CN106374115A - Multi-layer composite oxygen catalyst electrode and manufacturing method thereof - Google Patents
Multi-layer composite oxygen catalyst electrode and manufacturing method thereof Download PDFInfo
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- CN106374115A CN106374115A CN201610907046.0A CN201610907046A CN106374115A CN 106374115 A CN106374115 A CN 106374115A CN 201610907046 A CN201610907046 A CN 201610907046A CN 106374115 A CN106374115 A CN 106374115A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 26
- 239000001301 oxygen Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 239000006260 foam Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 34
- 238000006555 catalytic reaction Methods 0.000 claims description 32
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- HBAGRTDVSXKKDO-UHFFFAOYSA-N dioxido(dioxo)manganese lanthanum(3+) Chemical compound [La+3].[La+3].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O HBAGRTDVSXKKDO-UHFFFAOYSA-N 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 22
- -1 poly tetrafluoroethylene Polymers 0.000 claims description 19
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 19
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 239000006230 acetylene black Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 238000000875 high-speed ball milling Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000011017 operating method Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims description 3
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009738 saturating Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009700 powder processing Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000004247 hand Anatomy 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a multi-layer composite oxygen catalyst electrode and a manufacturing method thereof. The oxygen catalyst electrode comprises a current collection layer composed of a nickel foam net, a first catalyst layer, a second catalyst layer, a gas-permeable layer and a waterproof gas-permeable film, wherein both surfaces of the current collection layer are covered with the inner surface of the first catalyst layer and the inner surface of the second catalyst layer respectively; the inner surface of the gas-permeable layer is in contact with the outer surface of the first catalyst layer; and the outer surface of the gas-permeable layer is in contact with the inner surface of the waterproof gas-permeable film. A multi-layer structure of the catalyst layer, the current collection layer, the catalyst layer, the gas-permeable layer and the waterproof gas-permeable film is adopted for compounding, the electrode is stable in structure, high in durability, high in catalytic activity, simple in process, good in pole piece uniformity and safe in process, the electrode can be produced automatically and continuously, the actual current density can reach 110 mA/cm<2>, the production process is safe and pollution-free, and the production cost is low, and the product can be recycled; and the manufactured air electrode is stable in performance and high in durability, can be produced automatically in large scale, and has wide practicability.
Description
Technical field
The present invention relates to the technical field of aluminium-air cell, more particularly, to a kind of MULTILAYER COMPOSITE oxygen catalysis electrode and its making
Method.
Background technology
Aluminium-air cell is that air electrode is the metal battery of positive pole using aluminum as negative pole, compared with other metal batteries,
The specific energy height that itself has, low production cost, safe and environment-friendly the features such as, can be good at solving current power battery continuing
Boat is low, charge that inconvenient, production cost is high, produce and using process is dangerous, pollution environment the problems such as, there is huge market
Space and application prospect.
Aluminium-air cell electrolyte is potassium hydroxide aqueous solution or sodium hydrate aqueous solution, and reaction product aluminium oxide can follow
Ring using or be directly used as the raw material of industry, produce more high added value.Using process safety and reliability, blast, burning will not be produced
With phenomenons such as electric leakages, it is excellent honest and clean, safe and stable, the long-acting, zero-emission of a kind of abundant raw material source, price, free of contamination a new generation
Electrokinetic cell.
Current application extensive tesla lithium battery energy density is 200wh/kg, and actual energy density is 120-150wh/
Kg, and the theoretical energy density of aluminium-air cell is up to 8100wh/kg, the aluminium-air cell actual energy density being currently known is
1000wh/kg about, the air electrode of this aluminium-air cell using dehydrated alcohol as dispersant, as catalyst, adopt by silver-based
Formed with Catalytic Layer-current collector layer-air-permeable layer structure fabrication.This air electrode is relatively costly, and production process is dangerous, can only half handss
Work formula makes, structural instability, and durability is not strong, thus mass production difficulty is it is also difficult to commercially be widely popularized use.
Content of the invention
For weak point present in above-mentioned technology, a kind of present invention processing technology of offer is simple, production process safety
Environmental protection, can be mass, stable performance, the MULTILAYER COMPOSITE oxygen catalysis electrode of long service life and preparation method thereof.
