CN110289387A - A kind of all solid state neutral zinc-air battery - Google Patents
A kind of all solid state neutral zinc-air battery Download PDFInfo
- Publication number
- CN110289387A CN110289387A CN201910411399.5A CN201910411399A CN110289387A CN 110289387 A CN110289387 A CN 110289387A CN 201910411399 A CN201910411399 A CN 201910411399A CN 110289387 A CN110289387 A CN 110289387A
- Authority
- CN
- China
- Prior art keywords
- battery
- air
- zinc
- electrolyte
- solid state
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007787 solid Substances 0.000 title claims abstract description 37
- 230000007935 neutral effect Effects 0.000 title claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011701 zinc Substances 0.000 claims abstract description 62
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 238000002347 injection Methods 0.000 claims abstract description 25
- 239000007924 injection Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000013589 supplement Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229940047670 sodium acrylate Drugs 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 229910000314 transition metal oxide Inorganic materials 0.000 claims 1
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000006259 organic additive Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000007581 slurry coating method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000005588 carbonic acid salt group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to a kind of zinc-air battery field more particularly to a kind of all solid state zinc-air batterys of neutral electrolyte and its battery preparation method.A kind of all solid state zinc-air battery provided by the present invention, comprising: neutral gel electrolyte, air cathode, metal zinc load, cell support frame, threaded upper cover.Organogel wraps up neutral electrolyte wherein, forms neutral gel electrolyte.Air cathode is made of current collector layer, hydrophobic breathable layer and Catalytic Layer.Cell support frame and threaded upper cover provide protection support.Metal zinc pipe or zinc bar are assemblied in the groove of battery frame.Air cathode coats the side of catalyst inwardly, is fixed in the card slot of battery frame.Configured neutral electrolyte is injected by the liquid injection hole of threaded upper cover in the gap of air cathode and metal zinc load, is stood, gel.It is assembled into neutral all solid state zinc-air battery.After battery dehydration, fresh electrolyte can be supplemented by the liquid injection hole of threaded upper cover, restore battery performance.
Description
Technical field
The present invention relates to a kind of zinc-air battery field more particularly to a kind of all solid state zinc-air battery of neutral electrolyte and
Its battery preparation method.
Background technique
All solid state zinc-air battery, be it is a kind of with oxygen in air for anode, metallic zinc is cathode, and organogel is electrolysis
The all solid state metal-air battery of matter.All solid state zinc-air battery has energy density high, and stable operating voltage is pollution-free, at
The features such as this is low, is widely used in the power supply of various portable mobile power supplies or wearable electronic.
Currently, the electrolyte of most of all solid state zinc-air battery is alkaline organogel electrolyte, principle is by alkali
Property aqueous solution is wrapped in organogel.Since zinc-air battery is semi-open system, the meeting of organogel electrolyte and air
It directly contacts, the sour gas in air, such as CO2It can react with the alkaline matter in organogel electrolyte and generate carbonic acid
Salt causes the conductivity of electrolyte to decline, and battery performance reduces.Alkaline matter in organogel also can be anti-with inhibitor of metal zinc electrode
It answers, causes self-discharge of battery, inhibitor of metal zinc electrode corrosion consumption, the capacity of battery and service life greatly shorten.In addition, organogel is electric
Xie Zhizhong contains a large amount of alkaline aqueous solution, and the humidity of cell operating conditions is smaller, battery it is long-term placement or it is worked
Cheng Zhong will cause organogel electrolyte and dry up because of dehydration, and deformation occurs for battery, electrolyte and zinc load and air cathode
Contact area is reduced, and electrolyte ion conductivity reduces, the penalty of battery, the lost of life.More importantly when complete solid
When state zinc-air battery is applied to wearable electronic, battery can be contacted directly or indirectly with human skin, alkaline electrolyte
Potential danger can be constituted to human body.Therefore, all solid state zinc-air battery for developing neutral electrolyte can evade these and dive
Danger, be applied to wearable electronic field with more extensive market prospects.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of all solid state zinc air electricity of neutral long-life
Pond.The all solid state zinc-air battery structure that the present invention designs can reduce scattering and disappearing for organogel electrolyte moisture, utilize simultaneously
The characteristic of organogel water suction can be replenished in time electrolyte in organogel electrolyte of the later period to dehydration, restore battery
Performance.Thus, all solid state zinc-air battery provided by the present invention has a longer life expectancy.In addition, neutral electrolyte of the present invention
Instead of alkaline electrolyte, the influence of acidic gas in air is reduced, it is suppressed that the self discharge of battery extends the longevity of battery
Life, reduces potential danger.
