CN116130672A - Zinc powder negative electrode of zinc-manganese quasi-solid state flow battery and semi-dry method electrode manufacturing method thereof - Google Patents
Zinc powder negative electrode of zinc-manganese quasi-solid state flow battery and semi-dry method electrode manufacturing method thereof Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000007787 solid Substances 0.000 title claims abstract description 46
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 40
- 239000000843 powder Substances 0.000 claims abstract description 72
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 29
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 29
- 239000010935 stainless steel Substances 0.000 claims abstract description 29
- 239000011888 foil Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 19
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 238000013329 compounding Methods 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 11
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- 239000002245 particle Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
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- 239000000693 micelle Substances 0.000 claims description 11
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052621 halloysite Inorganic materials 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910052900 illite Inorganic materials 0.000 claims description 4
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000010731 rolling oil Substances 0.000 claims description 3
- 239000006245 Carbon black Super-P Substances 0.000 claims description 2
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- 150000002736 metal compounds Chemical group 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000005488 sandblasting Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 239000011701 zinc Substances 0.000 abstract description 13
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000011572 manganese Substances 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 4
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- 238000001035 drying Methods 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000009966 trimming Methods 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
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- 239000013078 crystal Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—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
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- 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
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- H01M4/8673—Electrically conductive fillers
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- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- H—ELECTRICITY
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- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- 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
Abstract
The invention provides a zinc powder negative electrode of a zinc-manganese quasi-solid state flow battery and a semi-dry electrode manufacturing method thereof, wherein zinc powder, a conductive agent, a toughening conductive agent, a cation slow release agent and a hydrogen evolution inhibitor are uniformly mixed in a mixer; friction is carried out under the wet condition by ball milling equipment, so that the molecular chain of polytetrafluoroethylene is stretched, opened and wiredrawn to form a net structure and physically adhered with powder, and simultaneously, a hydrogen evolution inhibitor and the surface of zinc powder undergo a reduction reaction to passivate zinc; and then carrying out banburying and granulation, hot-pressing to prepare a negative electrode film, and carrying out semi-drying, and then thermally compounding the semi-dried negative electrode film on two sides of a stainless steel foil to prepare the electrode. The prepared zinc powder cathode has high porosity, stable electrode structure and three-dimensional conductivityThe network has a cation slow-release function, and can effectively slow down cations (Mn) in the electrolyte caused by stripping/depositing of the active zinc ions 2+ ，H + ，Zn 2+ ) The surface of the zinc powder is inerted to avoid hydrogen evolution, and the hydrophobic effect of PTFE entanglement network can protect the zinc powder.
Description
Technical Field
The invention relates to a zinc powder negative electrode of a zinc-manganese quasi-solid state flow battery and a semi-dry electrode manufacturing method thereof, belonging to the field of new energy materials.
Background
Today, the explosive growth of electric vehicles, wearable and portable electronic products has spawned a great demand for high energy density and safety devices. At present, the global product mainly comprises lithium batteries, the annual lithium consumption is 30 ten thousand tons, the annual lithium consumption is continuously increased at the speed of 7-11% per year, the exponential rising trend is presented, the price of lithium resources is increased, and the material cost of the lithium batteries is extremely high, so that the development of secondary batteries of non-lithium systems becomes industry consensus and hot spots. Aqueous zinc-manganese secondary batteries are receiving increasing attention from academia and industry due to their low raw materials, high safety, long life and high energy density in aqueous batteries. The negative electrode of the high-performance water-based zinc-manganese secondary battery is hindered by dendrite growth, hydrogen evolution reaction and corrosion, so that short circuit is caused, and the coulomb efficiency is low. Therefore, inhibition of dendrite growth and corresponding side reactions is urgently needed to obtain a high-performance zinc battery. In order to solve the above problems, construction of a three-dimensional structure, zinc surface engineering, and the like have been proposed. Based on the principle, in order to realize long service life and high capacity of the battery, uniform electrochemical deposition is required to be carried out on the surface of the zinc cathode, and certain protection is required to be carried out on the surface of the zinc cathode, so that the anode is prevented from being continuously passivated by unavoidable byproducts in the charge and discharge process. The electrode should have a richer pore canal system, so as to facilitate the permeation of the water-based electrolyte; the electrode has an excellent three-dimensional conductive carbon network, and can provide a large number of dissolution/deposition reaction active sites; the electrode itself needs to have a cation slow release capability to reduceRetarding cations (Mn) in the electrolyte caused by stripping/deposition of zinc ions 2+ ，H + ，Zn 2+ ) Greatly fluctuates, stabilizes the pH value of the electrolyte and provides high reversibility of the system.