In order to achieve the above object, the manufacture method of a kind of MULTILAYER COMPOSITE of present invention oxygen catalysis electrode, operates including following
Step:
A1, that catalyst pulp is spread evenly across current collector layer nickel foam is online, catalyst pulp is filled up the mesh of foam nickel screen,
Carry out precompressed after drying；
A2, using spraying equipment, catalyst pulp is sprayed at the pre- foam nickel screen two sides pressing through, repeatedly spraying, dry, roller shape
Become Catalytic Layer；
A3, foam nickel screen one side Catalytic Layer surface spraying waterproof and breathable slurry, dry, roll-in formed air-permeable layer；
A4, using film sticking equipment, poly tetrafluoroethylene is covered on ventilative layer surface, after drying more repeatedly roll-in to form waterproof saturating
Air film；
A5, cut into slices using microtome, burn-on nickel bar in the point of the pole piece cutting, obtain finished product air electrode.
Wherein, the preparation process of catalyst pulp used in a1 is as follows:
A11, in Muffle furnace, insulation after manganese dioxide powder roasting is cooled to room temperature, acetylene black is incubated cold after toasting in the baking oven
But to room temperature；
A12, using chemical synthesiss preparation generate perovskite type catalyst lanthanum manganate；
A13, the mangaic acid that will generate in the acetylene black after processing in the manganese dioxide powder after processing in graphite, a11, a11 and a12
Lanthanum is mixed, in ball mill high speed ball milling；
A14, Carboxymethyl cellulose sodium is taken to be dissolved in deionized water as dispersant, the raw material that ball milling in a13 is crossed adds dispersion
Agent, adds ptfe emulsion after high-speed stirred, is stirred for, obtains catalyst pulp.
Wherein, the chemical synthesiss in a12 prepare lanthanum manganate to implement process as follows:
Slaine containing lanthanum ion and substitution ion is configured to aqueous solution stir at normal temperatures, weighs citric acid, be uniformly dissolved
Afterwards, to Deca dust technology in solution, adjust stirring at normal temperature after ph value, dehydration obtains gel, gel is put in thermostatic drying chamber first
It is dried, then be positioned over Muffle furnace roasting, last natural cooling, obtain Ca-Ti ore type and be combined VPO catalysts lanthanum manganate.
Wherein, in a3, the preparation process of waterproof and breathable slurry is as follows:
A31, in ptfe emulsion add short carbon fiber, quick dispersed with stirring；
A32, the dispersion that will synthesize in active carbon powder addition a31, obtain waterproof and breathable slurry after stirring.
The invention also discloses a kind of manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode, including following operating procedure:
B1, the waterproof and breathable raw material of doughy catalyst raw material dough-making powder bulk is repeatedly squeezed into using roll-in extruder respectively
Laminar Catalytic Layer and air-permeable layer；
B2, the Catalytic Layer pressing and air-permeable layer are overlying on respectively current collector layer foam nickel screen both sides, reuse twin rollers continuous several times
Roll-in, make Catalytic Layer and air-permeable layer to be attached to nickel foam online；
B3, using film sticking equipment, poly tetrafluoroethylene is covered on ventilative layer surface, after drying, roll-in forms waterproof ventilated membrane again；
B4, cut into slices using microtome, burn-on nickel bar in the point of the pole piece cutting, obtain finished product air electrode.
Wherein, in b1, the preparation process of doughy catalyst raw material is as follows:
B11, in Muffle furnace by after manganese dioxide powder roasting, insulation is cooled to room temperature, after acetylene black is toasted in the baking oven, insulation
It is cooled to room temperature；
B12, prepare perovskite type catalyst lanthanum manganate using chemical synthesiss；
B13, by the acetylene black processing in the manganese dioxide powder processing in b11, b11, in b12, the lanthanum manganate generating and graphite enter
Row mixing, in ball mill high speed ball milling；
B14, take in b13 generate ball-milled mixtures, add deionized water, be stirring evenly and then adding into ptfe emulsion, mix
Close uniformly to thick-pasty, using dough kneading equipment, pastel is integrated into dough, obtain doughy catalyst raw material.