The present invention provides a kind of completely new all solid state zinc-air battery structure (Fig. 1) of neutral long-life, comprising: on screw thread
Lid, metal zinc load, cell support frame, air cathode, neutral gel electrolyte.
The threaded upper cover (Fig. 3) preferably organic glass, polyethylene, polypropylene, polyvinyl chloride or ABS plastics.Screw thread
There are liquid injection holes and gas vent for upper cover, for the injection of initial stage electrolyte and the supplement of later period electrolyte.
The zinc bar or zinc pipe of the preferred sanding and polishing of metal zinc load.
The air cathode is made of current collector layer, hydrophobic breathable layer, Catalytic Layer.
One or more of the current collector layer preferred foams nickel, nickel screen, foam copper, copper mesh.
The preferred hydrophobic, air-permeability carbon paper of the hydrophobic breathable layer, hydrophobic, air-permeability carbon cloth, porous carbon felt etc..
The Catalytic Layer is made of conductive carbon material, binder, catalyst material.The catalyst and conductive carbon material
Mass percent preferably 0.5~1.5.The preferred platinum of the catalyst material, metal oxide, without metal carbon material, carbon-based compound
One or more of material.One of the preferred conductive black of the conductive carbon material, activated carbon, graphene and carbon nanotubes
Or it is several.The mass ratio of the binder and catalyst material preferably 0.01~0.1.The preferred silica solution of the binder,
One or more of Nafion solution, PVP lotion, PTFE emulsion.
The cell support frame (Fig. 2) preferably organic glass, polyethylene, polypropylene, polyvinyl chloride, in ABS plastics
It is one or more of.The hole of cell support frame surrounding increases the contact area of air cathode and ambient enviroment, bottom it is recessed
Slot is used to fix metal zinc load and air cathode.
The neutral gel electrolyte includes organogel and organic additive.
The mass percent of the organogel and organic additive preferably 0.05~1.The preferred PANa of organogel
One or more of (Sodium Polyacrylate), PAK (polyacrylic acid potassium) and PAM (polyacrylamide).The preferred second of organic additive
One or more of the organic matter containing hydroxyl such as alcohol, isopropanol, ethylene glycol, glycerol.
The all solid state neutral zinc-air battery the preparation method is as follows:
The preparation of air cathode: conductive carbon material and catalyst material are weighed by 0.5~2 mass ratio, with 10~200ml
Ethyl alcohol mixing, is added dropwise the Nafion solution of 50~500ul 5wt%, is ultrasonically treated 0.5~4 hour, forms finely dispersed urge
Agent slurry.Using hydrophobic, air-permeability carbon cloth as matrix, configured catalyst pulp is applied by way of spraying or being added dropwise
It in the side of hydrophobic, air-permeability carbon cloth, is heated 1~5 hour on 60~150 DEG C of warm table, forming catalyst loadings is 0.5
~5mg cm-2Air cathode.Using roll-in is carried out to air cathode and nickel foam respectively on roll squeezer, integrated knot is made
Structure.
The preparation of zinc load:
Selection one end diameter is 6~8mm, and length is 41~45mm, and other end diameter is 4~6mm, and length is 6~7mm
Zinc bar or zinc pipe.It is polished with sand paper it, removes the oxide layer on surface.
The fixation of zinc load and air cathode and frame:
Air cathode is rolled into cylindrical shape, Catalytic Layer inwardly, is fixed in the card slot of battery frame.By one end of zinc load
It is assembled in the groove of battery frame, positions, screw thread upper cover.