Disclosure of Invention
In order to overcome the defects, the invention provides the zinc powder cathode of the zinc-manganese quasi-solid flow battery and the manufacturing method of the semi-dry electrode thereof, and the prepared zinc powder cathode has high porosity, stable electrode structure, three-dimensional conductive network and cation slow release function, and can effectively slow down cations (Mn) in electrolyte caused by stripping/depositing zinc ions 2+ ，H + ，Zn 2+ ) The surface of the zinc powder is inerted to avoid hydrogen evolution, and the hydrophobic effect of PTFE entangled network also protects the zinc powder.
The aim of the invention is achieved by the following technical scheme:
the semi-dry electrode manufacturing method of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery is characterized by comprising the following steps of:
uniformly mixing zinc powder, a conductive agent, a toughening conductive agent, a cationic slow-release agent and a hydrogen evolution inhibitor in a mixer until powder A is obtained;
uniformly mixing polytetrafluoroethylene powder and powder A in a mixer until powder B is obtained; the mixing process is carried out under the temperature condition that Polytetrafluoroethylene (PTFE) is in a glass state;
in ball milling equipment, the mixed solvent of the powder B and the alcohol water continuously rubs in high-speed rotation through ball milling beads to enable PTFE wiredrawing to be in a net structure, molecular chains of polytetrafluoroethylene in the powder B are extended and opened to form physical adhesion with powder in A, a hydrogen evolution inhibitor and the surface of zinc powder undergo a reduction reaction, and after the process is finished, a micelle C is obtained through filtration;
the glue group C is banburying to form uniform glue groups, and then shearing and granulating to prepare millimeter-sized particles E with uniform size;
the particles E are hot-pressed by a horizontal hot roller press to prepare a negative electrode film F, porous release paper is used as a supporting carrier tape to finish rolling, the negative electrode film F coated with the release paper is coiled and dried, and part of solvent is removed;
and (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
Further, the zinc powder is powdery particles with the particle size of 5-20 mu m; the conductive agent is one or two of super-P, ECP, and the toughening conductive agent is one or a mixture of two of artificial graphite and high-purity graphite; the cation slow release agent is inorganic powder which has electronegativity and swells when meeting water. The hydrogen evolution inhibitor is a metal compound which can generate reduction reaction with zinc powder in an alcohol-water solvent.
Further, the cationic slow release agent is one or more of bentonite, montmorillonite powder, illite powder, kaolin powder and halloysite powder.
Further, the hydrogen evolution inhibitor is preferably one or more of indium chloride, copper chloride, indium sulfate and copper sulfate.
Further, the zinc powder, the conductive agent, the toughening conductive agent, the cationic slow release agent, the polytetrafluoroethylene and the hydrogen evolution inhibitor powder comprise 60-90% by weight: 1% -10%:1% -10%:1% -10%:3% -15%:0.1% -5%.
Further, the alcohol-water mixed solvent is a mixed solvent of water and isopropanol, propylene glycol or ethanol, and the volume percentage of water and alcohol is as follows: 40vol% -80vol%:20vol% to 60vol%; the solid content of the uniform micelle is 40-60 wt%.
Further, the granular material E is rolled once by a horizontal hot roll press to reach the thickness of the anode film F of 90-200 mu m, and the hot rolling temperature is 55-95 ℃.