Wherein, the chemical synthesiss in b12 prepare lanthanum manganate to implement process as follows:
Slaine containing lanthanum ion and substitution ion is configured to aqueous solution stir at normal temperatures, weighs citric acid, be uniformly dissolved
Afterwards, to Deca dust technology in solution, adjust stirring at normal temperature after ph value, dehydration obtains gel, gel is put in thermostatic drying chamber first
It is dried, then be positioned over Muffle furnace roasting, last natural cooling, obtain Ca-Ti ore type and be combined VPO catalysts lanthanum manganate.
Wherein, in b1, the preparation process of doughy waterproof and breathable raw material is as follows:
B15, add a certain amount of short carbon fiber in ptfe emulsion, quick dispersed with stirring；
B16, by appropriate active carbon powder be added in b15 generate dispersion in, after stirring, rubbed using dough kneading equipment
Synthesis dough, obtains doughy waterproof and breathable raw material.
The invention also discloses a kind of MULTILAYER COMPOSITE oxygen catalysis electrode, including the current collector layer being made up of foam nickel screen, first
Catalytic Layer, the second Catalytic Layer, air-permeable layer and waterproof ventilated membrane, the inner surface of described first Catalytic Layer is overlying on the one of current collector layer
Face, the inner surface of described second Catalytic Layer is overlying on the another side of current collector layer, the inner surface of described air-permeable layer and the first Catalytic Layer
Outer surface contacts, and the outer surface of described air-permeable layer is contacted with the inner surface of waterproof ventilated membrane.
Wherein, described first Catalytic Layer is identical with the second catalyst layer structure, and all includes polytetrafluoroethylene floor, multiple dioxy
Change manganese block, multiple acetylene black patch and multiple lanthanum manganate block, the plurality of manganese dioxide block, multiple acetylene black patch and multiple manganese
Sour lanthanum block is uniformly embedded in polytetrafluoroethylene floor；Described air-permeable layer includes polytetrafluoroethylene floor, multiple short carbon fiber block and many
Individual activated carbon block, the plurality of short carbon fiber block and multiple activated carbon block are uniformly embedded in polytetrafluoroethylene floor；Described waterproof
Ventilated membrane is polytetrafluoroethylene floor.
The invention has the beneficial effects as follows:
Compared with prior art, MULTILAYER COMPOSITE oxygen catalysis electrode of the present invention and preparation method thereof, the sky that this manufacture method makes
The dispersant that pneumoelectric pole adopts, catalyst, conductive agent are safety, cheap raw material, using Catalytic Layer-current collector layer-Catalytic Layer-
Air-permeable layer-waterproof ventilated membrane multiple structure is combined, Stability Analysis of Structures, and durability is strong, and catalysis activity is high, process is simple, and pole piece is uniform
Good, the process safety of property, can automatic continuous production, actual energy density can reach 110ma/cm2, the no dirt of production process safety
Dye, low production cost, product is recyclable, the air electrode stable performance of making, and durability is strong, can with automatization,
Large-scale production, commercially has wide applicability.
Brief description
Fig. 1 is the flow chart of the manufacture method of first embodiment of the invention MULTILAYER COMPOSITE oxygen catalysis electrode；
Fig. 2 is the flow chart of the manufacture method of second embodiment of the invention MULTILAYER COMPOSITE oxygen catalysis electrode；
Fig. 3 is the schematic cross-section of MULTILAYER COMPOSITE oxygen catalysis electrode of the present invention；
Fig. 4 is electric current density and the durability contrast schematic diagram of catalyst component of the present invention.
Main element symbol description is as follows:
10th, current collector layer 11, the first Catalytic Layer
12nd, the second Catalytic Layer 13, air-permeable layer
14th, waterproof ventilated membrane.
Specific embodiment
In order to more clearly state the present invention, below in conjunction with the accompanying drawings the present invention is further described.