The injection and supplement of electrolyte:
Electrolyte configuration: organic additive and distilled water are weighed by 0.2~2 mass ratio, uniformly mixes, it is molten to form 1#
Liquid.One or more of sodium acrylate (ANa), potassium acrylate (AK) and acrylamide (AM) solution are weighed, by itself and N, N '-
1# solution is added according to 2~10 mass ratioes in methylene-bisacrylamide (MBAM), uniformly mixes, and forms 2# mixed liquor.According to
Initiator potassium persulfate is added in 2# mixed liquor in 0.001~0.05 mass ratio, stirs evenly, and it is mixed to form neutral gel electrolyte
Liquid is closed, for use.
Electrolyte injection: using syringe or liquid-transfering gun by the liquid injection hole of battery threaded upper cover by configured neutrality
Gel electrolyte mixed liquor injects in the gap of air cathode and zinc load, stands, and after gel, screws liquid injection hole and gas vent
Bolt realizes sealing.
Electrolyte supplement: twisting off the bolt of liquid injection hole and gas vent, passes through battery screw thread using syringe or liquid-transfering gun
The liquid injection hole of upper cover injects electrolyte or distilled water in the gap of air cathode and zinc load, until gel back original state,
The bolt of liquid injection hole and gas vent is screwed, is sealed.
Self-discharge of battery test result (Fig. 4 (a)) shows that all solid state neutral zinc-air battery provided by the invention (uses
Glycerol is electrolyte) 300 hours voltage decline 0.04V, and all solid state alkaline zinc-air battery of same procedure preparation (uses
KOH is electrolyte) voltage decline 0.4V.The charge and discharge cycles test result (Fig. 4 (b)) of battery shows provided by the present invention
The method of supplement electrolyte can restore battery performance, extend battery life.
Detailed description of the invention
Fig. 1 is all solid state neutral zinc-air battery structure chart of the invention
Fig. 2 is all solid state neutral zinc-air battery frame of the invention
Fig. 3 is the planing surface figure of threaded upper cover of the invention
Fig. 4 (a) is that all solid state zinc-air battery of neutral long-life and KOH alkaline battery self-discharge performance of the invention are tested
Curve；Fig. 4 (b) is all solid state zinc-air battery cycle charge discharge electric performance test curve of neutral long-life of the invention
Specific embodiment 1:
The braced frame of battery: cell support frame is Open architecture, is provided with enough holes and guarantees that air enters air
Cathode.There are grooves to be used for fixed metal electrode for threaded upper cover and bottom, and limitation metal zinc load moves horizontally.By screwing
Threaded upper cover can limit the axial movement of metal zinc load with fastening metal zinc load.Braced frame also sets up air cathode
Fixed card slot prevents air cathode deformation or mobile.
The preparation of metal zinc load: metal zinc load is the high pure metal zinc bar bright with fine sandpaper polishing.Metal zinc load
One end having a size of diameter 5mm, long 40mm, the other end is having a size of diameter 3mm, long 5mm.
Air cathode preparation: 24mg conductive black (VXC-72) and 24mg La are weighed0.8Sr0.2Co0.6Fe0.4O3Catalyst
It is stirred in 30ml ethyl alcohol, the Nafion binder of 100ul 5wt% is added dropwise, be ultrasonically treated 2 hours, form finely dispersed urge
Agent slurry.Using the hydrophobic, air-permeability carbon cloth of 6cm × 4cm as matrix, by configured catalysis by way of spraying or being added dropwise
Agent slurry coating heats 1 hour, forming catalyst loadings is in the side of hydrophobic, air-permeability carbon cloth on 80 DEG C of warm table
1mg cm-2Air cathode.Using roll-in is carried out to air cathode and nickel foam respectively on roll squeezer, integrated knot is made
Structure, for use.Air cathode with a thickness of 1.3mm.
The preparation of gel electrolyte: 15g glycerol, 30g distilled water uniformly mix, and form 1# solution.4g propylene is weighed respectively
Sour potassium solution, 1g N, N '-methylene-bisacrylamide are added 1# solution, uniformly mix, form 2# mixed liquor.Weigh 0.5g mistake
Potassium sulfate is added in 2# mixed liquor, stirs evenly, and forms neutral gel electrolyte mixed liquor, for use.
