CN114005949A - Zinc battery cathode protected by hydrophobic layer, preparation method and battery - Google Patents
Zinc battery cathode protected by hydrophobic layer, preparation method and battery Download PDFInfo
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- CN114005949A CN114005949A CN202011595304.9A CN202011595304A CN114005949A CN 114005949 A CN114005949 A CN 114005949A CN 202011595304 A CN202011595304 A CN 202011595304A CN 114005949 A CN114005949 A CN 114005949A
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000011701 zinc Substances 0.000 title claims abstract description 81
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 81
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000006182 cathode active material Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 25
- 239000001257 hydrogen Substances 0.000 abstract description 25
- 239000011241 protective layer Substances 0.000 abstract description 18
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 239000013543 active substance Substances 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 19
- 239000004615 ingredient Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 206010016766 flatulence Diseases 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0008—Phosphoric acid-based
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A zinc battery cathode protected by a hydrophobic layer, a preparation method and a battery belong to the technical field of electrochemistry. The invention is characterized in that a layer of titanate and hydrophobic binder mixture is arranged on the surface of the cathode active substance of the zinc battery to form a zinc cathode protective layer, the protective layer has certain hydrophobicity and stable structure, can effectively inhibit hydrogen evolution of the zinc cathode and zinc dendrite, and the zinc cathode with the hydrophobic protective layer and the battery adopting the cathode can obviously improve the charge-discharge cycle performance.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and relates to a zinc battery cathode, a preparation method and a battery.
Background
Since petrochemical energy is a non-renewable resource and serious pollution, most countries are currently developing new energy batteries to replace petrochemical energy, and lithium ion batteries have been developed for a long time in the aspects of electric vehicles and energy storage, whereas commercial lithium ion batteries adopt flammable organic electrolyte, and the assembly and production conditions are harsh, and in addition, the lithium resources are scarce, so that the cost of the lithium ion batteries is high. The metal zinc (Zn) has the theoretical capacity as high as 820 mAhg < -1 >, a zinc-manganese secondary battery prepared by adopting a zinc cathode has very high energy density, but the problems of hydrogen evolution and zinc dendrite of the zinc cathode are difficult to solve, the surface of the zinc cathode is coated with a nano porous coating which can inhibit the zinc dendrite to a certain extent, but the discharge performance of the battery is influenced if the coating is too thick, the coating is too thin and is easy to crack, particularly, the anode coating cannot crack under large-scale mass production in the processes of battery assembly and long-time circulation, the coating cannot completely inhibit the hydrogen evolution of the battery, and the hydrogen evolution of the zinc cathode can be aggravated if the coating cracks. Therefore, the development of a technology capable of inhibiting zinc dendrite and inhibiting hydrogen evolution of a zinc negative electrode has important practical value.
The spinel structure of lithium titanate has a three-dimensional ion diffusion channel, has a fast ion diffusion speed and a stable structure, is called as a zero-strain material, and is widely used in lithium ion batteries. The research of the inventor finds that the lithium titanate also has certain proton and zinc ion diffusion and transmission performance, the mixture of the lithium titanate and the strong hydrophobic material also has certain characteristic of inhibiting hydrogen evolution of a zinc cathode, and the research of the inventor finds that other titanates, such as sodium titanate, magnesium titanate, zinc titanate and the like, also have certain performance of inhibiting hydrogen evolution when mixed with the strong hydrophobic material. .
Disclosure of Invention
The development of the zinc ion battery is seriously restricted by the problems of hydrogen evolution of the zinc cathode of the zinc battery and dendrite problems, the inventor combines the characteristic that the hydrogen evolution can be inhibited by mixing titanate and a hydrophobic material, and a great deal of research finds that the hydrogen evolution of the zinc cathode can be effectively inhibited by coating a layer of mixture of titanate and a hydrophobic binder on the surface of the zinc cathode, the hydrogen evolution of the zinc cathode can be effectively inhibited even if the coating is slightly damaged, and meanwhile, the dendrite of the zinc cathode can be inhibited by the coating. The invention provides a zinc battery cathode protected by a hydrophobic layer, a preparation method and a battery, aiming at solving the problems that hydrogen evolution of a zinc cathode and zinc dendrite restrict the development of a zinc ion battery.
The technical scheme of the invention is as follows:
a zinc battery cathode protected by a hydrophobic layer is characterized in that the hydrophobic layer is arranged on the surface of a cathode active material and is a mixture of titanate and a hydrophobic binder, wherein the binder accounts for 6-90% of the mass of the cathode active material.