First embodiment refers to Fig. 1, a kind of manufacture method of present invention MULTILAYER COMPOSITE oxygen catalysis electrode, operates including following
Step:
A1, lanthanum manganate can be purchased or synthesize as follows: the slaine containing lanthanum ion and substitution ion is configured to aqueous solution
Stir 0.5h at normal temperatures, weigh citric acid, after being uniformly dissolved, the Deca dust technology in solution, adjust stirring at normal temperature 5h after ph value,
Dehydration obtains gel, puts in 100 DEG C of thermostatic drying chambers and 24h is dried, be then placed into Muffle furnace roasting 20h, natural cooling, obtain
It is combined VPO catalysts lanthanum manganate to Ca-Ti ore type；
A2, by manganese dioxide powder roasting 20 hours, the lanthanum manganate being obtained with acetylene black, graphite and a1 is mixed puts into ball in ball mill
Mill 20h；
A3, will Carboxymethyl cellulose sodium add deionized water in stir after the good mixture of a2 ball milling is added thereto, high-speed stirring
Mix addition ptfe emulsion, then stirring at low speed, obtain Catalytic Layer slurry；Carbon fiber and activated carbon are added politef
In emulsion, stirring 4h obtains waterproof ventilative layer 13 slurry；
A4, the slurry that a3 is obtained uniformly are brushed in nickel screen, carry out precompressed after 80 DEG C of drying；
A5, the slurry flush coater that a3 is obtained repeatedly are sprayed at the pole piece two sides that a4 compacting obtains on a small quantity repeatedly, and spraying is dried；
A6, in pole piece wherein one side spraying waterproof ventilative layer 13 to then sticking waterproof ventilated membrane 14；
A7, the pole piece obtaining a6 carry out progressively roll-in by 50% compression ratio, spot welding nickel bar wherein after section, obtain this
The air pole piece of invention.
The catalyst that the present invention uses does not contain noble metal, ensure that catalysis activity is higher than the catalysis making using noble metal
While electrode, production cost greatly reduces；It is used deionized water to replace conventional dehydrated alcohol conduct in metal battery
Dispersant is it is ensured that the safety of production process；Mixed with high speed ball-milling method, when shortening the dispersion in pulping process
Between, save the manpower and materials needed for production process, improve the efficiency of large-scale production.
Second embodiment further regards to Fig. 2, a kind of manufacture method of present invention MULTILAYER COMPOSITE oxygen catalysis electrode, including with
Lower operating procedure:
B1, pretreatment of raw material: by manganese dioxide powder roasting 20h in Muffle furnace, insulation is cooled to room temperature, and acetylene black is in baking oven
Toast 2h at 120 DEG C, insulation is cooled to room temperature；
B2, the preparation of Ca-Ti ore type catalysis material: prepare perovskite type catalyst lanthanum manganate using chemical synthesiss；
B3, mechanical lapping: manganese dioxide powder, lanthanum manganate, graphite, acetylene black 5:2:3:2 in mass ratio is mixed, high in ball mill
Fast ball milling 10h；
B4, take ball-milled mixtures, add deionized water, stir 0.5h, add ptfe emulsion, mix homogeneously to sticky paste
Shape, becomes bulk using dough kneading equipment kneading 2h, obtains Catalytic Layer raw material；
B5, in ptfe emulsion add short carbon fiber, quick dispersed with stirring 2h；
B6, appropriate active carbon powder is added in above-mentioned dispersion, stir 2h, become bulk using dough kneading equipment kneading 2h, both
Obtain waterproof ventilative layer 13 raw material of the present invention；
B7, Catalytic Layer raw material and waterproof ventilative layer 13 raw material are repeatedly extruded slabbing using roll-in extruder respectively；
B8, the Catalytic Layer of compacting and waterproof ventilative layer 13 skin are overlying on foam nickel screen both sides respectively, reuse twin rollers continuously many
Secondary roll-in, makes Catalytic Layer and waterproof ventilative layer 13 firmly be attached on nickel screen；
B9, using film sticking equipment, poly tetrafluoroethylene is covered on waterproof ventilative layer 13 surface, roll-in again after drying；
B10, cut into slices using microtome, burn-on nickel bar in the point of the pole piece cutting, obtain the air electrode of the present invention.
Equipment and process is simple that this preparation method that the present invention provides uses, the per pass manufacturing procedure time is shorter, raw
Produce seriality strong, pole piece uniformity is good, high yield rate, wastage of material is few, with short production cycle, low production cost, production efficiency
High.
The oxygen catalysis electrode obtaining with second embodiment making with further reference to Fig. 3, first embodiment, including by nickel foam
Current collector layer 10, the first Catalytic Layer 11, the second Catalytic Layer 12, air-permeable layer 13 and waterproof ventilated membrane 14 that net is constituted, the first catalysis
The inner surface of layer 11 is overlying on the one side of current collector layer 10, and the inner surface of the second Catalytic Layer 12 is overlying on the another side of current collector layer 10, breathes freely
The inner surface of layer 13 is contacted with the outer surface of the first Catalytic Layer 11, the interior table of the outer surface of air-permeable layer 13 and waterproof ventilated membrane 14
Face contacts.