The preparation and test of all solid state zinc-air battery:
Inwardly by the Catalytic Layer of air cathode, it is fixed in the card slot of battery frame.Metal zinc load is assembled to battery
In the groove of frame, positioning, screw thread upper cover.Configured gel electrolyte is mixed by the liquid injection hole of battery threaded upper cover
It in the gap for closing liquid injection air cathode and metal zinc load, stands, gel, sealing.It is all solid state to be assembled into the neutral long-life
Zinc-air battery.Later-stage utilization syringe supplements electrolyte to battery by liquid injection hole.
Self-discharge of battery test result shows under 300 hours voltage of all solid state neutral zinc-air battery provided by the invention
0.045V drops.
Specific embodiment 2:
The braced frame of battery: there are grooves to be used for fixed metal electrode for threaded upper cover and bottom, limits metal zinc load
Move horizontally.By screw thread upper cover the axial movement of metal zinc load can be limited with fastening metal zinc load.Support frame
Frame also sets up the fixed card slot of air cathode, prevents air cathode deformation or mobile.
The preparation of metal zinc load: metal zinc load is the high pure metal zinc bar bright with fine sandpaper polishing.Metal zinc load
One end having a size of diameter 5mm, long 40mm, the other end is having a size of diameter 3mm, long 5mm.
Air cathode preparation: 24mg conductive black (VXC-72) and 24mg La are weighed0.8Sr0.2Co0.6Fe0.4O3Catalyst
It is stirred in 30ml ethyl alcohol, the Nafion binder of 100ul 5wt% is added dropwise, be ultrasonically treated 2 hours, form finely dispersed urge
Agent slurry.Using the hydrophobic, air-permeability carbon cloth of 6cm × 4cm as matrix, by configured catalysis by way of spraying or being added dropwise
Agent slurry coating heats 1 hour, forming catalyst loadings is in the side of hydrophobic, air-permeability carbon cloth on 80 DEG C of warm table
1mg cm-2Air cathode.Using roll-in is carried out to air cathode and nickel foam respectively on roll squeezer, integrated knot is made
Structure, for use.Air cathode with a thickness of 1.3mm.
The preparation of gel electrolyte: 30g ethylene glycol, 30g distilled water uniformly mix, and form 1# solution.6g third is weighed respectively
Olefin(e) acid sodium solution, 1g N, N '-methylene-bisacrylamide are added 1# solution, uniformly mix, form 2# mixed liquor.Weigh 0.5g
Potassium peroxydisulfate is added in 2# mixed liquor, stirs evenly, and forms neutral gel electrolyte mixed liquor, for use.
The preparation and test of all solid state zinc-air battery:
Inwardly by the Catalytic Layer of air cathode, it is fixed in the card slot of battery frame.Metal zinc load is assembled to battery
In the groove of frame, positioning, screw thread upper cover.Configured gel electrolyte is mixed by the liquid injection hole of battery threaded upper cover
It in the gap for closing liquid injection air cathode and metal zinc load, stands, gel, sealing.It is all solid state to be assembled into the neutral long-life
Zinc-air battery.Later-stage utilization syringe keeps the skin wet to battery by liquid injection hole.
Self-discharge of battery test result shows under 300 hours voltage of all solid state neutral zinc-air battery provided by the invention
0.049V drops.
Specific embodiment 3:
The braced frame of battery: there are grooves to be used for fixed metal electrode for threaded upper cover and bottom, limits metal zinc load
Move horizontally.By screw thread upper cover the axial movement of metal zinc load can be limited with fastening metal zinc load.Support frame
Frame also sets up the fixed card slot of air cathode, prevents air cathode deformation or mobile.
The preparation of metal zinc load: metal zinc load is the high pure metal zinc bar bright with fine sandpaper polishing.Metal zinc load
One end having a size of diameter 5mm, long 40mm, the other end is having a size of diameter 3mm, long 5mm.
Air cathode preparation: 24mg conductive black (VXC-72) and 24mg La are weighed0.8Sr0.2Co0.6Fe0.4O3Catalyst
It is stirred in 30ml ethyl alcohol, the Nafion binder of 100ul 5wt% is added dropwise, be ultrasonically treated 2 hours, form finely dispersed urge
Agent slurry.Using the hydrophobic, air-permeability carbon cloth of 6cm × 4cm as matrix, by configured catalysis by way of spraying or being added dropwise
Agent slurry coating heats 1 hour, forming catalyst loadings is in the side of hydrophobic, air-permeability carbon cloth on 80 DEG C of warm table
1mg cm-2Air cathode.Using roll-in is carried out to air cathode and nickel foam respectively on roll squeezer, integrated knot is made
Structure, for use.Air cathode with a thickness of 1.3mm.
The preparation of gel electrolyte: 25g ethyl alcohol, 30g distilled water uniformly mix, and form 1# solution.4g propylene is weighed respectively
Amide, 1g N, N '-methylene-bisacrylamide are added 1# solution, uniformly mix, form 2# mixed liquor.Weigh 0.5g over cure
Sour potassium is added in 2# mixed liquor, stirs evenly, and forms neutral gel electrolyte mixed liquor, for use.
The preparation and test of all solid state zinc-air battery:
Inwardly by the Catalytic Layer of air cathode, it is fixed in the card slot of battery frame.Metal zinc load is assembled to battery
In the groove of frame, positioning, screw thread upper cover.Configured gel electrolyte is mixed by the liquid injection hole of battery threaded upper cover
It in the gap for closing liquid injection air cathode and metal zinc load, stands, gel, sealing.It is all solid state to be assembled into the neutral long-life
Zinc-air battery.Later-stage utilization syringe keeps the skin wet to battery by liquid injection hole.
Self-discharge of battery test result shows under 300 hours voltage of all solid state neutral zinc-air battery provided by the invention
0.039V drops.
Specific embodiment 4:
The braced frame of battery: there are grooves to be used for fixed metal electrode for threaded upper cover and bottom, limits metal zinc load
Move horizontally.By screw thread upper cover the axial movement of metal zinc load can be limited with fastening metal zinc load.Support frame
Frame also sets up the fixed card slot of air cathode, prevents air cathode deformation or mobile.
The preparation of metal zinc load: metal zinc load is the high pure metal zinc bar bright with fine sandpaper polishing.Metal zinc load
One end having a size of diameter 5mm, long 40mm, the other end is having a size of diameter 3mm, long 5mm.
Air cathode preparation: 24mg conductive black (VXC-72) and 24mg La are weighed0.8Sr0.2Co0.6Fe0.4O3Catalyst
It is stirred in 30ml ethyl alcohol, the Nafion binder of 100ul 5wt% is added dropwise, be ultrasonically treated 2 hours, form finely dispersed urge
Agent slurry.Using the hydrophobic, air-permeability carbon cloth of 6cm × 4cm as matrix, by configured catalysis by way of spraying or being added dropwise
Agent slurry coating heats 1 hour, forming catalyst loadings is in the side of hydrophobic, air-permeability carbon cloth on 80 DEG C of warm table
1mg cm-2Air cathode.Using roll-in is carried out to air cathode and nickel foam respectively on roll squeezer, integrated knot is made
Structure, for use.Air cathode with a thickness of 1.3mm.
The preparation of gel electrolyte: 15g glycerol, 30g distilled water uniformly mix, and form 1# solution.4g propylene is weighed respectively
Sour potassium solution, 1g N, N '-methylene-bisacrylamide are added 1# solution, uniformly mix, form 2# mixed liquor.Weigh 0.5g mistake
Potassium sulfate is added in 2# mixed liquor, stirs evenly, and forms neutral gel electrolyte mixed liquor, for use.
The preparation and test of all solid state zinc-air battery:
Inwardly by the Catalytic Layer of air cathode, it is fixed in the card slot of battery frame.Metal zinc load is assembled to battery
In the groove of frame, positioning, screw thread upper cover.Configured gel electrolyte is mixed by the liquid injection hole of battery threaded upper cover
It in the gap for closing liquid injection air cathode and metal zinc load, stands, gel, sealing.It is all solid state to be assembled into the neutral long-life
Zinc-air battery.Later-stage utilization syringe supplements above-mentioned 1# solution to battery by liquid injection hole.
Self-discharge of battery test result shows under 300 hours voltage of all solid state neutral zinc-air battery provided by the invention
0.036V drops.
Claims (7)
1. providing a kind of all solid state neutral zinc-air battery, comprising: gel electrolyte, air cathode, metal zinc load, battery
Braced frame, threaded upper cover.Preparation step is as follows: (1) gel electrolyte: preferred sodium acrylate (ANa), potassium acrylate (AK) and
One or more of acrylamide (AM) solution, by itself and N, N '-methylene-bisacrylamide (MBAM) is according to 4~10 mass
Than mixing, water is added to be made into the solution that total concentration is 5~35%.Ethylene glycol, isopropanol, ethyl alcohol and glycerol are added in the solution
One of or it is several, add water be made into concentration be 20~60% electrolyte solution.0.1-0.5% is added in the solution
Quality is sufficiently stirred than initiator potassium persulfate, forms uniform electrolyte solution.(2) zinc is fixed in cell support frame
Cathode and air cathode.(3) electrolyte is injected into the gap between air cathode and metal zinc load by liquid injection hole, stood,
Gel is assembled into all solid state zinc-air battery.(4) after battery operation or after placing a period of time, by liquid injection hole to battery
Electrolyte is supplemented, to restore battery performance.
2. the preferred hydrophobic, air-permeability carbon cloth of hydrophobic breathable layer or hydrophobic, air-permeability carbon paper.
3. Catalytic Layer is made of conductive carbon material and catalyst material.The mass ratio of the conductive carbon material and catalyst material is excellent
Select 0.5~1.5.One or more of the preferred conductive black of the conductive carbon material, activated carbon, graphene.The catalyst
The preferred platinum of material, transition metal oxide, without one or more of metal carbon material, C-base composte material.
4. the preferred high purity zinc metal bar of activity zinc load according to claim 1 or metal tube.
5. the preferred organic glass of cell support frame according to claim 1, polyethylene, polypropylene, polyvinyl chloride or
ABS plastic.
6. the preferred organic glass of threaded upper cover according to claim 1, polyethylene, polypropylene, polyvinyl chloride or ABS modeling
Material.
7. one of the preferred ethylene glycol of supplement electrolyte according to claim 1, ethyl alcohol, glycerol or aqueous isopropanol
Or it is several.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910411399.5A CN110289387B (en) | 2019-05-17 | 2019-05-17 | All-solid-state neutral zinc-air battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910411399.5A CN110289387B (en) | 2019-05-17 | 2019-05-17 | All-solid-state neutral zinc-air battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110289387A true CN110289387A (en) | 2019-09-27 |
| CN110289387B CN110289387B (en) | 2021-10-29 |
Family
ID=68002345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910411399.5A Active CN110289387B (en) | 2019-05-17 | 2019-05-17 | All-solid-state neutral zinc-air battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110289387B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110828855A (en) * | 2019-11-07 | 2020-02-21 | 上海电力大学 | Flexible self-oxygen-supply rechargeable zinc-air battery pack module |
| CN113675506A (en) * | 2021-09-17 | 2021-11-19 | 安徽朔代科技有限公司 | Cell unit structure and metal fuel cell |
| CN113937304A (en) * | 2021-09-30 | 2022-01-14 | 华中科技大学 | Flexible neutral zinc-air battery and preparation method thereof |
| CN114204167A (en) * | 2021-12-10 | 2022-03-18 | 辽宁大学 | Preparation method of rechargeable iron or zinc-air battery based on hydrogel electrolyte |
| CN115207367A (en) * | 2022-07-11 | 2022-10-18 | 燕山大学 | Air electrode, preparation method and application thereof, and photo-assisted charging zinc-air battery |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794812A (en) * | 2014-01-02 | 2014-05-14 | 河南科技大学 | Gel polymer electrolyte, preparation method of gel polymer electrolyte and silicon air battery using gel polymer electrolyte |
| CN104518223A (en) * | 2013-09-30 | 2015-04-15 | 西安福安创意咨询有限责任公司 | Air electrode of zinc-air battery |
| CN104900943A (en) * | 2015-04-26 | 2015-09-09 | 渤海大学 | Plug-in control gel electrolyte lithium empty electric pile and preparation method thereof |
| WO2017159803A1 (en) * | 2016-03-18 | 2017-09-21 | 国立大学法人信州大学 | Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof |
| CN107482282A (en) * | 2017-09-20 | 2017-12-15 | 深圳美能动力科技有限公司南京分公司 | A kind of locomotive and its application method for delivering power supply |
| CN107579312A (en) * | 2017-08-03 | 2018-01-12 | 中国科学技术大学 | A kind of zinc and air cell with takeup type structure |
| CN107799854A (en) * | 2016-09-05 | 2018-03-13 | 中国科学院宁波材料技术与工程研究所 | A kind of high-temperature solid sodium ion air oxygen compound energy-storage battery |
| CN107871917A (en) * | 2017-11-12 | 2018-04-03 | 湖南科技大学 | Zinc-air battery and its manufacture method in a kind of neutral solution |
| CN107978727A (en) * | 2017-12-28 | 2018-05-01 | 张树雄 | A kind of metal-air battery system |
| CN108539330A (en) * | 2018-02-06 | 2018-09-14 | 宁波大学 | A kind of all solid state zinc-air battery and its gel electrolyte |
| CN108987857A (en) * | 2018-07-18 | 2018-12-11 | 北京化工大学 | A kind of zinc air flow battery based on faintly acid electrolyte |
| US20190140315A1 (en) * | 2017-11-07 | 2019-05-09 | City University Of Hong Kong | Rechargeable polyacrylamide based polymer electrolyte zinc-ion batteries |
-
2019
- 2019-05-17 CN CN201910411399.5A patent/CN110289387B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104518223A (en) * | 2013-09-30 | 2015-04-15 | 西安福安创意咨询有限责任公司 | Air electrode of zinc-air battery |
| CN103794812A (en) * | 2014-01-02 | 2014-05-14 | 河南科技大学 | Gel polymer electrolyte, preparation method of gel polymer electrolyte and silicon air battery using gel polymer electrolyte |
| CN104900943A (en) * | 2015-04-26 | 2015-09-09 | 渤海大学 | Plug-in control gel electrolyte lithium empty electric pile and preparation method thereof |
| WO2017159803A1 (en) * | 2016-03-18 | 2017-09-21 | 国立大学法人信州大学 | Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof |
| US20190019629A1 (en) * | 2016-03-18 | 2019-01-17 | Shinshu University | Lithium composite negative electrode and hybrid capacitor, and manufacturing methods thereof |
| CN107799854A (en) * | 2016-09-05 | 2018-03-13 | 中国科学院宁波材料技术与工程研究所 | A kind of high-temperature solid sodium ion air oxygen compound energy-storage battery |
| CN107579312A (en) * | 2017-08-03 | 2018-01-12 | 中国科学技术大学 | A kind of zinc and air cell with takeup type structure |
| CN107482282A (en) * | 2017-09-20 | 2017-12-15 | 深圳美能动力科技有限公司南京分公司 | A kind of locomotive and its application method for delivering power supply |
| US20190140315A1 (en) * | 2017-11-07 | 2019-05-09 | City University Of Hong Kong | Rechargeable polyacrylamide based polymer electrolyte zinc-ion batteries |
| CN107871917A (en) * | 2017-11-12 | 2018-04-03 | 湖南科技大学 | Zinc-air battery and its manufacture method in a kind of neutral solution |
| CN107978727A (en) * | 2017-12-28 | 2018-05-01 | 张树雄 | A kind of metal-air battery system |
| CN108539330A (en) * | 2018-02-06 | 2018-09-14 | 宁波大学 | A kind of all solid state zinc-air battery and its gel electrolyte |
| CN108987857A (en) * | 2018-07-18 | 2018-12-11 | 北京化工大学 | A kind of zinc air flow battery based on faintly acid electrolyte |
Non-Patent Citations (2)
| Title |
|---|
| LONG JUNLI,.ET AL: "《Long-Life, High-Voltage Acidic Zn-Air Batteries》", 《ADVANCED MATERIALS》 * |
| 于华章等: "锌空气电池准中性电解液的研究", 《应用化学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110828855A (en) * | 2019-11-07 | 2020-02-21 | 上海电力大学 | Flexible self-oxygen-supply rechargeable zinc-air battery pack module |
| CN110828855B (en) * | 2019-11-07 | 2022-09-06 | 上海电力大学 | Flexible self-oxygen-supply rechargeable zinc-air battery pack module |
| CN113675506A (en) * | 2021-09-17 | 2021-11-19 | 安徽朔代科技有限公司 | Cell unit structure and metal fuel cell |
| CN113937304A (en) * | 2021-09-30 | 2022-01-14 | 华中科技大学 | Flexible neutral zinc-air battery and preparation method thereof |
| CN114204167A (en) * | 2021-12-10 | 2022-03-18 | 辽宁大学 | Preparation method of rechargeable iron or zinc-air battery based on hydrogel electrolyte |
| CN115207367A (en) * | 2022-07-11 | 2022-10-18 | 燕山大学 | Air electrode, preparation method and application thereof, and photo-assisted charging zinc-air battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110289387B (en) | 2021-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110289387A (en) | A kind of all solid state neutral zinc-air battery | |
| CN100483812C (en) | Integrated pole dual-pole board for oxidation deoxidization liquid energy-storing battery and its preparation | |
| CN102013527B (en) | Rechargeable zinc ion battery | |
| Li et al. | Improved performance of a tubular microbial fuel cell with a composite anode of graphite fiber brush and graphite granules | |
| CN102544526B (en) | Preparation method of graphite felt modified electrode and all vanadium flow battery | |
| CN104701555B (en) | A kind of air electrode of zinc-air cell and preparation method thereof based on graphene | |
| BR0007732A (en) | Cathode for use in an electrochemical cell, metal-air battery, and electrochemical cell to provide electrical power | |
| Cheng et al. | Performance gains in single flow zinc–nickel batteries through novel cell configuration | |
| US20180269511A1 (en) | Microbial fuel cell and microbial fuel cell system | |
| CN107919234B (en) | A kind of enhanced supercapacitor and preparation method thereof | |
| CN107731566A (en) | A kind of preparation method and application of three-dimensional petal-shaped nickel cobalt sulfide electrode material | |
| CN106684392B (en) | Cathode air electrode, water power generation metal-air battery and preparation method | |
| CN110492176A (en) | A kind of alkaline-resisting double-network hydrogel flexible electrolyte and the preparation method and application thereof | |
| Chartouni et al. | Air–metal hydride secondary battery with long cycle life | |
| Giordano et al. | An investigation of the effects of electrode preparation parameters on the performance of phosphoric acid fuel cell cathodes | |
| CN111416129A (en) | Acid-base asymmetric electrolyte zinc-quinone battery | |
| JP3866534B2 (en) | Fuel cell | |
| JP7191039B2 (en) | metal air fuel cell | |
| CN104078689B (en) | Graphene attaches the preparation method of plastics load P dNi hydrogen peroxide electric reduction catalyst | |
| CN108047486B (en) | Chitosan-graphene oxide sponge, preparation method and application | |
| CN207677041U (en) | A kind of magnesium air battery | |
| CN104716327A (en) | Cathodic electrode material for lithium air batteries and application | |
| CN204614844U (en) | A kind of lithium ion battery function pad | |
| CN108604719A (en) | Air MH secondary battery | |
| CN215418226U (en) | Metal-air battery cathode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240626 Address after: Room 102, Building 9, No. 19 Yangcheng Road, Pingyao Town, Yuhang District, Hangzhou City, Zhejiang Province, 311115 Patentee after: Hangzhou Lvcong Hydrogen Energy Technology Co.,Ltd. Country or region after: China Address before: 315000 Fenghua Road, Jiangbei District, Ningbo, Zhejiang Province, No. 818 Patentee before: Ningbo University Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240905 Address after: No. 301-548, 3rd Floor, Building 2, No. 1188 Dayuan Road, Qingshanhu Street, Lin'an District, Hangzhou City, Zhejiang Province 310000 Patentee after: Hangzhou Eloi Composite Materials Co.,Ltd. Country or region after: China Address before: Room 102, Building 9, No. 19 Yangcheng Road, Pingyao Town, Yuhang District, Hangzhou City, Zhejiang Province, 311115 Patentee before: Hangzhou Lvcong Hydrogen Energy Technology Co.,Ltd. Country or region before: China |