CN116666636A - Zinc ion battery negative electrode plate protective coating and preparation method and application thereof - Google Patents
Zinc ion battery negative electrode plate protective coating and preparation method and application thereof Download PDFInfo
- Publication number
- CN116666636A CN116666636A CN202310784076.7A CN202310784076A CN116666636A CN 116666636 A CN116666636 A CN 116666636A CN 202310784076 A CN202310784076 A CN 202310784076A CN 116666636 A CN116666636 A CN 116666636A
- Authority
- CN
- China
- Prior art keywords
- zinc
- ion battery
- negative electrode
- bentonite
- protective coating
- 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.)
- Pending
Links
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000011253 protective coating Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 56
- 239000011701 zinc Substances 0.000 claims abstract description 56
- -1 zinc modified bentonite Chemical class 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 29
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 24
- 229910000278 bentonite Inorganic materials 0.000 claims description 21
- 229940092782 bentonite Drugs 0.000 claims description 21
- 239000000440 bentonite Substances 0.000 claims description 21
- 150000003751 zinc Chemical class 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical group O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 5
- 229940080314 sodium bentonite Drugs 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000281 calcium bentonite Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 25
- 210000001787 dendrite Anatomy 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QNDQILQPPKQROV-UHFFFAOYSA-N dizinc Chemical compound [Zn]=[Zn] QNDQILQPPKQROV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 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
- H01M4/62—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of preparation of coatings for negative electrode plates of zinc ion secondary batteries, and particularly relates to a protective coating for a negative electrode plate of a zinc ion secondary battery, and a preparation method and application thereof. When the zinc modified bentonite is applied to the zinc ion battery, side reactions such as dendrite growth, hydrogen evolution corrosion and the like can be inhibited, the cycle performance and coulomb efficiency of the negative electrode of the zinc ion battery are obviously improved, and the zinc modified bentonite can be widely applied to a zinc ion battery system based on aqueous electrolyte.
Description
Technical Field
The invention belongs to the technical field of preparation of coatings for negative electrode plates of zinc ion secondary batteries, and particularly relates to a protective coating for a negative electrode plate of a zinc ion secondary battery, and a preparation method and application thereof.
Background
The increasing energy demand and serious environmental pollution problems have forced us to drive the transition from fossil fuels to renewable energy sources, which are rapidly increasing in demand. The installed capacity of renewable energy power generation based on solar energy, wind energy and the like is dramatically increased, and development of efficient, inexpensive, clean and safe energy storage technology is required.
The water-based zinc ion battery has the characteristics of good safety, high cost advantage, environmental friendliness and the like, and is particularly valued. The zinc ion battery adopts a zinc negative electrode with good stability in aqueous solution as a battery negative electrode, and metal zinc is an ideal negative electrode material of the water-based battery. In aqueous zinc ion batteries, on the one hand, the zinc negative side can lead to dendrite growth due to uneven zinc dissolution deposition; on the other hand, side reactions such as hydrogen evolution corrosion between metallic zinc and water limit the stability and life of the battery.
The current inhibition method for dendrite growth and side reaction of the metallic zinc cathode mainly starts from aspects of organic/water hybridization electrolyte, electrolyte additive, coating modification and the like. Compared with other methods, the negative electrode coating has the advantages of low cost, simple process, safety, green color and the like, and is most widely used. However, the negative electrode coating protection still has problems to be improved, for example, how to further suppress dendrite growth and side reactions of metallic zinc negative electrodes, etc.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems that dendrite growth is easy to occur on the negative electrode plate of the zinc ion battery in the prior art, and how to improve the cycle stability and the service life of the battery, and the like, thereby providing a protective coating for the negative electrode plate of the zinc ion battery, and a preparation method and application thereof.
For this purpose, the invention provides the following technical scheme.
The invention provides application of zinc modified bentonite in a zinc ion battery.
The invention provides a zinc ion battery negative electrode protective coating, which comprises raw materials of zinc modified bentonite and a binder.
The mass ratio of the zinc modified bentonite to the binder is (4-9): 1.
The raw materials of the zinc modified bentonite comprise zinc salt and bentonite.