First Catalytic Layer 11 is identical with the second Catalytic Layer 12 structure, and all includes polytetrafluoroethylene floor, multiple manganese dioxide
Block, multiple acetylene black patch and multiple lanthanum manganate block, multiple manganese dioxide blocks, multiple acetylene black patch and multiple lanthanum manganate block are equal
In even embedded polytetrafluoroethylene floor；Air-permeable layer 13 includes polytetrafluoroethylene floor, multiple short carbon fiber block and multiple activated carbon block,
Multiple short carbon fiber blocks and multiple activated carbon block are uniformly embedded in polytetrafluoroethylene floor；Waterproof ventilated membrane 14 is politef
Layer.
Further regard to figure, 4, electrolytic manganese dioxide powder (emd) catalysis activity is high, and under constant voltage 1.2v, electric current density can reach
110ma/cm2, but durability is not strong, and 8h attenuation is 13.6%, and lanthanum manganate (cmd) catalysis activity of chemical synthesiss preparation
Low, under constant voltage 1.2v, electric current density is 63ma/cm2, but durability is strong, and 8h attenuation is 1.6%.This programme take cmd and
Emd is used in mixed way according to a certain percentage, strengthens durability, the air making according to this programme while ensureing its catalysis activity
Pole piece, under constant voltage 1.2v, electric current density is 75ma/cm2, 8h attenuation is 4%.
The several specific embodiments being only the present invention disclosed above, but the present invention is not limited to this, any ability
What the technical staff in domain can think change all should fall into protection scope of the present invention.
Claims (10)
1. a kind of manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode is it is characterised in that include following operating procedure:
A1, that catalyst pulp is spread evenly across current collector layer nickel foam is online, catalyst pulp is filled up the mesh of foam nickel screen,
Carry out precompressed after drying；
A2, using spraying equipment, catalyst pulp is sprayed at the pre- foam nickel screen two sides pressing through, repeatedly spraying, dry, roller shape
Become Catalytic Layer；
A3, foam nickel screen one side Catalytic Layer surface spraying waterproof and breathable slurry, dry, roll-in formed air-permeable layer；
A4, using film sticking equipment, poly tetrafluoroethylene is covered on ventilative layer surface, after drying more repeatedly roll-in to form waterproof saturating
Air film；
A5, cut into slices using microtome, burn-on nickel bar in the point of the pole piece cutting, obtain finished product air electrode.
2. the manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 1 is it is characterised in that used in a1
The preparation process of catalyst pulp is as follows:
A11, in Muffle furnace, insulation after manganese dioxide powder roasting is cooled to room temperature, acetylene black is incubated cold after toasting in the baking oven
But to room temperature；
A12, using chemical synthesiss preparation generate perovskite type catalyst lanthanum manganate；
A13, the mangaic acid that will generate in the acetylene black after processing in the manganese dioxide powder after processing in graphite, a11, a11 and a12
Lanthanum is mixed, in ball mill high speed ball milling；
A14, Carboxymethyl cellulose sodium is taken to be dissolved in deionized water as dispersant, the raw material that ball milling in a13 is crossed adds dispersion
Agent, adds ptfe emulsion after high-speed stirred, is stirred for, obtains catalyst pulp.
3. the manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 2 is it is characterised in that chemistry in a12
Synthetic method prepare lanthanum manganate to implement process as follows:
Slaine containing lanthanum ion and substitution ion is configured to aqueous solution stir at normal temperatures, weighs citric acid, be uniformly dissolved
Afterwards, to Deca dust technology in solution, adjust stirring at normal temperature after ph value, dehydration obtains gel, gel is put in thermostatic drying chamber first
It is dried, then be positioned over Muffle furnace roasting, last natural cooling, obtain Ca-Ti ore type and be combined VPO catalysts lanthanum manganate.
4. MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 1 manufacture method it is characterised in that in a3 waterproof saturating
The preparation process of gas slurry is as follows:
A31, in ptfe emulsion add short carbon fiber, quick dispersed with stirring；
A32, the dispersion that will synthesize in active carbon powder addition a31, obtain waterproof and breathable slurry after stirring.