Further, when the semi-dry negative electrode film F is thermally compounded with the stainless steel foil, the glued stainless steel foil is clamped between the two negative electrode films F which are stripped off from the release paper, the glue is unreeled at the same speed, the glue enters into two horizontal hot roller presses which rotate relatively, the rolling temperature is 30-120 ℃, the width of the roller gap is regulated, and the pressure is controlled, so that the negative electrode film F can be just compounded on the glued stainless steel foil, and the situation that the deformation of the negative electrode film F is overlarge and even the stainless steel foil is broken due to overlarge rolling pressure is avoided.
Furthermore, the glue-coated stainless steel foil is formed by printing high-conductivity slurry on two sides of the stainless steel foil by adopting a gravure printing machine, wherein the surface of the stainless steel foil is required to be subjected to sand blasting treatment before glue coating, surface rolling oil is removed, and the high-conductivity slurry consists of high-purity graphite, a non-hydrophilic adhesive and a non-aqueous solvent.
The zinc powder cathode of the zinc-manganese quasi-solid state flow battery is prepared by the semi-dry electrode manufacturing method of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery.
Compared with the prior art, the semi-dry electrode of the zinc powder cathode prepared by the method has the following characteristics: (1) dendrite inhibition can be effectively performed; (2) has the function of cation slow release; (3) An excellent three-dimensional conductive network with more peeled/deposited active sites; (4) the PTFE entanglement network structure is stable; (5) The porosity is large (6), so that hydrogen evolution of the zinc cathode can be effectively avoided.
According to the invention, inorganic powder such as bentonite, montmorillonite powder, illite powder, kaolin powder, halloysite powder and the like is introduced into the semi-dry electrode, the volume of the semi-dry electrode expands several times to tens times when the semi-dry electrode is contacted with water, the moisture is effectively fixed, the solid content of the micelle is reduced, the micelle is prevented from sticking to a roller in the subsequent film pressing process due to excessive solvent, the inorganic powder is contracted in volume in the drying process after film forming, and the pore canal is introduced, so that the porosity of the semi-dry electrode is improved. Inorganic powders such as bentonite, montmorillonite powder, illite powder, kaolin powder, halloysite powder and the like have strong electronegativity, and excessive cations (Mn) in the electrolyte are effectively absorbed through a layered crystal structure 2+ ，H + ，Zn 2+ ) Plays a role of cation slow release, and slows down the cation (Mn 2+ ，H + ，Zn 2+ ) Greatly fluctuates, stabilizes the pH value of the electrolyte and provides high reversibility of the system.
According to the invention, the hydrogen evolution inhibitor is directly introduced in the ball milling and fiberizing process, and the hydrogen evolution inhibitor and the surface of the zinc powder undergo a sufficient reduction reaction while the slurry is ball milled, so that the surface of the zinc powder is sufficiently passivated, and the hydrogen evolution is effectively inhibited after the electrode is manufactured. In addition, the hydrophobic nature of the PTFE entanglement network can also provide protection to zinc dust.
The semi-dry method negative electrode film after primary film pressing and film forming is low in solid content and tensile strength, and cannot be wound in a self-supporting manner like a full-dry method electrode.
The current collector adopts the adhesive coated and sandblasted stainless steel, rolling oil is removed from the surface of the sandblasted stainless steel, the adhesion force between the rough surface and the conductive layer and the zinc powder negative electrode film is stronger, and the coated conductive adhesive layer is a mixture of high-purity graphite and a non-hydrophilic adhesive, so that the corrosion of water to the stainless steel current collector can be effectively prevented, and the electrode film and the current collector foil are prevented from falling off.
Drawings
SEM images of the surface of the negative electrode film described in fig. 1.
SEM images of the spatially entangled network structure of PTFE of the cross section of the negative electrode film described in fig. 2.
Fig. 3 is a charge-discharge graph of the assembled zinc-manganese quasi-solid state flow battery of embodiment 1 assembled at room temperature 25 ℃ and a current density of 0.1C;
fig. 4 is a cycle chart of the zinc-manganese quasi-solid state flow battery assembly assembled in example 1 at room temperature 25 ℃ and 0.2C current density.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. Elements and features described in one embodiment of the invention may be combined with elements and features shown in one or more other embodiments. It should be noted that the illustration and description of components and processes known to those of ordinary skill in the art, which are not relevant to the present invention, have been omitted for clarity. All other embodiments, which can be made by a person skilled in the art based on the embodiments of the invention without any inventive effort, are intended to fall within the scope of the invention.