The zinc salt is at least one of zinc sulfate, zinc chloride, zinc triflate, zinc chloride and zinc acetate;
preferably, the mass ratio of the zinc salt solution to the bentonite is (20-30): 1;
preferably, the mass fraction of zinc salt in the zinc salt solution is 20-40%;
preferably, the binder is polyvinylidene fluoride and/or polytetrafluoroethylene;
preferably, the bentonite is sodium bentonite and/or calcium bentonite.
In addition, the invention also provides a preparation method of the zinc ion battery anode protective coating, which comprises the following steps:
(1) Dispersing bentonite in zinc salt solution, and drying to obtain zinc modified bentonite;
(2) Mixing the zinc modified bentonite and a binder, and ball milling to obtain slurry;
(3) The slurry was coated on a current collector and dried.
The specific steps of the step (1) comprise: dispersing bentonite in zinc salt solution, stirring for 8-12h at 80-100 ℃, and standing for 2-4h to obtain a reaction product; washing, centrifuging and drying to obtain zinc modified bentonite;
preferably, in the step (2), the zinc-modified bentonite and the binder are mixed in a solvent;
preferably, the solvent is at least one of N-methylpyrrolidone, water and ethanol;
preferably, the rotation speed of the ball milling is 280-350rpm/min, and the time is 2-6h.
The current collector is zinc foil;
preferably, the thickness of the zinc ion battery anode protective coating is 10-100 μm.
The invention provides a zinc ion battery negative electrode plate, which comprises the protective coating for the zinc ion battery negative electrode plate or the zinc ion battery negative electrode protective coating prepared by the preparation method.
The invention further provides a zinc ion battery, which comprises the zinc ion battery negative electrode plate.
The technical scheme of the invention has the following advantages:
1. the application of the zinc modified bentonite in the zinc ion battery provided by the invention can inhibit side reactions such as dendrite growth and hydrogen evolution corrosion when the zinc modified bentonite is applied to the zinc ion battery, so that the cycle performance and coulomb efficiency of the negative electrode of the zinc ion battery are obviously improved, and the zinc modified bentonite can be widely applied to a zinc ion battery system based on aqueous electrolyte.
2. The raw materials of the zinc ion battery negative electrode plate protective coating provided by the invention comprise zinc modified bentonite and a binder, and when the coating is used for a zinc ion battery negative electrode, side reactions such as dendrite growth, hydrogen evolution corrosion and the like can be inhibited, so that the cycle performance of the zinc ion battery negative electrode and the stripping and depositing coulomb efficiency can be obviously improved, the growth condition of zinc ion battery negative electrode dendrite can be improved, the cycle performance of the zinc ion battery can be improved, and the effect of protecting the zinc negative electrode can be achieved. The zinc ion battery negative electrode protective coating provided by the invention can be widely applied to a zinc ion battery system based on aqueous electrolyte.
The zinc ion battery in the prior art mostly has the reasons that zinc ion concentration is uneven and can be deposited in certain areas preferentially, so that loose porous dendrites appear.
When the protective coating of the zinc ion battery negative electrode plate provided by the invention is used as a battery negative electrode, the coating can reduce the contact between the zinc negative electrode and water molecules, and can more effectively block the gassing reaction between the zinc negative electrode and water and the self-corrosion phenomenon of the zinc negative electrode. In addition, the coating can solve the problem of micro short circuit in the battery caused by zinc dendrite, is favorable for inhibiting the growth of dendrite in the zinc ion battery and improves the cycle life of the zinc cathode.
Furthermore, the protective coating of the invention adopts cheap and natural bentonite which is easy to obtain as a raw material, is a natural nonmetallic mineral product, has rich sources, low cost and simple subsequent preparation.
3. The zinc ion battery negative electrode plate protective coating provided by the invention has good chemical stability and excellent mechanical strength, has excellent stability in a water-based electrolyte, and also has certain hydrophobicity, and the zinc ion battery negative electrode plate protective coating can be used as a binder to uniformly and stably coat zinc modified bentonite on the surface of a zinc negative electrode, so that the contact between the zinc negative electrode and water molecules is reduced, and the gassing reaction between the zinc negative electrode and water and the self-corrosion phenomenon of the zinc negative electrode are effectively blocked.
4. According to the preparation method of the zinc ion battery negative electrode plate protective coating, provided by the invention, the interlayer ions of bentonite are mainly sodium ions and potassium ions, the interlayer ions can be replaced by zinc ions by dispersing bentonite in zinc salt solution, when the electrode plate forms the coating, the transmission rate of the zinc ions can be improved, the ion transmission impedance and the polarization of the battery are reduced, and meanwhile, after the bentonite is doped with the zinc ions, the coating has better zinc ion transmission capacity.
The preparation method provided by the invention has the advantages of simple process, low raw material cost and easiness in industrialization.
Further, the invention can promote the substitution speed of zinc ions by doping zinc ions in bentonite at 80-100 ℃.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a test result of a comparative experiment provided in test example 1 of the present invention;
fig. 2 is a test result of a battery with assembled negative electrode provided in example 1 of the present invention;
fig. 3 is a test result of a battery after the negative electrode assembly provided in example 2 of the present invention.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The following example provides a protective coating for a negative electrode plate of a zinc ion battery, which comprises raw materials of zinc modified bentonite and a binder, wherein the mass ratio of the zinc modified bentonite to the binder is (4-9): 1.
The preparation method of the zinc ion battery negative electrode plate protective coating is also provided, and comprises the following steps:
(1) Dispersing bentonite in zinc salt solution, stirring for 8-12h at 80-100 ℃, and then standing for 2-4h to obtain a reaction product; washing, centrifuging and drying the reaction product to obtain granular zinc modified bentonite;
(2) Dispersing zinc modified bentonite and a binder in a solvent, and ball milling to obtain slurry;
(3) And coating the slurry on a current collector, and drying to obtain the zinc ion battery anode protective coating.
The current collector is a zinc cathode of the battery, and the formed coating can play a role in protecting the zinc cathode.
When the slurry is applied to the current collector, the slurry may be applied by a doctor blade or may be applied by a spin coater.
The thickness of the coating layer is 10 to 100. Mu.m, specifically, any one of 10. Mu.m, 20. Mu.m, 30. Mu.m, 40. Mu.m, 50. Mu.m, 60. Mu.m, 70. Mu.m, 80. Mu.m, 90. Mu.m, 100. Mu.m.
The negative electrode plate of the zinc ion battery comprises the protective coating.
The zinc ion battery comprises the negative electrode plate.
Example 1
The embodiment provides a zinc ion battery negative electrode plate protective coating, which comprises the following raw materials of zinc modified bentonite and PVDF in a mass ratio of 4:1.
The embodiment also provides a preparation method of the zinc ion battery negative electrode plate protective coating, which comprises the following steps:
(1) Dispersing 20g of sodium bentonite in 600g of 30wt% zinc sulfate solution, stirring for 12 hours at 85 ℃, and standing for 3 hours to obtain a reactant; washing the reactant by deionized water for several times until zinc salt on the surface of bentonite is washed out, centrifuging, drying for 24 hours in a vacuum oven at 80 ℃, taking out, grinding and sieving for standby, and obtaining the zinc modified bentonite.
(2) Mixing 0.8g of zinc modified bentonite with 2g of 10wt% PVDF solution, rotating at 300rpm/min in a ball mill, ball milling for 3 hours, and uniformly mixing to obtain slurry; wherein the solvent in the PVDF solution is NMP.
(3) And uniformly coating the slurry on the surface of clean zinc foil by using a scraper to form a composite coating, and then placing the composite coating in a drying oven for drying for 12 hours, wherein the thickness of the coating is 10 mu m.
The embodiment also provides a zinc ion battery negative electrode plate, which comprises the protective coating.
Example 2
The embodiment provides a zinc ion battery negative electrode plate protective coating, which comprises the following raw materials of zinc modified bentonite and PVDF in a mass ratio of 4:1.
The embodiment also provides a preparation method of the zinc ion battery negative electrode plate protective coating, which comprises the following steps:
(1) Dispersing 20g of sodium bentonite in 600g of 30wt% zinc sulfate solution, stirring for 12 hours at 85 ℃, and standing for 3 hours to obtain a reaction solution; washing the reaction solution with deionized water for several times until zinc salt on the surface of bentonite is washed away, centrifuging, drying in a vacuum oven at 80 ℃ for 24 hours, taking out, grinding and sieving for standby use, and obtaining the zinc modified bentonite.
(2) Mixing 0.8g of zinc modified bentonite with 2g of 10wt% PVDF solution, rotating at 300rpm/min in a ball mill, ball milling for 3 hours, and uniformly mixing to obtain slurry; wherein the solvent in the PVDF solution is NMP.
(3) And uniformly coating the slurry on the surface of the clean zinc foil by using a spin coater to form a composite coating, and then placing the composite coating in a drying oven for drying for 12 hours, wherein the thickness of the coating is 10 mu m. Wherein the rotation speed of the spin coater is 2000rpm, and the spin coating time is 60s.
The embodiment also provides a zinc ion battery negative electrode plate, which comprises the protective coating.
Example 3
The embodiment provides a zinc ion battery negative electrode plate protective coating, which comprises the following raw materials of zinc modified bentonite and PVDF in a mass ratio of 9:1.
The embodiment also provides a preparation method of the zinc ion battery negative electrode plate protective coating, which comprises the following steps:
(1) Dispersing 20g of sodium bentonite in 600g of 30wt% zinc sulfate solution, stirring for 10 hours at 95 ℃, and standing for 2.5 hours to obtain a reaction solution; washing the reaction solution with deionized water for several times until zinc salt on the surface of bentonite is washed away, centrifuging, drying in a vacuum oven at 85 ℃ for 24 hours, taking out, grinding and sieving for standby use, and obtaining the zinc modified bentonite.
(2) Mixing 0.9g of zinc modified bentonite with 1g of 10wt% PVDF solution, and uniformly mixing in a ball mill with the rotation speed of 300rpm for 3 hours to obtain slurry; wherein the solvent in the PVDF solution is NMP.
(3) And uniformly coating the slurry on the surface of the clean zinc foil by using a scraper to form a composite coating, and drying the composite coating in a drying oven for 12 hours, wherein the thickness of the coating is 10 mu m.
The embodiment also provides a zinc ion battery negative electrode plate, which comprises the protective coating.
Test examples
The negative electrode tabs obtained in examples 1-2 were assembled into batteries, and the battery performance was tested as follows:
and (3) battery assembly: and (3) assembling a zinc-zinc symmetrical battery, wherein a diaphragm is AGM, an electrolyte comprises water and zinc sulfate, the concentration of the zinc sulfate in the electrolyte is 2.0mol/L, and the negative electrode plate provided in the embodiment 1-2 is cut into a wafer with the diameter of 14 mm. The zinc sheet without any treatment was used as a comparative experiment.
And (3) battery testing: at 25 ℃,1 mAh.cm -2 For operation at a specific surface area of (2), the battery generally uses a test method with a specific surface area, i.e., 1mAh cm -2 Charging for 1h and discharging for 1h. Comparing the experimental test results with the graph of fig. 1, it can be seen that after the unprotected zinc cathode is cycled for 180 hours, the symmetrical battery is short-circuited due to the penetration of dendrite growth through the separator; examples 1-2 the test results are shown in fig. 2-3, and example 1 shows that the zinc anode coated with the bentonite protective layer has no short circuit after 1000 hours of cycling at the same current density and capacity; the bentonite protective layer prepared by spin coating in the embodiment 2 has a certain protective effect on the zinc cathode, and short circuit does not occur after 600 hours of circulation, so that the circulation stability of the battery is greatly improved.
In conclusion, when the zinc ion battery negative electrode plate protective coating is used for the negative electrode plate, the coating can be favorable for inhibiting dendrite growth in the zinc ion battery, reducing battery short circuit and prolonging the cycle life of the zinc negative electrode.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The application of the zinc modified bentonite in zinc ion batteries.
2. The negative electrode protective coating of the zinc ion battery is characterized by comprising raw materials of zinc modified bentonite and a binder.
3. The zinc-ion battery anode protective coating according to claim 2, wherein the mass ratio of the zinc-modified bentonite to the binder is (4-9): 1.
4. A zinc ion battery anode protective coating according to claim 2 or 3, wherein the raw materials of the zinc modified bentonite include zinc salt and bentonite.
5. The zinc-ion battery negative electrode protective coating of claim 4, wherein the zinc salt is at least one of zinc sulfate, zinc chloride, zinc triflate, zinc chloride, and zinc acetate;
preferably, the mass ratio of the zinc salt solution to the bentonite is (20-30): 1;
preferably, the mass fraction of zinc salt in the zinc salt solution is 20-40%;
preferably, the binder is polyvinylidene fluoride and/or polytetrafluoroethylene;
preferably, the bentonite is sodium bentonite and/or calcium bentonite.
6. The preparation method of the zinc ion battery negative electrode protective coating is characterized by comprising the following steps of:
(1) Dispersing bentonite in zinc salt solution, and drying to obtain zinc modified bentonite;
(2) Mixing the zinc modified bentonite and a binder, and ball milling to obtain slurry;
(3) The slurry was coated on a current collector and dried.
7. The method according to claim 6, wherein the specific steps of step (1) include: dispersing bentonite in zinc salt solution, stirring for 8-12h at 80-100 ℃, and standing for 2-4h to obtain a reaction product; washing, centrifuging and drying to obtain zinc modified bentonite;
preferably, in the step (2), the zinc-modified bentonite and the binder are mixed in a solvent;
preferably, the solvent is at least one of N-methylpyrrolidone, water and ethanol;
preferably, the rotation speed of the ball milling is 280-350rpm/min, and the time is 2-6h.
8. The method of manufacturing according to claim 6 or 7, wherein the current collector is zinc foil;
preferably, the thickness of the zinc ion battery anode protective coating is 10-100 μm.
9. A negative electrode sheet of a zinc ion battery, comprising the protective coating for a negative electrode sheet of a zinc ion battery according to any one of claims 2 to 6 or the protective coating for a negative electrode of a zinc ion battery produced by the production method according to any one of claims 7 to 8.
10. A zinc ion battery comprising the zinc ion battery negative electrode tab of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310784076.7A CN116666636A (en) | 2023-06-28 | 2023-06-28 | Zinc ion battery negative electrode plate protective coating and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310784076.7A CN116666636A (en) | 2023-06-28 | 2023-06-28 | Zinc ion battery negative electrode plate protective coating and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116666636A true CN116666636A (en) | 2023-08-29 |
Family
ID=87717173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310784076.7A Pending CN116666636A (en) | 2023-06-28 | 2023-06-28 | Zinc ion battery negative electrode plate protective coating and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116666636A (en) |
-
2023
- 2023-06-28 CN CN202310784076.7A patent/CN116666636A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113054165B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN110504423B (en) | Preparation method of polydopamine ion electron conductive network coated lithium ion battery positive electrode material | |
| CN111792633A (en) | Method for directly recycling lithium iron phosphate in waste lithium iron phosphate battery | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN113258070A (en) | Metal zinc cathode interface modification method for water-based zinc ion battery | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN114883748B (en) | Composite diaphragm for lithium ion battery and preparation method thereof | |
| CN114284567A (en) | Preparation method of high-energy-density cathode-free lithium metal battery | |
| CN112018387A (en) | Preparation method of preformed film negative electrode material and lithium ion battery | |
| CN112736245A (en) | Lithium ion battery cathode material and preparation method and application thereof | |
| CN110190258B (en) | Silicon-carbon composite material water-based composite slurry, preparation method thereof and lithium ion battery | |
| CN114551883A (en) | Aqueous zinc ion battery coating, cathode and battery | |
| CN112615057B (en) | Preparation method of solid-state lithium ion battery and solid-state lithium ion battery | |
| CN109273670A (en) | A kind of lithium anode and preparation method thereof with high-specific-surface mesoporous protective film | |
| CN116613298A (en) | Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN115064651B (en) | Double-functional protective layer modified zinc anode and preparation method thereof | |
| CN110911662A (en) | Lithium cathode with protective layer and preparation method and application thereof | |
| CN113782744B (en) | Method for improving negative performance of high-specific-energy-density silicon monoxide by using lithium ion modified binder | |
| CN113991086B (en) | Zinc ion battery negative electrode composite material and preparation method and application thereof | |
| CN112234175B (en) | Preparation method of high-reversible aqueous zinc ion battery negative electrode material | |
| CN116666636A (en) | Zinc ion battery negative electrode plate protective coating and preparation method and application thereof | |
| CN114142032A (en) | Zinc ion battery and method for improving zinc negative electrode cycle performance of zinc ion battery | |
| CN115172774A (en) | Cyano group modified Zr-Fe MOF, preparation method thereof and zinc negative electrode material of zinc-based flow battery | |
| CN116487584A (en) | Positive electrode composite material, preparation method thereof, positive electrode and lithium ion secondary battery | |
| CN112038699A (en) | Method for improving stability of electrolyte of lithium iron phosphate battery and manufacturing method of battery |
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 |