissolved in 200mL deionized water, obtains sodium perchlorate aqueous solution；
(B) 10mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) being placed in electrolytic cell, carbon cloth is used as working electrode, silver-colored/
Silver chloride electrode is used as to electrode as reference electrode, platinum plate electrode, is electrolysed 50s under 2.0V voltage, obtains being coated on carbon cloth
Polypyrrole film；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 0.5g ferric acetate is dissolved in 20mL water, obtains acetic acid water solution, be placed in 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film that carbon cloth is coated on obtained in step (1) is placed in acetic acid water solution, at 100 DEG C
Heat 20h.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
The precursor of iron obtained in step (2)-polypyrrole film-carbon cloth material is placed in tube furnace, it is mixed in hydrogen and argon gas
It closes under atmosphere, 900 DEG C of heating 5h are to get to the metallic iron carboritride self-supporting electrode for being carried on carbon cloth.
In the metallic iron carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metallic iron carbon nitrification
The thickness of object is about 15nm.
The stability of the metallic iron carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 360mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.
The metallic iron carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Embodiment 5
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 14g anhydrous sodium perchlorate is dissolved in 200mL deionized water, obtaining sodium perchlorate aqueous solution, (sodium perchlorate is dense
Degree is 0.5mol/L)；
(B) 20mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) being placed in electrolytic cell, carbon cloth is used as working electrode, silver-colored/
Silver chloride electrode is used as to electrode as reference electrode, platinum plate electrode, is electrolysed 500s under 0.5V voltage, obtains being coated on carbon cloth
Polypyrrole film；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 6.5g cobalt chloride is dissolved in 20mL water, obtains cobalt chloride solution (cobalt chloride concentration 2.5mol/L), sets
In 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film that carbon cloth is coated on obtained in step (1) is placed in cobalt chloride solution, at 160 DEG C
Heat 72h.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
Cobalt precursors-polypyrrole film-carbon cloth material obtained in step (2) is placed in tube furnace, under an argon atmosphere,
1200 DEG C of heating 0.5h are to get to the metallic cobalt carboritride self-supporting electrode for being carried on carbon cloth.
In the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metallic cobalt carbon nitrification
The thickness of object is about 20nm.
The stability of the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 330mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.
The metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Embodiment 6
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 0.28g anhydrous sodium perchlorate is dissolved in 200mL deionized water, obtains sodium perchlorate aqueous solution (sodium perchlorate
Concentration is 0.01mol/L)；
(B) 10mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) being placed in electrolytic cell, carbon cloth is used as working electrode, silver-colored/
Silver chloride electrode is used as to electrode as reference electrode, platinum plate electrode, is electrolysed 1000s under 0.1V voltage, obtains being coated on carbon
The polypyrrole film of cloth；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 5.8g cobalt nitrate is dissolved in 20mL water, obtains cobalt nitrate aqueous solution (nitric acid cobalt concentration is 1mol/L), is placed in
In 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film that carbon cloth is coated on obtained in step (1) is placed in cobalt nitrate aqueous solution, at 160 DEG C
Heat 12h.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
Cobalt precursors-polypyrrole film-carbon cloth material obtained in step (2) is placed in tube furnace, it is mixed in hydrogen and argon gas
Close atmosphere (in the mixed atmosphere, the volume fraction of hydrogen be 5%) under, 900 DEG C of heating 2h are to get to the metal for being carried on carbon cloth
Cobalt carboritride self-supporting electrode.
In the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metallic cobalt carbon nitrification
The thickness of object is about 2nm.
The stability of the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 340mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.
The metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Embodiment 7
The present embodiment provides a kind of preparation method of self-supporting electrode, method particularly includes:
(1) the galavanic growth polypyrrole coating film on carbon cloth, specifically includes the following steps:
(A) 5.6g anhydrous sodium perchlorate is dissolved in 20mL deionized water, obtaining sodium perchlorate aqueous solution, (sodium perchlorate is dense
Degree is 2mol/L)；
(B) 20mL pyrrole monomer is added obtained by step (A) in sodium perchlorate solution, stirs to clarify transparent, obtain pyrrole
Cough up-sodium perchlorate aqueous solution；
(C) pyrroles-sodium perchlorate aqueous solution obtained by step (B) being placed in electrolytic cell, carbon cloth is used as working electrode, silver-colored/
Silver chloride electrode is used as to electrode as reference electrode, platinum plate electrode, is electrolysed 500s under 0.5V voltage, obtains being coated on carbon cloth
Polypyrrole film；
(D) the obtained polypyrrole film for being coated on carbon cloth deionized water is rinsed three times；
(2) metal precursor, detailed process are grown on the carbon cloth of polypyrrole film cladding are as follows:
(A) 2.8g cobaltous sulfate is dissolved in 20mL water, obtains cobalt sulfate solution (cobalt sulfate concentration 0.5mol/L), sets
In 100mL polytetrafluoro reaction kettle；
(B) polypyrrole film that carbon cloth is coated on obtained in step (1) is placed in cobalt sulfate solution, at 200 DEG C
Heat 7h.