The titanate is preferably any one or a combination of several of lithium titanate, sodium titanate, magnesium titanate and zinc titanate, the titanate is preferably a powder material with the particle size of less than 20 mu m, and a large number of microporous ion channels can be formed after the micron and nanometer materials with small particle sizes are mixed with a binder, so that zinc dendrite can be inhibited.
According to the zinc battery cathode protected by the hydrophobic layer, the binder is preferably polytetrafluoroethylene, and the mass ratio of the binder is preferably 50-70%.
According to the zinc battery cathode protected by the hydrophobic layer, the thickness of the hydrophobic layer is not more than 300 micrometers, the using amount of a binder can be reduced when a thick hydrophobic layer is adopted, and the using amount of the binder can be increased when the hydrophobic layer is thin.
The negative electrode of the zinc battery protected by the hydrophobic layer is any one of zinc plating or zinc alloy plating, zinc foil or zinc alloy foil, zinc powder or zinc alloy powder of an aluminum foil current collector or a carbon material current collector.
A preparation method of a zinc battery cathode protected by a hydrophobic layer comprises the following steps:
(1) mixing titanate and a binder, stirring uniformly, coating the mixture on the surface of a negative electrode, and drying;
(2) and (3) hot-pressing the cathode coated with the mixture in the step (1) at 200-350 ℃ to obtain the target product.
According to the preparation method of the zinc battery cathode protected by the hydrophobic layer, a hydrophilic porous battery diaphragm can be adhered to the surface of the target product obtained in the step (2) to serve as a reinforcing layer.
A preparation method of a zinc battery cathode protected by a hydrophobic layer comprises the following steps:
(1) mixing titanate and a binder, stirring uniformly, and coating the mixture on a battery diaphragm and drying;
(2) and (3) hot-pressing the diaphragm coated with the mixture in the step (1) on the surface of the zinc cathode, and enabling the mixture layer to be tightly attached to the surface of the zinc cathode to obtain the target product.
A preparation method of a zinc battery cathode protected by a hydrophobic layer comprises the following steps:
(1) mixing titanate and a binder, stirring uniformly, and pressing to form a film;
(2) and (3) pasting the film formed by mixing and pressing the titanate obtained in the step (1) and the binder on the surface of a zinc cathode to obtain the target product.
A zinc battery with a cathode protected by a hydrophobic layer adopts a zinc cathode protected by any hydrophobic layer.
In the zinc battery with the hydrophobic layer-protected negative electrode, the positive electrode of the zinc battery is not limited and can be a conventional choice in the field, for example, the positive electrode of the zinc battery can be at least one of manganese dioxide, vanadium pentoxide, lithium manganate, graphite or carbon materials.
According to the invention, a layer of titanate and hydrophobic binder mixture is arranged on the surface of a zinc battery cathode active substance to form a zinc cathode protective layer, particularly, the titanate and polytetrafluoroethylene mixture protective layer has a stable structure and excellent hydrogen evolution inhibiting performance, the protective layer has certain hydrophobic performance, the zinc cathode adopting the protective layer has very good discharge performance and cycle stability, the zinc cathode battery containing the hydrophobic protective layer circulates for 300 circles, the highest capacity retention rate is 99%, the zinc cathode without the protective layer and the zinc cathode protected by a hydrophilic layer have certain hydrogen evolution, and the capacity of the battery manufactured by the zinc cathode without the protective layer and the zinc cathode protected by the hydrophilic layer can be reduced to below 70% after 50 circles of charge and discharge.
In conclusion, the beneficial effects of the invention are as follows:
the invention provides a zinc battery cathode protected by a hydrophobic layer, a preparation method and a battery.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention will be described in detail below by way of examples.
The cell described in the following example was assembled into a pouch cell and tested, in which the positive electrode was graphite paper-loaded α -manganese dioxide, the electrolyte was 2mol/L zinc sulfate +0.2mol/L manganese sulfate aqueous solution, the negative electrode was a negative electrode sheet made by pressing a metal zinc foil or a mixture of metal zinc powder and a binder, and the separator was a glass fiber separator.
In the preparation method of the zinc battery cathode protected by the hydrophobic layer, the related proportions are mass ratios, wherein the slurry is prepared by using polytetrafluoroethylene emulsion with 60% of solid content, but the blending proportion is calculated according to the mass of the polytetrafluoroethylene solid.
Example 1
Weighing ingredients according to the weight ratio of lithium titanate (800 nm) to polytetrafluoroethylene to water =50:50:130, mixing and stirring the ingredients uniformly, coating a hydrophobic protective layer with the thickness of 20-30 microns on the surface of a zinc foil negative electrode, drying the zinc foil negative electrode at 80 ℃ and forming a film by hot pressing at 320 ℃ to obtain the zinc negative electrode protected by the hydrophobic layer, and carrying out charge-discharge cycle test on the battery assembled by the negative electrode and a manganese dioxide positive electrode.
Example 2
Weighing the ingredients according to the proportion of magnesium titanate (1 mu m), polytetrafluoroethylene and water =30:70:130, mixing and stirring the ingredients uniformly, coating a hydrophobic protective layer of 10 mu m-20 mu m on the surface of a zinc foil cathode, drying the zinc foil cathode at 80 ℃, sticking a porous alumina-doped polypropylene battery diaphragm as a reinforcing layer, hot-pressing the reinforcing layer at 150 ℃ to form a film, namely the zinc cathode protected by the hydrophobic layer, and assembling the battery with a manganese dioxide anode to perform charge-discharge cycle test.
Example 3
Weighing the ingredients according to the ratio of sodium titanate (1 mu m) to polytetrafluoroethylene to water =40:60:130, mixing and stirring the ingredients uniformly, coating the mixture on a porous alumina-doped polypropylene battery diaphragm, wherein the thickness of a hydrophobic protective layer is 10 mu m to 20 mu m, drying the mixture at 60 ℃, attaching one side with the hydrophobic coating on a zinc foil negative electrode, forming a film by hot pressing at 150 ℃ to obtain a zinc negative electrode protected by the hydrophobic layer, and performing charge-discharge cycle test on a battery assembled by the negative electrode and a manganese dioxide positive electrode.
Example 4
Weighing ingredients of lithium titanate (6 mu m), polytetrafluoroethylene and ethanol =50:50:50, mixing and stirring the ingredients uniformly, pressing the mixture into a film with the thickness of 40 mu m, hot-pressing the film at 320 ℃ to form a film, attaching the film to the surface of a zinc foil cathode to obtain a zinc cathode protected by a hydrophobic layer, and assembling the battery by using the cathode and a manganese dioxide cathode to perform charge-discharge cycle test.
Example 5
Weighing ingredients of lithium titanate (20 mu m), polytetrafluoroethylene and water =94:6:130, mixing and stirring the ingredients uniformly, coating a hydrophobic protective layer with the thickness of 300 mu m on the surface of a zinc powder pressing negative electrode, drying the mixture at 80 ℃ and forming a film by hot pressing at 350 ℃ to obtain the zinc negative electrode protected by the hydrophobic layer, and carrying out charge-discharge cycle test on a battery assembled by the negative electrode and a manganese dioxide positive electrode.
Example 6
Weighing ingredients according to the proportion of lithium titanate (5 nm), polytetrafluoroethylene and water =10:90:300, mixing and stirring the ingredients uniformly, coating a 0.1-1 mu m hydrophobic protective layer on the surface of a zinc foil cathode, drying the zinc foil cathode at 80 ℃, hot-pressing the zinc foil cathode at 200 ℃ to form a film, namely the zinc cathode protected by the hydrophobic layer, and performing charge-discharge cycle test on the battery assembled by the cathode and a manganese dioxide cathode.
Comparative example 1
Weighing ingredients according to the proportion of lithium titanate (800 nm), LA136D and water =50:50:130, mixing and stirring the ingredients uniformly, coating a protective layer with the thickness of 20-30 microns on the surface of a zinc foil negative electrode, drying and cold-pressing the protective layer at 80 ℃ to form a film, wherein the protective layer has certain hydrophilicity, and performing charge-discharge cycle test on a battery assembled by the negative electrode and a manganese dioxide positive electrode.
Comparative example 2
And (3) assembling the battery by using the pure metal zinc foil and the manganese dioxide positive electrode to perform charge-discharge cycle test.
| Examples | After circulating for 50 circles | Remarks for note |
| Example 1 | Capacity of 99% without hydrogen evolution | After 300 cycles of circulation, the capacity is kept at 99 percent without hydrogen evolution and gas expansion |
| Example 2 | The capacity is kept 91 percent without hydrogen evolution and flatulence | / |
| Example 3 | Capacity of 88% without hydrogen evolution | / |
| Example 4 | Capacity of 98% without hydrogen evolution | / |
| Example 5 | Capacity of 86% without hydrogen evolution | / |
| Example 6 | Capacity of 92% without hydrogen evolution | / |
| Comparative example 1 | The capacity is kept 68 percent, and the hydrogen evolution and the flatulence are obvious | After 189 cycles of circulation, the battery expands to cause leakage and is scrapped |
| Comparative example 2 | The capacity is kept to be 62 percent, and the hydrogen evolution and the flatulence are obvious | Battery short circuit scrap after 83 circles of circulation |
In the above tests, the batteries prepared by the zinc cathode protected by the hydrophobic layer in the embodiments 1 to 6 have no obvious hydrogen evolution and flatulence after 50 cycles of charge and discharge, the capacity is maintained at 99% at the highest and 86% at the lowest, and the capacity is maintained at 99% after 300 cycles in the example 1, but the battery assembled by the zinc cathode protected by the hydrophilic coating and the metal zinc cathode has obvious bulging due to hydrogen evolution, the capacity is reduced to below 70% after 50 cycles of cycle, and liquid leakage and short circuit scrap due to battery flatulence occur respectively after 200 cycles of cycle.
The embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The zinc battery cathode protected by the hydrophobic layer is characterized in that the hydrophobic layer is arranged on the surface of a cathode active material and is a mixture of titanate and a hydrophobic binder, wherein the binder accounts for 6-90% of the mass of the cathode active material.
2. The hydrophobic layer protected zinc battery negative electrode as claimed in claim 1, wherein the titanate is preferably any one or a combination of several of lithium titanate, sodium titanate, magnesium titanate and zinc titanate, and the titanate is preferably a powder material with a particle size of less than 20 μm.
3. The hydrophobic layer protected zinc battery anode of claim 1, wherein the binder is preferably polytetrafluoroethylene, and the mass ratio of the binder is preferably 50% to 70%.
4. A hydrophobic layer protected zinc battery anode according to claim 1, wherein said hydrophobic layer is no more than 300 μm thick.
5. The hydrophobic layer protected zinc battery negative electrode of claim 1, wherein the negative electrode is any one of zinc or zinc alloy plated, zinc foil or zinc alloy foil, zinc powder or zinc alloy powder plated on an aluminum foil current collector or a carbon material current collector.
6. A preparation method of a zinc battery cathode protected by a hydrophobic layer is characterized by comprising the following steps:
(1) mixing titanate and a binder, stirring uniformly, coating the mixture on the surface of a negative electrode, and drying;
(2) and (3) hot-pressing the cathode coated with the mixture in the step (1) at 200-350 ℃ to obtain the target product.
7. The method for preparing the negative electrode of the zinc battery with the hydrophobic layer protection as claimed in claim 6, wherein a hydrophilic porous battery diaphragm is adhered to the surface of the target product obtained in the step (2) to serve as a reinforcing layer.
8. A preparation method of a zinc battery cathode protected by a hydrophobic layer is characterized by comprising the following steps:
(1) mixing titanate and a binder, stirring uniformly, and coating the mixture on a battery diaphragm and drying;
(2) and (3) hot-pressing the diaphragm coated with the mixture in the step (1) on the surface of the zinc cathode, and enabling the mixture layer to be tightly attached to the surface of the zinc cathode to obtain the target product.
9. A preparation method of a zinc battery cathode protected by a hydrophobic layer is characterized by comprising the following steps:
(1) mixing titanate and a binder, stirring uniformly, and pressing to form a film;
(2) and (3) pasting the film formed by mixing and pressing the titanate obtained in the step (1) and the binder on the surface of a zinc cathode to obtain the target product.
10. A zinc cell with a negative electrode protected by a hydrophobic layer, characterized in that the cell is according to claims 1-5
The battery negative electrode of any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011595304.9A CN114005949A (en) | 2020-12-30 | 2020-12-30 | Zinc battery cathode protected by hydrophobic layer, preparation method and battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064651A (en) * | 2022-05-31 | 2022-09-16 | 福州大学 | Bifunctional protective layer modified zinc cathode and preparation method thereof |
| CN117254029A (en) * | 2023-09-27 | 2023-12-19 | 兰州城市学院 | Method for preparing zinc anode protected by zinc salt of variable-valence metal acid through in-situ growth |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115064651A (en) * | 2022-05-31 | 2022-09-16 | 福州大学 | Bifunctional protective layer modified zinc cathode and preparation method thereof |
| CN115064651B (en) * | 2022-05-31 | 2023-10-27 | 福州大学 | Double-functional protective layer modified zinc anode and preparation method thereof |
| CN117254029A (en) * | 2023-09-27 | 2023-12-19 | 兰州城市学院 | Method for preparing zinc anode protected by zinc salt of variable-valence metal acid through in-situ growth |
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