The specific manufacturing method comprises the following steps:
uniformly mixing zinc powder, a conductive agent, a toughening conductive agent, a cationic slow-release agent and a hydrogen evolution inhibitor in a mixer until powder A is obtained; uniformly mixing polytetrafluoroethylene powder and powder A in a mixer until powder B is obtained; the mixing process is carried out under the condition that the polytetrafluoroethylene is lower than 10 ℃ and is in a glass state; and adding an alcohol-water mixed solvent into the powder B in a planetary ball mill or other milling equipment, and continuously rubbing the powder B under a wet state by high-speed rotation of ball milling beads to enable wiredrawing to be in a net structure, so that the hydrogen evolution inhibitor fully reacts with the surface of zinc powder. After the process is finished, filtering to obtain a micelle C; the gel group C is banburying to form a uniform gel group, and the uniform gel group is shearing and granulating to prepare millimeter-sized particles E with uniform size; the particles E are hot-pressed by a horizontal hot roller press to prepare a negative electrode film F, porous release paper is used as a supporting carrier tape to finish rolling, the negative electrode film F coated with the release paper is coiled and dried, and part of solvent is removed; and (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
When the semi-dry negative electrode film F is thermally compounded with the stainless steel foil, the glued stainless steel foil is clamped between the two negative electrode films F which are stripped off from the paper, and the glue is unreeled at the same speed, enters into two horizontal hot roller presses which rotate relatively, the rolling temperature is 30-120 ℃, and the width of the roller gap is regulated and the pressure is controlled, so that the negative electrode film F can be just compounded on the glued stainless steel foil, and the situation that the deformation of the negative electrode film F is overlarge and even the stainless steel foil is broken due to overlarge rolling pressure is avoided.
Example 1:
zinc powder, ECP, high-purity graphite, montmorillonite powder and indium chloride are mixed according to the weight percentage of 74: 7 wt.%: 5 wt.%: 5 wt.%: 1 weight percent of the powder A is uniformly mixed in a mixer; uniformly mixing 8wt% of polytetrafluoroethylene powder and 92wt% of powder A in a mixer at 0 ℃ until powder B is obtained; adding a mixed solvent prepared from ethanol and deionized water according to a volume ratio of 1:1 into a planetary ball mill, continuously rubbing to enable PTFE wiredrawing to be in a net structure through high-speed rotation of ball milling beads in a wet state, carrying out reduction reaction on indium chloride and zinc powder, and filtering to obtain a micelle C after the process is finished; the gel group C is subjected to banburying to form uniform gel groups, and the gel groups are subjected to shearing and granulating to prepare millimeter-sized particles E with uniform size, wherein the solid content is 50%; the particles E were rolled once by a horizontal hot roll press to a 150 μm negative film F at a hot rolling temperature of 80 ℃. The negative electrode film F is subjected to trimming under the horizontal hot roller, the width requirement of the film is met, the trimming materials can be sheared again, and the trimming materials are put into the granular materials E to finish the recycling of the trimming materials. And (5) attaching the trimmed negative electrode film F to a supporting belt of the porous release paper to finish rolling. After winding, the whole roll is dried, part of the solvent is removed, and the solid content of the semi-dried negative electrode film F is 65%. The structure of the surface and the cross section of the negative electrode film F is shown in fig. 1 and 2, and the entangled network structure formed by PTFE can make the structure of the electrode more stable. And (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
And (3) assembling a zinc-manganese quasi-solid-state flow battery:
and (3) assembling: zinc ion solid diaphragm with sandwich composite structure of hydrophilic PE film/non-porous PPS solid diaphragm/cellulose film, semi-dry gamma-MnO 2 The positive pole piece, the semi-dry zinc powder negative pole lamination, the welding tab and the packaging are packaged into a shell, and the non-electrolyte-injected battery is assembled. Zn (otf) with a concentration of 3mol/L was injected 2 +0.1mol/L MnSO 4 And (3) vacuumizing and sealing the aqueous electrolyte to prepare the zinc-manganese quasi-solid flow battery. The zinc-manganese quasi-solid state flow battery assembly is shown in fig. 3 and 4 with a charge-discharge graph at room temperature of 25 ℃,0.1C and a cycle chart at a current density of 0.2C. By adopting the dry zinc powder cathode, the zinc-manganese secondary battery has lower internal resistance and higher capacity, the gas production of the battery is extremely low, the circulation stability is enhanced, and after long-term circulation, no dendrite is generated on the surface of the cathode after the battery is opened.