(3) the calcining carbonization of obtained polypyrrole metal precursor is obtained being carried on the electrode of the metal carbonitride chemical combination object of carbon cloth
Material:
Cobalt precursors-polypyrrole film-carbon cloth material obtained in step (2) is placed in tube furnace, it is mixed in hydrogen and argon gas
Close atmosphere (in the mixed atmosphere, the volume fraction of hydrogen be 5%) under, 900 DEG C of heating 2h are to get to the metal for being carried on carbon cloth
Cobalt carboritride self-supporting electrode.
In the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth, metallic cobalt carbon nitrification
Object with a thickness of about 15nm.
The stability of the metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth is high, catalysis effect
Rate is good, and electrocatalytic decomposition aquatic products oxygen performance can achieve current density 10mA/cm at overpotential 360mV (vs.RHE)2, urge
Changing efficiency can stablize 10 hours or more.
The metallic cobalt carboritride self-supporting electrode manufactured in the present embodiment for being carried on carbon cloth can be used for electrocatalytic decomposition
Water, electro-catalysis oxygen reduction or lithium ion battery applications etc..
Comparative example 1
Catalyst metals cobalt carboritride is attached to carbon cloth surfaces by spin-coating method by this comparative example, is introduced macromolecule and is led
Electric polymer Nafion reagent (i.e. perfluorosulfonic acid type polymer solution) is used as catalyst metals cobalt carboritride and electrode base
Adhesive between the carbon cloth of bottom prepares a kind of metallic cobalt carboritride electrode.In the metallic cobalt carboritride electrode, metallic cobalt
Thickness of the carboritride on carbon cloth is identical as the product of embodiment 1.
The product that this comparative example is prepared needs about 400mV (vs.RHE) in electrocatalytic decomposition aquatic products oxygen performance test
Overvoltage can be only achieved 10mA/cm2Current density.
It is high to can be seen that self-supporting electrode stability provided by the invention with comparative example based on the above embodiments, electronics passes
It is defeated high-efficient, high catalytic efficiency.The polypyrrole film of growth in situ is introduced in preparation method provided by the invention as carbon source and nitrogen
Source, metal carbonitride chemical combination object growth in situ simplifies synthesis self-supporting metal carbonitride in conductive substrates surface in carbonisation
The preparation method of object electrode is closed, and improves the catalytic efficiency of self-supporting metal carbonitride chemical combination object electrode, ensure that product is excellent
Good performance.Comparative example does not use the solution of the present invention, thus can not obtain effect of the invention.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of self-supporting electrode, which is characterized in that the self-supporting electrode includes conductive substrates and is supported on the conduction
Metal carbonitride chemical combination object electrode material in substrate.
2. self-supporting electrode according to claim 1, which is characterized in that the self-supporting electrode is conductive substrates and bears
The metal carbonitride chemical combination object electrode material being loaded in the conductive substrates；
Preferably, in the metal carbonitride chemical combination object, metallic element include in iron, cobalt, nickel, copper or molybdenum any one or at least
Two kinds of combination；
Preferably, the conductive substrates are carbon cloth；
Preferably, the metal carbonitride chemical combination object with a thickness of 2nm-20nm.
3. the preparation method of self-supporting electrode according to claim 1 or 2, which is characterized in that the method includes following
Step:
(1) polypyrrole film is grown in conductive substrates, obtains the conductive substrates of polypyrrole cladding；
(2) metal precursor is grown in the conductive substrates of step (1) the polypyrrole cladding, obtains electrode precursor；
(3) step (2) the electrode precursor calcining carbonization is obtained into the self-supporting electrode.
4. preparation method according to claim 3, which is characterized in that in step (1), the growth polypyrrole film is plating
Grow polypyrrole film；
Preferably, the galavanic growth polypyrrole film the following steps are included:
Using the conductive substrates as working electrode, electricity is formed with to electrode, reference electrode and electrolyte containing pyrrole monomer
Plating system is electroplated to obtain the conductive substrates of polypyrrole cladding in the plating system.