5. a kind of manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode is it is characterised in that include following operating procedure:
B1, the waterproof and breathable raw material of doughy catalyst raw material dough-making powder bulk is repeatedly squeezed into using roll-in extruder respectively
Laminar Catalytic Layer and air-permeable layer；
B2, the Catalytic Layer pressing and air-permeable layer are overlying on respectively current collector layer foam nickel screen both sides, reuse twin rollers continuous several times
Roll-in, make Catalytic Layer and air-permeable layer to be attached to nickel foam online；
B3, using film sticking equipment, poly tetrafluoroethylene is covered on ventilative layer surface, after drying, roll-in forms waterproof ventilated membrane again；
B4, cut into slices using microtome, burn-on nickel bar in the point of the pole piece cutting, obtain finished product air electrode.
6. the manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 5 is it is characterised in that doughy in b1
The preparation process of catalyst raw material is as follows:
B11, in Muffle furnace by after manganese dioxide powder roasting, insulation is cooled to room temperature, after acetylene black is toasted in the baking oven, insulation
It is cooled to room temperature；
B12, prepare perovskite type catalyst lanthanum manganate using chemical synthesiss；
B13, by the acetylene black processing in the manganese dioxide powder processing in b11, b11, in b12, the lanthanum manganate generating and graphite enter
Row mixing, in ball mill high speed ball milling；
B14, take in b13 generate ball-milled mixtures, add deionized water, be stirring evenly and then adding into ptfe emulsion, mix
Close uniformly to thick-pasty, using dough kneading equipment, pastel is integrated into dough, obtain doughy catalyst raw material.
7. the manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 6 is it is characterised in that change in b12
Learn synthetic method prepare lanthanum manganate to implement process as follows:
Slaine containing lanthanum ion and substitution ion is configured to aqueous solution stir at normal temperatures, weighs citric acid, be uniformly dissolved
Afterwards, to Deca dust technology in solution, adjust stirring at normal temperature after ph value, dehydration obtains gel, gel is put in thermostatic drying chamber first
It is dried, then be positioned over Muffle furnace roasting, last natural cooling, obtain Ca-Ti ore type and be combined VPO catalysts lanthanum manganate.
8. the manufacture method of MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 6 is it is characterised in that doughy in b1
The preparation process of waterproof and breathable raw material is as follows:
B15, add a certain amount of short carbon fiber in ptfe emulsion, quick dispersed with stirring；
B16, by appropriate active carbon powder be added in b15 generate dispersion in, after stirring, rubbed using dough kneading equipment
Synthesis dough, obtains doughy waterproof and breathable raw material.
9. a kind of MULTILAYER COMPOSITE oxygen catalysis electrode is it is characterised in that include current collector layer, the first catalysis being made up of foam nickel screen
Layer, the second Catalytic Layer, air-permeable layer and waterproof ventilated membrane, the inner surface of described first Catalytic Layer is overlying on the one side of current collector layer, institute
The inner surface stating the second Catalytic Layer is overlying on the another side of current collector layer, the outer surface of the inner surface of described air-permeable layer and the first Catalytic Layer
Contact, the outer surface of described air-permeable layer is contacted with the inner surface of waterproof ventilated membrane.
10. MULTILAYER COMPOSITE oxygen catalysis electrode according to claim 9 is it is characterised in that described first Catalytic Layer and second
Catalyst layer structure is identical, and all includes polytetrafluoroethylene floor, multiple manganese dioxide block, multiple acetylene black patch and multiple lanthanum manganate
Block, the plurality of manganese dioxide block, multiple acetylene black patch and multiple lanthanum manganate block are uniformly embedded in polytetrafluoroethylene floor；Described
Air-permeable layer includes polytetrafluoroethylene floor, multiple short carbon fiber block and multiple activated carbon block, the plurality of short carbon fiber block and
Multiple activated carbon blocks are uniformly embedded in polytetrafluoroethylene floor；Described waterproof ventilated membrane is polytetrafluoroethylene floor.
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| CN111276702A (en) * | 2019-12-23 | 2020-06-12 | 超威电源集团有限公司 | Preparation method of foam electrode for metal-air battery cathode, metal-air battery cathode and metal-air battery |
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