Example 2:
zinc powder, SP, high purity graphite, I Li Danfen, copper chloride in an amount of 50wt%:15 wt.%: 15 wt.%: 10wt%:2wt% of the powder A is uniformly mixed in a mixer; uniformly mixing 8wt% of polytetrafluoroethylene powder and 92wt% of powder A in a mixer at 5 ℃ until powder B is obtained; adding a certain alcohol solvent into a planetary ball mill, continuously rubbing to enable wiredrawing to be in a net structure through high-speed rotation of ball milling beads in a wet state, stretching and opening a molecular chain of polytetrafluoroethylene in the powder B, physically adhering the molecular chain with the powder in the powder A, carrying out reduction reaction on copper chloride and zinc powder, and filtering to obtain a micelle C after the process is finished; the gel group C is subjected to banburying to form uniform gel groups, and the gel groups are subjected to shearing and granulating to prepare millimeter-sized particles E with uniform size, wherein the solid content is 75%; the particles E were rolled once by a horizontal hot roll press to a negative electrode film F of 120. Mu.m, the hot rolling temperature being 90 ℃. The negative electrode film F is subjected to trimming under the horizontal hot roller, the width requirement of the film is met, the trimming materials can be sheared again, and the trimming materials are put into the granular materials E to finish the recycling of the trimming materials. And (5) attaching the trimmed negative electrode film F to a supporting belt of the porous release paper to finish rolling. After winding, the whole roll is dried, part of the solvent is removed, and the solid content of the semi-dried negative electrode film F is 60%. And (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
And (3) assembling a zinc-manganese quasi-solid-state flow battery:
and (3) assembling: zinc ion solid diaphragm with sandwich composite structure of hydrophilic PE film/non-porous PPS solid diaphragm/cellulose film, semi-dry beta-MnO 2 The positive pole piece, the semi-dry zinc powder negative pole lamination, the welding tab and the packaging are packaged into a shell, and the non-electrolyte-injected battery is assembled. ZnSO with injection concentration of 2mol/L 4 +0.1mol/L MnSO 4 And (3) vacuumizing and sealing the aqueous electrolyte to prepare the zinc-manganese quasi-solid flow battery.
Example 3:
zinc powder, ECP, artificial graphite, kaolin and indium sulfate are mixed according to the weight percentage of 60: 10wt%:8wt%:10wt%:4wt% of the powder A is uniformly mixed in a mixer; uniformly mixing 8wt% of polytetrafluoroethylene powder and 92wt% of powder A in a mixer at 5 ℃ until powder B is obtained; adding a certain alcohol solvent into a planetary ball mill, continuously rubbing to enable wiredrawing to be in a net structure through high-speed rotation of ball milling beads in a wet state, stretching and opening a molecular chain of polytetrafluoroethylene in the powder B, physically adhering the molecular chain with the powder in the powder A, carrying out reduction reaction on indium sulfate and zinc powder, and filtering to obtain a micelle C after the process is finished; the gel group C is subjected to banburying to form uniform gel groups, and the gel groups are subjected to shearing and granulating to prepare millimeter-sized particles E with uniform size, wherein the solid content is 75%; the particles E were rolled once by a horizontal hot roll press to a negative electrode film F of 120. Mu.m, the hot rolling temperature being 90 ℃. The negative electrode film F is subjected to trimming under the horizontal hot roller, the width requirement of the film is met, the trimming materials can be sheared again, and the trimming materials are put into the granular materials E to finish the recycling of the trimming materials. And (5) attaching the trimmed negative electrode film F to a supporting belt of the porous release paper to finish rolling. After winding, the whole roll is dried, part of the solvent is removed, and the solid content of the semi-dried negative electrode film F is 60%. And (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
And (3) assembling a zinc-manganese quasi-solid-state flow battery:
and (3) assembling: zinc ion solid diaphragm with sandwich composite structure of hydrophilic PE film/non-porous PPS solid diaphragm/cellulose film, semi-dry gamma-MnO 2 The positive pole piece, the semi-dry zinc powder negative pole lamination, the welding tab and the packaging are packaged into a shell, and the non-electrolyte-injected battery is assembled. Zn (otf) with a concentration of 3mol/L was injected 2 +0.5mol/L MnSO 4 And (3) vacuumizing and sealing the aqueous electrolyte to prepare the zinc-manganese quasi-solid flow battery.