5. the preparation method according to claim 4, which is characterized in that the conductive substrates are carbon cloth；
Preferably, described is platinum electrode and/or carbon-point, preferably platinum electrode to electrode；
Preferably, the reference electrode is silver/silver chloride electrode and/or saturated calomel electrode, preferably silver/silver chloride electrode；
Preferably, the electrolyte is the sodium perchlorate aqueous solution containing pyrrole monomer；
Preferably, the concentration of the sodium perchlorate aqueous solution is 0.01mol/L-2.0mol/L, preferably 0.5mol/L；
Preferably, in the electrolyte, the ratio between volume and the volume of sodium perchlorate aqueous solution of pyrrole monomer are 1:1-1:20, excellent
It is selected as 1:10；
Preferably, the volume of the electrolyte is 10mL-200mL, preferably 50mL；
Preferably, the voltage of the plating is 0.1V-2V, preferably 1.0V；
Preferably, the time of the plating is 50s-1000s, preferably 500s.
6. according to the described in any item preparation methods of claim 3-5, which is characterized in that in step (2), before the growth metal
Body the following steps are included:
The conductive substrates of step (1) the polypyrrole cladding are mixed with source metal solution, is reacted, obtains electrode precursor.
7. preparation method according to claim 6, which is characterized in that the source metal solution is source metal aqueous solution；
Preferably, the source metal solution is transition metal source solution；
Preferably, the transition metal source solution includes that source of iron solution, cobalt source solution, nickel source solution, copper source solution or molybdenum source are molten
In liquid any one or at least two combination；
Preferably, the cobalt source solution includes appointing in cobalt chloride solution, cobalt nitrate solution, cobalt sulfate solution or acetic acid cobalt liquor
It anticipates a kind of or at least two combinations；
Preferably, the source metal solution is transition metal source aqueous solution；
Preferably, the concentration of the source metal solution is 0.5mol/L-2.5mol/L, preferably 1mol/L；
Preferably, the temperature of the reaction is 80 DEG C -200 DEG C, preferably 160 DEG C；
Preferably, the time of the reaction is 5h-72h, preferably for 24 hours.
8. according to the described in any item preparation methods of claim 3-7, which is characterized in that in step (3), the calcining carbonization
Temperature is 800 DEG C -1200 DEG C, preferably 900 DEG C；
Preferably, in step (3), the time of the calcining carbonization is 0.5h-5h, preferably 2h；
Preferably, in step (3), the atmosphere of the calcining carbonization is the mixed gas of hydrogen and argon gas；
Preferably, in the mixed gas of the hydrogen and argon gas, the volume fraction of hydrogen is 5%.
9. according to the described in any item preparation methods of claim 3-8, which is characterized in that the preparation method includes following step
It is rapid:
(1) using the conductive substrates as working electrode, and to electrode, reference electrode and 0.5mol/L high containing pyrrole monomer
Sodium chlorate aqueous solution forms plating system, obtains polypyrrole cladding in the plating system with the voltage plating 500s of 1.0V
Conductive substrates；It is described to electrode be platinum electrode, the reference electrode be silver/silver chloride electrode, the volume of the pyrrole monomer with
The ratio between volume of sodium perchlorate aqueous solution is 1:10；
(2) conductive substrates of step (1) the polypyrrole cladding are mixed with the transition metal source aqueous solution of 1mol/L, 160
It is reacted at DEG C for 24 hours, obtains electrode precursor；
(3) by step (2) electrode precursor under the mixed gas of hydrogen and argon gas 900 DEG C of calcinings carbonization 2h obtain it is described from
In the mixed gas of support electrode, the hydrogen and argon gas, the volume fraction of hydrogen is 5%.
10. the purposes of self-supporting electrode according to claim 1 or 2, which is characterized in that the self-supporting electrode is for electricity
Water, electro-catalysis oxygen reduction or lithium ion battery is catalytically decomposed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810005771.8A CN109994715B (en) | 2018-01-03 | 2018-01-03 | Self-supporting electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810005771.8A CN109994715B (en) | 2018-01-03 | 2018-01-03 | Self-supporting electrode and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109994715A true CN109994715A (en) | 2019-07-09 |
| CN109994715B CN109994715B (en) | 2021-08-24 |
Family
ID=67129019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810005771.8A Active CN109994715B (en) | 2018-01-03 | 2018-01-03 | Self-supporting electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109994715B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111359611A (en) * | 2020-04-18 | 2020-07-03 | 台州学院 | Preparation method of FeCu/C electrocatalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101411986A (en) * | 2007-10-19 | 2009-04-22 | 中国科学院大连化学物理研究所 | Carbon-supported transitional metal carbon nitride compound as well as preparation and application thereof |
