CN108802138A - A kind of membrane electrode, electrochemical gas sensor and its application - Google Patents
A kind of membrane electrode, electrochemical gas sensor and its application Download PDFInfo
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- CN108802138A CN108802138A CN201810885715.8A CN201810885715A CN108802138A CN 108802138 A CN108802138 A CN 108802138A CN 201810885715 A CN201810885715 A CN 201810885715A CN 108802138 A CN108802138 A CN 108802138A
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- membrane electrode
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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Abstract
The present invention provides a kind of membrane electrode, electrochemical gas sensor and its application, which is covered with the material layer of spitball shape grapheme material or the formation of spitball shape composite on the substrate using thin polymer film as substrate；Preparation method is：Spitball shape grapheme material or spitball shape composite are sufficiently mixed with ptfe emulsion, obtain mixed liquor；Obtained mixed liquor is transferred to forming material layer on thin polymer film, membrane electrode is prepared.The membrane electrode can be directly used for electrochemical gas sensor, and have the advantages that gas response is high, response is fast, high sensitivity and detection limit are low.
Description
Technical field
The invention belongs to electrochemical sensor field, it is related to a kind of membrane electrode, electrochemical gas sensor and its application.
Background technology
With the improvement of people ' s living standards and to environmental protection pay attention to day by day, to various toxic, pernicious gases (such as formaldehyde,
H2、SO2、NOx、CO、H2S、Cl2、NH3And O3Deng) monitoring, the monitoring to atmosphere pollution, industrial waste gas and people's living environment
Monitoring/detection of quality etc. becomes particularly important, therefore develops effective gas detection equipment and have become the task of top priority.
Electrochemical gas sensor with high sensitivity, easy to operate, portable convenient, can scene directly and continuous detection etc. is excellent
Point, increasingly has been favored by people.The key technology of electrochemical sensor is the design of electrode material, electrode material catalytic
The quality of energy directly affects the performance of sensor.Electrochemical gas sensor generally use noble metal nano particles
It is expensive as elctro-catalyst.Since precious metal based catalysts are in direct contact with electrolyte for a long time, under working environment not
Stablize, this affects the service life of elctro-catalyst to a certain extent, eventually leads to transducer sensitivity and reduces and even fails.
Graphene is by sp2The two dimensional crystal structure of the single atomic thickness of carbon atom hydridization composition, this structure can be with
Regard one layer of graphite flake layer being stripped as, there is excellent mechanics and electrology characteristic, good biocompatibility, big ratio table
The characteristics such as area.These properties are conducive to the absorption of gas molecule on the surface of graphene, to which the carrier for changing graphene is dense
Degree, causes the variation of graphene electrical properties, and then be detected to gas molecule.For example, being prepared using chemical vapor deposition
Monolithic graphite alkene can be used to build highly sensitive gas sensor and individual molecule can be detected.Compared to chemical gaseous phase
The graphene prepared is deposited, redox graphene (rGO) with defect and functional group's isoreactivity site because being widely used in gas
During physical examination is surveyed, including NO2、NH3、H2And organic gas.In electrochemical sensor application aspect, the unique structure of graphene makes it
It shows unusual property, good sensitization is played to the electrochemical sensing of biological micromolecule.
Currently, in electrochemical sensor application, generally using the graphene prepared as raw material using graphene oxide
And composite.However, in application, inevitably will produce stone during graphene oxide restores
Black alkene interlayer stacks, and the bigger serface for causing graphene intrinsic seriously reduces.Simultaneously as the hydrophobicity of graphene itself,
Electrochemistry can not will be led to gas to be detected and electrolyte contacts forever by burying the electrochemical active material between graphene layer
The utilization rate of active material is extremely low, seriously constrains application of the graphene-based material in electrochemical gas sensor.Therefore, exist
In presently disclosed technology, graphene and its composite material focus mostly in semiconductor-type testing principle, such as gas sensor
What is by graphene or graphene-based nano-composite catalyst applied to there has been no relevant reports in electrochemical gas sensor.
CN108033440A discloses a kind of preparation method of the porous fold graphene of high specific area：(1) by graphite oxide
Alkene solution and water-soluble nitrogenous compound mix, and pore creating material is added and mixes to obtain mixed liquor；(2) heating of mixed liquor ultrasonic atomizatio is made
Solvent volatilizees to obtain graphene oxide/pore creating material powder particle；(3) it is thermally treated resulting in high-specific surface area pleat under inert gas protection
Wrinkle graphene product.The porous fold graphene of specific area prepared by the invention has very high free volume and excellent resistance to compression
Performance, but not yet applied in electrochemical gas sensor.
CN104477886A discloses a kind of graphene with pleated structure, and structure is by making stone in liquid phase environment
The height that black alkene shrinks and forms surface rises and falls, these folds are in sharp cone distal, and height, width and the distribution density of fold are all equal
Even, controllable.The pleated structure graphene of the invention can be used for the fields such as new energy, sensor, but it be not disclosed whether
It can be applied to gas sensor.
CN107748181A discloses one kind and being based on graphene-based gas sensor, forms one layer of titanium dioxide on a silicon substrate
Silicon insulating layer forms a metal layer on the silicon dioxide insulating layer, and one layer of composite graphite alkene layer is formed in the metal layer, multiple
The side for closing graphene layer contact metal layer is formed with granules of stannic oxide layer, the side shape of composite graphite alkene layer not contact metal layer
At gold nano grain, graphene is modified simultaneously by granules of stannic oxide and gold nano grain, and adjust its electric property,
So that it is met the requirement of gas sensor, needs to be modified graphene in the invention and can be only achieved gas sensor and want
It asks, and what it utilized is semiconductor-type gas sensor testing principle.
Therefore, the low electrochemical gas sensor of a kind of good electrochemical gas sensing effect, high sensitivity, detection limit is developed
Still it is of great significance.
Invention content
In view of the deficiencies of the prior art, the present invention intends to provide a kind of membrane electrode, electrochemical gas sensing
Device and its application using the electrochemical gas sensor of inventive film electrode there is good sensing effect, high sensitivity and detection to limit
Low advantage.
To reach the invention purpose, the present invention uses following technical scheme：
One of the objects of the present invention is to provide a kind of membrane electrode, the membrane electrode is using thin polymer film as substrate, in institute
State the material layer that spitball shape grapheme material or the formation of spitball shape composite are covered in substrate.
Spitball shape grapheme material or spitball shape composite used in the present invention have excellent power
It learns and electrology characteristic, good biocompatibility and larger specific surface area, these properties is conducive to gas molecule in graphene
The absorption on surface causes the variation of graphene electrical properties to change the carrier concentration of graphene so that using film electricity
When being extremely detected to gas molecule, the sensitivity of its detection can be improved.
In the present invention, the thin polymer film be polytetrafluoroethylene film, polyurethane film or polyacrylonitrile film, preferably poly- four
Fluoride film.
In the present invention, the stone for including in the spitball shape grapheme material or spitball shape composite
Black alkene ingredient is redox graphene.
In the present invention, the grain size of the spitball shape grapheme material is 500nm-1 μm, such as 500nm, 550nm,
600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm or 1 μm.
In the present invention, the grain size of the spitball shape composite is 500nm-1 μm, such as 500nm,
550nm, 600nm, 650nm, 700nm, 750nm, 800nm, 850nm, 900nm, 950nm or 1 μm.
In the present invention, other electrochemical active materials are also contained in the spitball shape composite.
In the present invention, other described electrochemical active materials are metal salt, metal nanoparticle or metal alloy particle
In any one or at least two combination.
In the present invention, the metal salt includes gold chloride, potassium chloroaurate, chloroplatinic acid, potassium chloroplatinate, palladium bichloride, chlorination
Iron, nickel chloride, cobalt chloride, manganese chloride, Lvization Molybdenum, copper chloride, ferric nitrate, nickel nitrate, cobalt nitrate, Xiao Suan Molybdenum, copper nitrate, acetic acid
In iron, nickel acetate, cobalt acetate, manganese acetate, acetic acid molybdenum or copper acetate any one or at least two combination, preferred iron chloride
And/or copper chloride.
In the present invention, the metal nanoparticle includes in gold nano grain, Pt nanoparticle or palladium nano-particles
Any one or at least two combination.
In the present invention, the metal alloy particle includes platinum alloy particle, lead billon particle, platinum metal
Grain, golden nickel alloy particles, gold cobalt alloy particle, bule gold particle, gold copper particle, platinum-nickel alloy particle, platinum cobalt alloy
Particle, platinum-iron alloy particles, Mock gold particle, palladium-nickel alloy particle, Pd-Co alloy particle, palladium-copper alloy particle or palladium iron close
In gold particle any one or at least two combination, preferably platinum alloy particle and/or Mock gold particle.
In the present invention, the spitball shape composite can be spitball shape graphene/Jenner's grain of rice
Son, spitball shape graphene/platinum nano particle, spitball shape graphene/Pd nano particle, spitball shape graphene/precious metal alloys are received
Rice grain, spitball shape graphene/transient metal chalcogenide compound and spitball shape graphene/transition metal oxide etc. meet material
Material.
Preferably, the thickness of the material layer is 5-20 μm, such as 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 17 μm, 19 μm
Or 20 μm.
In the present invention, the spitball shape grapheme material or spitball shape composite by preparing as follows
Method is prepared：Graphene oxide dispersion or the graphene oxide dispersion containing other electrochemical active materials are passed through into spray
The spitball shape grapheme material is prepared with the combination of high-temperature process method for mist method or electrostatic spraying processes or spitball shape is graphene-based
Nanocomposite.
Spitball shape grapheme material is prepared with the combination of high-temperature process method using spray-on process or electrostatic spraying processes in the present invention
Or spitball shape composite, the intrinsic bigger serface of graphene is not interfered with and changed, graphene is prevented
Lamella stacks, and the advantages that ensure that big specific surface area, increase gas permeability, therefore can increase the utilization rate of electrochemical active material
And service life.
Preferably, the preparation method is that by graphene oxide dispersion or oxidation stone containing other electrochemical active materials
The spitball shape grapheme material or paper nodular graphite is prepared by spray-on process and the combination of high-temperature process method in black alkene dispersion liquid
Alkenyl nanocomposite.
Preferably, it the preparation method is that using protective gas as carrier gas, carries containing graphene oxide dispersion or contains
The graphene oxide dispersion of other electrochemical active materials enters diamond heating area and carries out high-temperature process together.
Preferably, the protective gas is nitrogen or argon gas.
Preferably, the flow velocity of carrier gas be 10-200mL/h, such as 10mL/h, 20mL/h, 40mL/h, 60mL/h, 80mL/h,
100mL/h, 120mL/h, 140mL/h, 150mL/h, 170mL/h, 190mL/h or 200mL/h.
Preferably, the Heating Zone Temperature be 400-900 DEG C (such as 400 DEG C, 420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C,
530 DEG C, 550 DEG C, 580 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or 900 DEG C), heating time 1-
3min (such as 1min, 1.3min, 1.5min, 2min, 2.5min or 3min).
In the present invention, in the graphene oxide dispersion graphene oxide a concentration of 0.5-20mg/mL, such as
0.5mg/mL、1mg/mL、2mg/mL、3mg/mL、4mg/mL、5mg/mL、6mg/mL、7mg/mL、8mg/mL、9mg/mL、10mg/
mL、11mg/mL、12mg/mL、13mg/mL、14mg/mL、15mg/mL、16mg/mL、17mg/mL、18mg/mL、19mg/mL、
20mg/mL etc.；It is preferred that 10-15mg/mL, such as 10mg/mL, 11mg/mL, 12mg/mL, 13mg/mL, 14mg/mL, 15mg/mL.
In the present invention, solvent is water, ethyl alcohol, methanol, dimethylformamide (DMF) in the graphene oxide dispersion
In any one or at least two combination.
In the present invention, other electrochemistry in the graphene oxide dispersion containing other electrochemical active materials are lived
A concentration of 0.1-50mg/mL of property material, such as 0.5mg/mL, 5mg/mL, 10mg/mL, 15mg/mL, 20mg/mL, 25mg/
ML, 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL, 50mg/mL etc.；It is preferred that 20-40mg/mL, such as 20mg/mL, 25mg/
ML, 30mg/mL, 35mg/mL, 40mg/mL etc..
The second object of the present invention is the provision of a kind of preparation method of the membrane electrode based on grapheme material, feature
It is, the preparation method comprises the following steps：：
(1) spitball shape grapheme material or spitball shape composite and ptfe emulsion is abundant
Mixing, obtains mixed liquor；
(2) mixed liquor that step (1) obtains is transferred to forming material layer on thin polymer film, obtains the membrane electrode.
The present invention is using spitball shape grapheme material or spitball shape composite as catalyst, polytetrafluoro
Vac emulsion, as base material, prepares waterproof and breathable membrane electrode, can not only increase catalysis as binder and thin polymer film
The specific surface area of agent material, the utilization rate for improving electrochemical active material reduce catalyst material price, improve elctro-catalyst body
Stability and service life of system etc., and can be directly used for electrochemical gas sensor.
In the present invention, step (1) the spitball shape grapheme material or spitball shape composite with
The mass ratio of ptfe emulsion is 2.3:1-19:1, such as 2.3:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:
1,11:1,12:1,13:1,14:1,15:1,16:1,17:1,18:1,19:1 etc..
The ratio of graphite alkenes active material and ptfe emulsion is not easy to form a film if too high, if too low
Electric conductivity is too poor, unfavorable to sensing.
In the present invention, step (2) mixed liquor for obtaining step (1) is transferred to forming material on thin polymer film
Layer is realized using injection cladding process or screen printing technique.
In the present invention, after step (2) mixed liquor for obtaining step (1) is transferred on thin polymer film, pass through
Dry, elution and sintering, obtain the membrane electrode.
The third object of the present invention is to provide a kind of electrochemical gas sensor, and the electrochemical gas sensor is with step
Suddenly the membrane electrode that prepared by (2) is as working electrode.
It is applied to electrochemical gas using " spitball shape " graphene-based material as the membrane electrode of catalyst preparation in the present invention
It can express out fast gas response height, response, high sensitivity and detection in sensor and limit low advantage.
In the present invention, the electrochemical gas sensor includes working electrode, to electrode and reference electrode.
In the present invention, the electrochemical gas sensor is applied in gas detection.
In the present invention, the gas includes formaldehyde, chlorine, oxygen, carbon monoxide, hydrogen sulfide, sulfur dioxide, nitrogen oxidation
Object or hydrogen.
Compared with the existing technology, the invention has the advantages that：
The present invention urging as membrane electrode using " spitball shape " grapheme material or spitball shape composite
Agent can increase the specific surface area of catalyst material, the utilization rate for improving electrochemical active material, reduce catalyst material valence
Lattice, the stability and service life for improving elctro-catalyst system；" spitball shape " grapheme material or the graphene-based nanometer of spitball shape
Composite material can be applied to electrochemical gas sensor as the membrane electrode that catalyst is formed, and show gas response it is high,
Response is fast, high sensitivity and detection limit low advantage.
Description of the drawings
Fig. 1 is the TEM figures of the graphene oxide raw material used in the embodiment of the present invention 1, and scale is 1 μm；
Fig. 2 is the TEM figures for the spitball shape grapheme material that the embodiment of the present invention 1 is prepared, scale 200nm；
Fig. 3 is the XPS figures for the graphene that the embodiment of the present invention 1 is prepared；
Spitball grapheme materials of the Fig. 4 to be prepared using embodiment 1 tests the sound of 100ppm chlorine as catalyst
Answer curve graph.
Specific implementation mode
The technical solution further illustrated the present invention below by specific implementation mode.Those skilled in the art should be bright
, the embodiment, which is only to aid in, understands the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape grapheme material formation, the graphene ingredient for including in the spitball shape grapheme material is oxygen
The grain size of graphite alkene, spitball shape grapheme material is 500-700nm, and layer thickness is 10 μm.
Wherein spitball shape grapheme material is to be prepared by the following method to obtain：Graphene oxide is dispersed in water, oxygen
A concentration of 15mg/mL of graphite alkene, then by with nitrogen as carrier gas, carrying graphene oxide dispersion and entering tube furnace together
Heating zone.The flow velocity of carrier gas is in 100mL/h.Heating Zone Temperature is 500 DEG C, and the spitball is prepared in heating time 1min
Shape grapheme material.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape grapheme material and ptfe emulsion in mass ratio 9:1 is sufficiently mixed, and obtains mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
The raw material used in the present embodiment is aoxidized using transmission electron microscope (JEOL, JSM-6700F, Japan, Japan Electronics)
Graphene and the spitball shape grapheme material being prepared are characterized.The SEM of graphene oxide schemes as shown in Figure 1, oxidation
Two-dimension plane structure is presented in grapheme material itself.Spitball shape grapheme material characterization result is as shown in fig. 2, it can be seen that system
Spitball shape is presented in standby obtained grapheme material, has abundant pore structure.
X-ray photoelectron spectroscopy (PE companies of U.S. PHI-5400 types) to the spitball shape grapheme material that is prepared into
Row characterization, Fig. 3 are the XPS figures for the spitball shape grapheme material being prepared in the present embodiment, it can be seen that graphene restores journey
Degree is very high.
Embodiment 2
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape grapheme material formation, the graphene ingredient for including in the spitball shape grapheme material is oxygen
The grain size of graphite alkene, spitball shape grapheme material is 500-800nm, and layer thickness is 20 μm.
Wherein spitball shape grapheme material is to be prepared by the following method to obtain：In ethanol by graphene oxide dispersion,
A concentration of 10mg/mL of graphene oxide, by with nitrogen as carrier gas, carrying graphene oxide dispersion and entering tube furnace together
Heating zone.The flow velocity of carrier gas is in 100mL/h.Heating Zone Temperature is 500 DEG C, and the spitball is prepared in heating time 1min
Shape grapheme material.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape grapheme material and ptfe emulsion in mass ratio 4:1 is sufficiently mixed, and obtains mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 3
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape grapheme material formation, the graphene ingredient for including in the spitball shape grapheme material is oxygen
The grain size of graphite alkene, spitball shape grapheme material is 600-700nm, and layer thickness is 10 μm.
Wherein spitball shape grapheme material is to be prepared by the following method to obtain：In ethanol by graphene oxide dispersion,
So that a concentration of 20mg/mL of graphene oxide, by with nitrogen as carrier gas, carrying graphene oxide dispersion and entering together
Diamond heating area.The flow velocity of carrier gas is in 200mL/h.Heating Zone Temperature is 400 DEG C, and institute is prepared in heating time 1min
State spitball shape grapheme material.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape grapheme material and ptfe emulsion in mass ratio 3:1 is sufficiently mixed, and obtains mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 4
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape grapheme material formation, the graphene ingredient for including in the spitball shape grapheme material is oxygen
The grain size of graphite alkene, spitball shape grapheme material is 800nm-1 μm, and layer thickness is 5 μm.
Wherein spitball shape grapheme material is to be prepared by the following method to obtain：In ethanol by graphene oxide dispersion,
So that a concentration of 5mg/mL of graphene oxide, by with nitrogen as carrier gas, carrying graphene oxide dispersion and entering together
Diamond heating area.The flow velocity of carrier gas is in 100mL/h.Heating Zone Temperature is 500 DEG C, and institute is prepared in heating time 1min
State spitball shape grapheme material.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape grapheme material and ptfe emulsion in mass ratio 12:1 is sufficiently mixed, and obtains mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 5
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape grapheme material formation, the graphene ingredient for including in the spitball shape grapheme material is oxygen
The grain size of graphite alkene, spitball shape grapheme material is 500nm-800nm, and layer thickness is 15 μm.
Wherein spitball shape grapheme material is to be prepared by the following method to obtain：In ethanol by graphene oxide dispersion,
So that a concentration of 0.5mg/mL of graphene oxide, by using argon gas as carrier gas, carrying graphene oxide dispersion together into
Enter diamond heating area.The flow velocity of carrier gas is in 50mL/h.Heating Zone Temperature is 600 DEG C, and institute is prepared in heating time 1min
State spitball shape grapheme material.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape grapheme material and ptfe emulsion in mass ratio 19:1 is sufficiently mixed, and obtains mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 6
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape composite formation, in the spitball shape composite
Including graphene ingredient be graphene oxide and electrochemical active material copper chloride, spitball shape composite
Grain size be 500nm-800nm, layer thickness be 5 μm.
Wherein spitball shape composite is to be prepared by the following method to obtain：Graphene oxide is disperseed
In ethanol, a concentration of 12mg/mL of graphene oxide, then electrochemical active material copper chloride is distributed to graphite oxide dispersion
In, wherein electrochemical active material copper chloride concentration is 30mg/mL, finally by with nitrogen as carrier gas, carries graphite oxide
Alkene dispersion liquid enters diamond heating area together.The flow velocity of carrier gas is in 10mL/h.Heating Zone Temperature is 400 DEG C, and heating time is
The spitball shape composite is prepared in 1min.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape composite and ptfe emulsion in mass ratio 4:1 is sufficiently mixed, and obtains
To mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 7
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape composite formation, in the spitball shape composite
Including graphene ingredient be graphene oxide and electrochemical active material gold nano grain, spitball shape is graphene-based nano combined
The grain size of material is 500nm-700nm, and layer thickness is 20 μm.
Wherein spitball shape composite is to be prepared by the following method to obtain：Graphene oxide is disperseed
In ethanol, a concentration of 12mg/mL of graphene oxide, then electrochemical active material gold nano grain is distributed to graphite oxide point
In dispersion liquid, wherein electrochemical active material gold nano grain concentration is 20mg/mL, finally by with nitrogen as carrier gas, is carried
Graphene oxide dispersion enters diamond heating area together.The flow velocity of carrier gas is in 150mL/h.Heating Zone Temperature is 800 DEG C, is added
The hot time is 1min, and the spitball shape composite is prepared.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape composite and ptfe emulsion in mass ratio 9:1 is sufficiently mixed, and obtains
To mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 8
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape composite formation, in the spitball shape composite
Including graphene ingredient be graphene oxide and electrochemical active material platinum alloy particle, the graphene-based nanometer of spitball shape is multiple
The grain size of condensation material is 500nm-800nm, and layer thickness is 10 μm.
Wherein spitball shape composite is to be prepared by the following method to obtain：Graphene oxide is disperseed
In ethanol, a concentration of 15mg/mL of graphene oxide, then electrochemical active material platinum alloy particle is distributed to graphite oxide
In dispersion liquid, wherein electrochemical active material platinum alloy granule density is 40mg/mL, finally by with nitrogen as carrier gas,
It carries graphene oxide dispersion and enters diamond heating area together.The flow velocity of carrier gas is in 200mL/h.Heating Zone Temperature is 400
DEG C, the spitball shape composite is prepared in heating time 1min.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape composite and ptfe emulsion in mass ratio 9:1 is sufficiently mixed, and obtains
To mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 9
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape composite formation, in the spitball shape composite
Including graphene ingredient be graphene oxide and electrochemical active material (platinum alloy particle and gold nano grain mixing), paper
The grain size of nodular graphite alkenyl nanocomposite is 500nm-700nm, and layer thickness is 10 μm.
Wherein spitball shape composite is to be prepared by the following method to obtain：Graphene oxide is disperseed
In ethanol, a concentration of 15mg/mL of graphene oxide, then by electrochemical active material (platinum alloy particle and gold nano grain
Mixing) it is distributed in graphite oxide dispersion, wherein electrochemical active material (platinum alloy particle and gold nano grain mixing)
A concentration of 40mg/mL carries graphene oxide dispersion and enters diamond heating together finally by with nitrogen as carrier gas
Area.The flow velocity of carrier gas is in 60mL/h.Heating Zone Temperature is 900 DEG C, heating time 1min, and it is graphene-based to obtain the spitball shape
Nanocomposite.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape composite and ptfe emulsion in mass ratio 9:1 is sufficiently mixed, and obtains
To mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 10
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape composite formation, in the spitball shape composite
Including graphene ingredient be graphene oxide and electrochemical active material Mock gold particle, the graphene-based nanometer of spitball shape is multiple
The grain size of condensation material is 500nm-800nm, and layer thickness is 20 μm.
Wherein spitball shape composite is to be prepared by the following method to obtain：Graphene oxide is disperseed
In ethanol, wherein dispersion concentration is 15mg/mL, then electrochemical active material Mock gold particle is distributed to graphite oxide point
In dispersion liquid, wherein electrochemical active material Mock gold granule density is 50mg/mL, finally with nitrogen as carrier gas, carries oxygen
Graphite alkene dispersion liquid enters diamond heating area together.The flow velocity of carrier gas is in 80mL/h.Heating Zone Temperature is 700 DEG C, heating
Time is 1min, obtains the spitball shape composite.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape composite and ptfe emulsion in mass ratio 2.5:1 is sufficiently mixed,
Obtain mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 11
In the present embodiment, a kind of membrane electrode is provided, the membrane electrode is using polytetrafluoroethylene film as substrate, in the substrate
On be covered with the material layer of spitball shape composite formation, in the spitball shape composite
Including graphene ingredient be graphene oxide and electrochemical active material Mock gold particle, the graphene-based nanometer of spitball shape is multiple
The grain size of condensation material is 500nm-800nm, and layer thickness is 15 μm.
Wherein spitball shape composite is to be prepared by the following method to obtain：Graphene oxide is disperseed
In ethanol, a concentration of 15mg/mL of graphene oxide, then electrochemical active material Mock gold particle is distributed to graphite oxide
In dispersion liquid, wherein electrochemical active material Mock gold granule density is 0.1mg/mL, finally by with nitrogen as carrier gas,
It carries graphene oxide dispersion and enters diamond heating area together.The flow velocity of carrier gas is in 100mL/h.Heating Zone Temperature is 800
DEG C, the spitball shape composite is prepared in heating time 1min.
The preparation method of the membrane electrode includes the following steps：
(1) by spitball shape composite and ptfe emulsion in mass ratio 19:1 is sufficiently mixed,
Obtain mixed liquor；
(2) by dry, elution and sintering shape in the mixed liquor injection coating to polytetrafluoroethylene film obtained step (1)
At material layer, the membrane electrode is obtained.
Embodiment 12
The membrane electrode being prepared using embodiment 1-11 prepares electrochemical gas sensor, electrochemical gas sensing
Device includes working electrode, to electrode and reference electrode, and wherein working electrode is the membrane electrode that embodiment 1-11 is prepared, and is utilized
The membrane electrode that embodiment 1-11 is prepared is prepared electrochemical gas sensor and is denoted as a-k.
Gas detection, testing result such as table 1 are carried out using the electrochemical gas sensor being prepared：
Table 1
The present invention illustrates membrane electrode, electrochemical gas sensor and its application of the present invention by above-described embodiment, but
The invention is not limited in above-described embodiments, that is, do not mean that the present invention has to rely on above-described embodiment and could implement.Affiliated skill
The technical staff in art field is it will be clearly understood that any improvement in the present invention, equivalence replacement to raw material selected by the present invention and auxiliary
The addition of co-ingredients, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of membrane electrode, which is characterized in that the membrane electrode is covered with spitball on the substrate using thin polymer film as substrate
The material layer that shape grapheme material or spitball shape composite are formed.
2. membrane electrode according to claim 1, which is characterized in that the thin polymer film is polytetrafluoroethylene film, poly- ammonia
Ester film or polyacrylonitrile film, preferably polytetrafluoroethylene film；
Preferably, the graphene ingredient for including in the spitball shape grapheme material or spitball shape composite
For the graphene oxide of reduction；
Preferably, the grain size of the spitball shape grapheme material is 500nm-1 μm；
Preferably, the grain size of the spitball shape composite is 500nm-1 μm.
3. membrane electrode according to claim 1 or 2, which is characterized in that the spitball shape composite
In also contain other electrochemical active materials；
Preferably, other described electrochemical active materials are arbitrary in metal salt, metal nanoparticle or metal alloy particle
It is a kind of or at least two combination；
Preferably, the metal salt includes gold chloride, potassium chloroaurate, chloroplatinic acid, potassium chloroplatinate, palladium bichloride, iron chloride, chlorination
Nickel, cobalt chloride, manganese chloride, Lvization Molybdenum, copper chloride, ferric nitrate, nickel nitrate, cobalt nitrate, Xiao Suan Molybdenum, copper nitrate, ferric acetate, acetic acid
In nickel, cobalt acetate, manganese acetate, acetic acid molybdenum or copper acetate any one or at least two combination；
Preferably, the metal nanoparticle includes any one in gold nano grain, Pt nanoparticle or palladium nano-particles
Or at least two combination；
Preferably, the metal alloy particle includes platinum alloy particle, lead billon particle, platinum metal particle, golden nickel conjunction
Gold particle, gold cobalt alloy particle, bule gold particle, gold copper particle, platinum-nickel alloy particle, platinum cobalt alloy particle, platinum iron
In alloying pellet, Mock gold particle, palladium-nickel alloy particle, Pd-Co alloy particle, palladium-copper alloy particle or Pd-Fe alloy particle
Any one or at least two combination.
4. membrane electrode according to any one of claim 1-3, which is characterized in that the thickness of the material layer is 5-20 μ
m。
5. according to the membrane electrode described in any one of claim 1-4, which is characterized in that the spitball shape grapheme material or paper
Nodular graphite alkenyl nanocomposite by being prepared following preparation method：
Graphene oxide dispersion or graphene oxide dispersion containing other electrochemical active materials are passed through into spray-on process or quiet
The spitball shape grapheme material is prepared with the combination of high-temperature process method for electrospray or spitball shape is graphene-based nano combined
Material；
Preferably, the preparation method is that by graphene oxide dispersion or containing the graphene oxide of other electrochemical active materials
The spitball shape grapheme material is prepared with the combination of high-temperature process method by spray-on process for dispersion liquid or spitball shape is graphene-based
Nanocomposite；
Preferably, it the preparation method is that using protective gas as carrier gas, carries containing graphene oxide dispersion or contains other
The graphene oxide dispersion of electrochemical active material enters diamond heating area and carries out high-temperature process together；
Preferably, the protective gas is nitrogen or argon gas；
Preferably, the flow velocity of carrier gas is 10-200mL/h；
Preferably, the Heating Zone Temperature is 400-900 DEG C, heating time 1-3min.
6. membrane electrode according to claim 5, which is characterized in that graphene oxide in the graphene oxide dispersion
A concentration of 0.5-20mg/mL；
Preferably, solvent is appointing in water, ethyl alcohol, methanol or dimethylformamide (DMF) in the graphene oxide dispersion
It anticipates a kind of or at least two combinations；
Preferably, other electrochemical active materials in the graphene oxide dispersion containing other electrochemical active materials
A concentration of 0.1-50mg/mL.
7. the preparation method of the membrane electrode according to any one of claim 1-6, which is characterized in that the preparation method packet
Include following steps：
(1) spitball shape grapheme material or spitball shape composite and ptfe emulsion is fully mixed
It closes, obtains mixed liquor；
(2) mixed liquor that step (1) obtains is transferred to forming material layer on thin polymer film, obtains the membrane electrode.
8. preparation method according to claim 7, which is characterized in that step (1) the spitball shape grapheme material or paper
The mass ratio of nodular graphite alkenyl nanocomposite and ptfe emulsion is 2.3:1-19:1；
Preferably, it is to use that step (2) mixed liquor for obtaining step (1), which is transferred to forming material layer on thin polymer film,
What injection cladding process or screen printing technique were realized；
Preferably, after step (2) mixed liquor for obtaining step (1) is transferred on thin polymer film, by drying, elution
And sintering, obtain the membrane electrode.
9. a kind of electrochemical gas sensor, which is characterized in that the electrochemical gas sensor is with any in claim 1-6
Membrane electrode described in is as working electrode；
Preferably, the electrochemical gas sensor includes working electrode, to electrode and reference electrode.
10. application of the electrochemical gas sensor according to claim 9 in gas detection；
Preferably, the gas includes formaldehyde, chlorine, oxygen, carbon monoxide, hydrogen sulfide, sulfur dioxide, nitrogen oxides or hydrogen
Gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109725025A (en) * | 2019-02-22 | 2019-05-07 | 清华大学 | A kind of test equipment and method of the membrane electrode of solid oxide fuel cell |
| CN110057883A (en) * | 2019-03-12 | 2019-07-26 | 北京镭硼科技有限责任公司 | A kind of preparation method of electric chemical formula CO sensor sensing electrode material |
| CN110148523A (en) * | 2019-04-22 | 2019-08-20 | 南京邮电大学 | A kind of preparation method of indium sulphur nano thin-film |
| CN111307914A (en) * | 2018-12-11 | 2020-06-19 | 上海苏萨电子科技有限公司 | Working electrode, preparation method thereof and formaldehyde sensor comprising working electrode |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103310905A (en) * | 2012-11-08 | 2013-09-18 | 电子科技大学 | Method for manufacturing nano-composite conductive thin film and nano-composite conductive thin film |
| CN104247118A (en) * | 2012-03-29 | 2014-12-24 | 可隆工业株式会社 | Polymer electrolyte membrane, a method for fabricating the same, and a membrane-electrode assembly including the same |
| CN104483365A (en) * | 2014-12-17 | 2015-04-01 | 江西师范大学 | Electrochemical gas sensing device adopting precious metal and graphene composite material as sensing electrode and production method of electrochemical gas sensing device |
| CN104973805A (en) * | 2015-06-01 | 2015-10-14 | 浙江工业大学 | Electrically conductive polymer-graphene composite electrochromic film and preparation method thereof |
| CN105869892A (en) * | 2016-04-05 | 2016-08-17 | 上海交通大学 | High-performance graphene thin film electrode and preparation method thereof |
| US20170087519A1 (en) * | 2014-03-17 | 2017-03-30 | Washington University | Composite nanostructures having a crumpled graphene oxide shell |
| CN106966383A (en) * | 2017-04-28 | 2017-07-21 | 杭州高烯科技有限公司 | A kind of spitball shape graphene microballoon and preparation method thereof |
-
2018
- 2018-08-06 CN CN201810885715.8A patent/CN108802138A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104247118A (en) * | 2012-03-29 | 2014-12-24 | 可隆工业株式会社 | Polymer electrolyte membrane, a method for fabricating the same, and a membrane-electrode assembly including the same |
| CN103310905A (en) * | 2012-11-08 | 2013-09-18 | 电子科技大学 | Method for manufacturing nano-composite conductive thin film and nano-composite conductive thin film |
| US20170087519A1 (en) * | 2014-03-17 | 2017-03-30 | Washington University | Composite nanostructures having a crumpled graphene oxide shell |
| CN104483365A (en) * | 2014-12-17 | 2015-04-01 | 江西师范大学 | Electrochemical gas sensing device adopting precious metal and graphene composite material as sensing electrode and production method of electrochemical gas sensing device |
| CN104973805A (en) * | 2015-06-01 | 2015-10-14 | 浙江工业大学 | Electrically conductive polymer-graphene composite electrochromic film and preparation method thereof |
| CN105869892A (en) * | 2016-04-05 | 2016-08-17 | 上海交通大学 | High-performance graphene thin film electrode and preparation method thereof |
| CN106966383A (en) * | 2017-04-28 | 2017-07-21 | 杭州高烯科技有限公司 | A kind of spitball shape graphene microballoon and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| FENGFENG GAO等: "Electrical double layer ion transport with cell voltage-pulse potential coupling circuit for separating dilute lead ions from wastewater", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| HEE DONGJANG等: "Synthesis of grapheme based noble metal composites for glucose biosensor", 《MATERIALS LETTERS》 * |
| HONGWEI QIU等: "Evaporative assembly of graphene oxide for electric double-layer capacitor electrode application", 《POWDER TECHNOLOGY》 * |
| JIAYAN LUO等: "Compression and Aggregation-Resistant Particles of Crumpled Soft Sheets", 《ACS NANO》 * |
| JIAYAN LUO等: "Effect of Sheet Morphology on the Scalability of Graphene-Based Ultracapacitors", 《ACS NANO》 * |
| 范天吉等: "《煤矿监测监控综合技术手册》", 31 March 2004, 长春：吉林电子出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111307914A (en) * | 2018-12-11 | 2020-06-19 | 上海苏萨电子科技有限公司 | Working electrode, preparation method thereof and formaldehyde sensor comprising working electrode |
| CN109725025A (en) * | 2019-02-22 | 2019-05-07 | 清华大学 | A kind of test equipment and method of the membrane electrode of solid oxide fuel cell |
| CN109725025B (en) * | 2019-02-22 | 2020-12-08 | 清华大学 | Testing equipment and method for membrane electrode of solid oxide fuel cell |
| CN110057883A (en) * | 2019-03-12 | 2019-07-26 | 北京镭硼科技有限责任公司 | A kind of preparation method of electric chemical formula CO sensor sensing electrode material |
| CN110148523A (en) * | 2019-04-22 | 2019-08-20 | 南京邮电大学 | A kind of preparation method of indium sulphur nano thin-film |
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