Example 4:
zinc powder, SP, artificial graphite, halloysite powder and copper sulfate are mixed according to 67 weight percent: 5 wt.%: 5 wt.%: 10wt%:5wt% of the mixture is uniformly mixed in a mixer until powder A is obtained; uniformly mixing 8wt% of polytetrafluoroethylene powder and 92wt% of powder A in a mixer at 0 ℃ until powder B is obtained; adding a certain alcohol solvent into a planetary ball mill, continuously rubbing to enable wiredrawing to be in a net structure through high-speed rotation of ball milling beads in a wet state, stretching and opening a molecular chain of polytetrafluoroethylene in the powder B, physically adhering the molecular chain with the powder in the powder A, carrying out reduction reaction on copper sulfate and zinc powder, and filtering to obtain a micelle C after the process is finished; the gel group C is subjected to banburying to form uniform gel groups, and the gel groups are subjected to shearing and granulating to prepare millimeter-sized particles E with uniform size, wherein the solid content is 70%; the particles E were rolled once by a horizontal hot roll press to 100 μm negative electrode film F at a hot rolling temperature of 95 ℃. The negative electrode film F is subjected to trimming under the horizontal hot roller, the width requirement of the film is met, the trimming materials can be sheared again, and the trimming materials are put into the granular materials E to finish the recycling of the trimming materials. And (5) attaching the trimmed negative electrode film F to a supporting belt of the porous release paper to finish rolling. After winding, the whole roll is dried, part of the solvent is removed, and the solid content of the semi-dried negative electrode film F is 55%. And (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
And (3) assembling a zinc-manganese quasi-solid-state flow battery:
and (3) assembling: zinc ion solid diaphragm with sandwich composite structure of hydrophilic PE film/non-porous PPS solid diaphragm/cellulose film, semi-dry beta-MnO 2 The positive pole piece, the semi-dry zinc powder negative pole lamination, the welding tab and the packaging are packaged into a shell, and the non-electrolyte-injected battery is assembled. ZnSO with injection concentration of 2mol/L 4 +0.5mol/L MnSO 4 And (3) vacuumizing and sealing the aqueous electrolyte to prepare the zinc-manganese quasi-solid flow battery.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Furthermore, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, means, method and steps described in the specification. Those of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, apparatuses, means, methods, or steps.
Claims (10)
1. The semi-dry electrode manufacturing method of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery is characterized by comprising the following steps of:
uniformly mixing zinc powder, a conductive agent, a toughening conductive agent, a cationic slow-release agent and a hydrogen evolution inhibitor in a mixer until powder A is obtained;
uniformly mixing polytetrafluoroethylene powder and powder A in a mixer until powder B is obtained; the mixing process is carried out under the temperature condition that Polytetrafluoroethylene (PTFE) is in a glass state;
in ball milling equipment, the mixed solvent of the powder B and the alcohol water continuously rubs in high-speed rotation through ball milling beads to enable PTFE wiredrawing to be in a net structure, molecular chains of polytetrafluoroethylene in the powder B are extended and opened to form physical adhesion with powder in the powder A, a hydrogen evolution inhibitor and the surface of zinc powder undergo a reduction reaction, and after the process is finished, a micelle C is obtained through filtration;
the glue group C is banburying to form uniform glue groups, and then shearing and granulating to prepare millimeter-sized particles E with uniform size;
the granular material E is hot pressed by a horizontal hot roller press to prepare a negative electrode film F, a porous release paper is used as a supporting carrier tape to finish rolling, the negative electrode film F coated with the release paper is dried in a whole roll, and part of solvent is removed;
and (3) adopting a hot-pressing compounding process, and thermally compounding the semi-dried negative electrode film F after the release paper is removed on two sides of the glued stainless steel foil to prepare the electrode.
2. The method for manufacturing the semi-dry electrode of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery, which is characterized in that: the zinc powder is powdery particles with the particle size of 5-20 mu m; the conductive agent is one or two of super-P, ECP, and the toughening conductive agent is one or a mixture of two of artificial graphite and high-purity graphite; the cation slow release agent is inorganic powder which has electronegativity and swells when meeting water; the hydrogen evolution inhibitor is a metal compound which can generate reduction reaction with zinc powder in an alcohol-water solvent.
3. The method for manufacturing the semi-dry electrode of the zinc powder negative electrode of the zinc-manganese quasi-solid state flow battery, which is characterized by comprising the following steps of: the cation slow release agent is one or more of bentonite, montmorillonite powder, illite powder, kaolin powder and halloysite powder.
4. The method for manufacturing the semi-dry electrode of the zinc powder negative electrode of the zinc-manganese quasi-solid state flow battery, which is characterized by comprising the following steps of: the hydrogen evolution inhibitor is one or more of indium chloride, copper chloride, indium sulfate and copper sulfate.
5. The method for manufacturing the semi-dry electrode of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery, which is characterized in that: zinc powder, a conductive agent, a toughening conductive agent, a cationic slow-release agent, polytetrafluoroethylene and hydrogen evolution inhibitor powder in percentage by weight: 1% -10%:1% -10%:1% -10%:3% -15%:0.1% -5%.
6. The method for manufacturing the semi-dry electrode of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery, which is characterized in that: the alcohol-water mixed solvent is a mixed solvent of water and isopropanol, propylene glycol or ethanol, and the volume percentage of the water and the alcohol is as follows: 40% -80%:20% -60%; the solid content of the uniform micelle is 40% -60%.
7. The method for manufacturing the semi-dry electrode of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery, which is characterized in that: the particle material E is rolled once by a horizontal hot roller press to reach the thickness of the cathode film F of 90-200 mu m, and the hot rolling temperature is 55-95 ℃.
8. The method for manufacturing the semi-dry electrode of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery, which is characterized in that: when the semi-dry negative electrode film F is thermally compounded with the stainless steel foil, the glued stainless steel foil is clamped between the two negative electrode films F which are stripped off from the paper, and the glue is unreeled at the same speed, enters into two horizontal hot roller presses which rotate relatively, the rolling temperature is 30-120 ℃, and the width of the roller gap is regulated and the pressure is controlled, so that the negative electrode film F can be just compounded on the glued stainless steel foil, and the situation that the stainless steel foil is broken due to overlarge deformation of the negative electrode film F caused by overlarge rolling pressure is avoided.
9. The method for manufacturing the semi-dry electrode of the zinc powder cathode of the zinc-manganese quasi-solid state flow battery, which is characterized in that: the coated stainless steel foil is prepared by printing high-conductivity slurry on two sides of the stainless steel foil by adopting a gravure printing machine, wherein the surface of the stainless steel foil is required to be subjected to sand blasting treatment before coating, surface rolling oil is removed, and the high-conductivity slurry consists of high-purity graphite, a non-hydrophilic adhesive and a non-aqueous solvent.
10. The zinc powder anode of a zinc-manganese quasi-solid state flow battery prepared by the semi-dry electrode manufacturing method of the zinc powder anode of the zinc-manganese quasi-solid state flow battery according to any one of claims 1-9.
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