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
- spitball shape
- graphene oxide
- spitball
- graphene
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- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 111
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 229920006254 polymer film Polymers 0.000 claims abstract description 13
- 238000001514 detection method Methods 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 131
- 229910021389 graphene Inorganic materials 0.000 claims description 120
- 239000007789 gas Substances 0.000 claims description 59
- 239000002245 particle Substances 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 39
- -1 polytetrafluoroethylene Polymers 0.000 claims description 39
- 239000011149 active material Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000012159 carrier gas Substances 0.000 claims description 26
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 25
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 23
- 239000010931 gold Substances 0.000 claims description 23
- 229910052737 gold Inorganic materials 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 15
- 239000004615 ingredient Substances 0.000 claims description 14
- 238000010828 elution Methods 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910003460 diamond Inorganic materials 0.000 claims description 11
- 239000010432 diamond Substances 0.000 claims description 11
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002114 nanocomposite Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 239000002082 metal nanoparticle Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021069 Pd—Co Inorganic materials 0.000 claims description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 2
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 claims description 2
- PGDDJXSLIWMIRI-UHFFFAOYSA-N acetic acid;molybdenum Chemical compound [Mo].CC(O)=O PGDDJXSLIWMIRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 6
- 229910052759 nickel Inorganic materials 0.000 claims 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 3
- 229910021065 Pd—Fe Inorganic materials 0.000 claims 1
- 238000005275 alloying Methods 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims 1
- 239000002923 metal particle Substances 0.000 claims 1
- 229940073644 nickel Drugs 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 52
- 235000013339 cereals Nutrition 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000007590 electrostatic spraying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229960003284 iron Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Carbon And Carbon Compounds (AREA)
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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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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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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