| CN101909749A (en) * | 2008-01-18 | 2010-12-08 | 昭和电工株式会社 | Catalyst, process for production of the same, and use of the same |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| CN103903869A (en) * | 2014-03-27 | 2014-07-02 | 华中科技大学 | Paper super capacitor and preparing method thereof |
| CN105810963A (en) * | 2016-04-26 | 2016-07-27 | 中国科学院合肥物质科学研究院 | Preparation method and application of transition metal-nitrogen-carbon-based electrocatalyst |
| CN106757143A (en) * | 2016-11-29 | 2017-05-31 | 北京化工大学 | A kind of water decomposition reaction catalysis electrode and preparation method thereof |
| WO2017099910A1 (en) * | 2015-12-10 | 2017-06-15 | Board Of Regents, The University Of Texas System | Metal-air battery |
| CN107293758A (en) * | 2012-01-13 | 2017-10-24 | 昭和电工株式会社 | Oxygen reduction catalyst and its manufacture method |
-
2018
- 2018-01-03 CN CN201810005771.8A patent/CN109994715B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101411986A (en) * | 2007-10-19 | 2009-04-22 | 中国科学院大连化学物理研究所 | Carbon-supported transitional metal carbon nitride compound as well as preparation and application thereof |
| CN101909749A (en) * | 2008-01-18 | 2010-12-08 | 昭和电工株式会社 | Catalyst, process for production of the same, and use of the same |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| CN107293758A (en) * | 2012-01-13 | 2017-10-24 | 昭和电工株式会社 | Oxygen reduction catalyst and its manufacture method |
| CN103903869A (en) * | 2014-03-27 | 2014-07-02 | 华中科技大学 | Paper super capacitor and preparing method thereof |
| WO2017099910A1 (en) * | 2015-12-10 | 2017-06-15 | Board Of Regents, The University Of Texas System | Metal-air battery |
| CN105810963A (en) * | 2016-04-26 | 2016-07-27 | 中国科学院合肥物质科学研究院 | Preparation method and application of transition metal-nitrogen-carbon-based electrocatalyst |
| CN106757143A (en) * | 2016-11-29 | 2017-05-31 | 北京化工大学 | A kind of water decomposition reaction catalysis electrode and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI WANG等: ""Nitrogen, cobalt-codoped carbon electrocatalyst for oxygen reduction reaction using soy milk and cobalt salts as precursors"", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111359611A (en) * | 2020-04-18 | 2020-07-03 | 台州学院 | Preparation method of FeCu/C electrocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109994715B (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Nitrogen-doped graphitic carbon-supported ultrafine Co nanoparticles as an efficient multifunctional electrocatalyst for HER and rechargeable Zn–air batteries | |
| Kumar | NiCo 2 O 4 nano-/microstructures as high-performance biosensors: a review | |
| Zhu et al. | Enhancing electrocatalytic activity for hydrogen evolution by strongly coupled molybdenum nitride@ nitrogen-doped carbon porous nano-octahedrons | |
| Ma et al. | Fine Co nanoparticles encapsulated in a N-doped porous carbon matrix with superficial N-doped porous carbon nanofibers for efficient oxygen reduction | |
| CN109019559B (en) | Element-doped three-dimensional porous carbon material and preparation method and application thereof | |
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| CN109248703B (en) | Loaded Ni3Preparation method of Fe nitrogen-doped carbon nanocomposite material, and obtained material and application thereof | |
| CN106564868B (en) | A kind of preparation method of nitrogen-doped porous carbon material | |
| CN108940285A (en) | A kind of preparation method and application of flexibility electrolysis water catalysis material | |
| CN110534755B (en) | Zinc-based metal organic framework material and preparation method and application of iron-nitrogen co-doped carbon-based oxygen reduction electrocatalyst thereof | |
| CN104269566A (en) | Preparation method and application of nitrogen-doped porous carbon nano sheet composite material | |
| CN103545536A (en) | Carbon fiber supported metal catalyst as well as preparation method and application thereof | |
| CN111659401A (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| Wang et al. | Facile preparation of a Pt/Prussian blue/graphene composite and its application as an enhanced catalyst for methanol oxidation | |
| CN112968185B (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| Wang et al. | Freestanding non‐precious metal electrocatalysts for oxygen evolution and reduction reactions | |
| CN106848334B (en) | It is a kind of using pyrrole radicals tetrazine as oxygen reduction catalyst of presoma and preparation method thereof | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN108315758B (en) | Catalyst for producing hydrogen by electrolyzing water and preparation method thereof | |
| Cao et al. | Three-dimensional porous carbon nanofiber networks decorated with cobalt-based nanoparticles: A robust electrocatalyst for efficient water oxidation | |
| CN109921037A (en) | A kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction | |
| KR20160019423A (en) | Porous carbon catalyst, method for producing same, electrode and battery | |
| CN106783201A (en) | A kind of molybdenum sulfide/ferric oxide composite material and its preparation method and application | |
| CN108649237B (en) | Gel pyrolysis-based cobalt-nitrogen doped carbon composite material and preparation method and application thereof | |
| CN104707640A (en) | Non-noble metal oxygen reduction catalyst, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |