CN116387518A - Surface mesoporous SiO for protecting zinc cathode 2 Material and preparation method thereof - Google Patents
Surface mesoporous SiO for protecting zinc cathode 2 Material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011701 zinc Substances 0.000 title claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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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
- H01M4/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/02—Electrodes composed of, or comprising, active material
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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
- H01M4/02—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
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
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Abstract
The scheme relates to a surface mesoporous SiO for protecting a zinc cathode 2 The material and the preparation method thereof are that deionized water, ethanol and ammonia water are stirred and mixed, and tetraethyl silicate is added for reaction for 10min; then resorcinol and formaldehyde are added and stirred for reaction for 24 hours; and then centrifuging, washing with ethanol and water, and heating the solid to 400 ℃ and then calcining at 500-800 ℃ in a segmented manner under the air atmosphere to obtain the catalyst. The invention adopts a simple sol-gel and calcination two-step method to prepare the mesoporous SiO with controllable particle size and high specific surface 2 The material has simple preparation process, and does not need complex synthesis operation and special equipment; on SiO by resorcinol-formaldehyde system 2 Nanoparticle surface in situGrowing phenolic (RF) resin and forming a compact coating layer, and removing the RF coating layer in an air calcination stage to form a mesoporous structure; the prepared surface mesoporous SiO 2 The material can be used as a zinc metal negative electrode surface protection material, and the electrochemical performance is obviously improved.
Description
Technical Field
The invention relates to the technical field of secondary battery metal negative electrode surface protection, in particular to a surface mesoporous SiO for protecting a zinc negative electrode 2 A material and a preparation method thereof.
Background
Traditional lead storage battery technology is limited in volume/mass energy density and is not suitable for new energy automobiles. And lithium ion battery technology can provide high energy density; however, the theoretical specific capacity of the traditional intercalation anode material is smaller, and lithium metal can be adopted to further improve the energy density of the battery. However, the high-reactivity lithium metal can have a plurality of side reactions with organic electrolyte, such as gas production by decomposition of battery liquid, dendrite growth and the like, so that the battery is exposed to great safety risks of fire and explosion. On the other hand, the lithium carbonate raw material is expensive, and the cost of the trolley is multiplied, so the development of novel low-cost and safe secondary battery technology is urgent.
The water system secondary zinc battery adopts a water system electrolyte, so that the risk of ignition is avoided; the volume energy density is high, the environment is friendly, the cost is low, and the method is a novel secondary battery technology with great potential. However, similar to metallic lithium, zinc dendrites can also be generated in the electrolyte due to local current density non-uniformity of the zinc metal anode; and the near-neutral electrolyte has stronger water molecular reaction activity, can accelerate the surface corrosion of the zinc cathode, and generates hydrogen evolution side reaction. Therefore, development of a zinc metal anode surface protection material is needed, the cycle life of the zinc metal anode surface protection material is prolonged, and the zinc metal anode surface protection material has important scientific significance and strategic significance.
The oxide material can be used for protecting the surface of a metal negative electrode, can effectively lower the nucleation barrier of lithium and zinc, and induces both lithium and zincAnd (3) uniform deposition is carried out, so that the cycling stability of the metal cathode is improved. Wherein SiO is 2 The zinc anode surface modification material has abundant reserves, low cost and environmental friendliness, and has great potential. But of conventional SiO 2 The nano material is generally in the shape of a complete nano particle on the surface, and the zinc deposition inducing sites of the surface modification material are generally positioned on the surface of the material, so that the surface active sites are limited, and the improvement degree of the circulation performance of the metal negative electrode is limited. Therefore, siO with high specific surface (mesoporous structure) is developed 2 The material is particularly important.
Disclosure of Invention
In view of the deficiencies in the prior art, the present invention aims at providing a process for preparing SiO by simple steps 2 The nano structure is regulated and controlled to form mesoporous material, which can be used as the protecting material of zinc metal cathode.
In order to achieve the above purpose, the present invention provides the following technical solutions:
surface mesoporous SiO for protecting zinc cathode 2 The preparation method of the material comprises the following steps:
1) Mixing deionized water, ethanol and ammonia water under stirring, and adding tetraethyl silicate for reaction for 10min;
2) Adding resorcinol and formaldehyde into the step 1), and stirring for reacting for 24 hours to obtain a mixed solution;
3) Centrifuging the mixed solution, washing with ethanol and water to obtain SiO 2 An @ RF precursor material;
4) SiO is made of 2 Placing the @ RF precursor material into a crucible, and calcining from room temperature to 400 ℃ and then to 500-800 ℃ by sectional temperature rise under the air atmosphere.
Further, in the step 1), the volume ratio of deionized water, ethanol and ammonia water is 10:20:1.
Further, the volume ratio of the tetraethyl silicate to the mixed solution of deionized water, ethanol and ammonia water in the step 1) is 0.03-0.05.
Further, the concentration of resorcinol in the mixed solution in the step 2) is 4-5 g/L, and the volume ratio of formaldehyde to the mixed solution is 0.007-0.009.
Further, the reaction temperature of the step 1) and the step 2) is between 20 ℃ and 45 ℃.
The invention further provides the surface mesoporous SiO for protecting the zinc cathode, which is prepared by the preparation method 2 A material.
The beneficial effects of the invention are as follows: the invention adopts a simple sol-gel and calcination two-step method to prepare the mesoporous SiO with controllable particle size and high specific surface 2 The material has simple preparation process and does not need complex synthesis operation and special equipment. In SiO 2 Preparation of RF precursor Material at the stage of SiO by resorcinol-Formaldehyde System 2 In-situ growing RF resin on the surface of the nano-particles and forming a compact coating layer; during the air calcination stage, the SiO occupied during the RF nucleation growth stage is exposed by the removal of the RF cladding layer 2 The surface defect positions form a mesoporous structure. Transmission Electron Microscope (TEM) tests show that the SiO is calcined in air at 500-800 DEG C 2 Successfully preparing surface mesoporous SiO by the @ RF precursor material 2 The material, nitrogen adsorption-desorption test further shows that the surface mesopores exist, and the material can be used as a zinc metal anode surface protection material, so that the electrochemical performance is obviously improved.
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 graph of mesoporous SiO produced at different air calcination temperatures 2 TEM image of material.
FIG. 2 is mesoporous SiO 2 Materials and plain SiO 2 The nitrogen adsorption-desorption test curve of the material is shown as a graph with specific surface area (a) and pore size distribution (b).
FIG. 3 is mesoporous SiO 2 Zinc deposition first pass potential curve (a) versus coulombic efficiency (b) for both the modified and pure copper foils.
FIG. 4 is mesoporous SiO 2 Cycling stability performance profiles for the protection zinc foil and the pure zinc foil.
FIG. 5 is mesoporous SiO 2 And (3) modifying the early-stage cycle stability performance diagram of the zinc metal anode.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Examples
13mL of deionized water and 26mL of ethanol were added to a beaker, 1.3mL of ammonia water (28 wt%) was added, and the mixture was stirred at room temperature for 30min to be thoroughly mixed, and then 1.4mL of tetraethyl silicate (TEOS) was added to react for 10min, 0.2g of resorcinol and 0.3mL of formaldehyde (37 wt%) were added, and the mixture was stirred at room temperature for 24h. Centrifuging and washing to obtain SiO 2 Placing the @ RF precursor material in a crucible, heating to 400 ℃ and then 500 ℃ (or 600 ℃, 700 ℃ and 800 ℃) in a tube furnace under air atmosphere, and calcining for 2 hours to obtain mesoporous SiO at different calcining temperatures 2 A material.
Comparative example:
13mL of deionized water and 26mL of ethanol were added to the beaker, 1.3mL of ammonia water (28 wt%) was added, and the mixture was stirred at room temperature for 30min and thoroughly mixed, and 1.4mL of tetraethyl silicate was added to react for 10min, and the mixture was stirred at room temperature for 12h. Centrifuging and washing to obtain solid material, placing the solid material in a crucible, heating to 400 ℃ in a tube furnace under air atmosphere, heating to 600 ℃ and calcining for 2h to obtain common SiO 2 A material.
As shown in figure 1, mesoporous SiO is prepared by corresponding to different air calcination temperatures 2 TEM image of material, mesoporous SiO prepared 2 The material is in a monodispersed sphere shape, has uniform particle size (100 nm), has rough surface and rich pore structure. Without any provision forOrdinary SiO for RF sacrificial layer preparation 2 The material is in a monodispersed sphere shape and similar in particle size, but has complete surface and no obvious pore structure characteristics.
As shown in FIG. 2, the nitrogen adsorption-desorption test showed that the method was similar to that of ordinary SiO 2 Compared with the material, the mesoporous SiO prepared in the scheme 2 The material (both are 600 ℃ calcined samples) has larger specific surface area and more uniform surface mesoporous pore size distribution (-5 nm).
Application and effect verification:
the prepared mesoporous SiO 2 The material (calcined at 600 ℃), ketjen black, carbon nano tube and battery grade polyvinylidene fluoride powder are uniformly mixed according to the mass ratio of 7:1:1:1, ground uniformly, then dispersed into methyl pyrrolidone solvent, and stirred to prepare active material slurry. And then respectively coating the electrode on the surfaces of commercial copper foil and zinc foil, and drying in vacuum to obtain the working electrode (the electrode plate with the diameter of 12mm is manufactured). Then assembling the Cu-Zn button half cell and the Zn-Zn symmetrical cell, wherein the electrolyte is 1mol/L ZnSO 4 The aqueous solution and the glass fiber are diaphragms. The charge and discharge test of the battery was performed on a blue battery test system.
As shown in FIG. 3, mesoporous SiO is compared with pure copper foil 2 The copper foil modified by the material can effectively reduce the zinc deposition potential barrier, and improve the cycle stability and cycle life of the battery.
As shown in fig. 4 and 5, mesoporous SiO compared to pure zinc metal anode 2 The zinc cathode modified by the material can effectively reduce potential polarization in circulation, and improves circulation stability and battery life.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (6)
1. Surface mesoporous SiO for protecting zinc cathode 2 Method for producing a material, whichIs characterized by comprising the following steps:
1) Mixing deionized water, ethanol and ammonia water under stirring, and adding tetraethyl silicate for reaction for 10min;
2) Adding resorcinol and formaldehyde into the step 1), and stirring for reacting for 24 hours to obtain a mixed solution;
3) Centrifuging the mixed solution, washing with ethanol and water to obtain SiO 2 An @ RF precursor material;
4) SiO is made of 2 Placing the @ RF precursor material into a crucible, and calcining from room temperature to 400 ℃ and then to 500-800 ℃ by sectional temperature rise under the air atmosphere.
2. The surface mesoporous SiO for protecting zinc anode according to claim 1 2 The preparation method of the material is characterized in that the volume ratio of deionized water, ethanol and ammonia water in the step 1) is 10:20:1.
3. The surface mesoporous SiO for protecting zinc anode according to claim 1 2 The preparation method of the material is characterized in that the volume ratio of the tetraethyl silicate to the mixed solution of deionized water, ethanol and ammonia water in the step 1) is 0.03-0.05.
4. The surface mesoporous SiO for protecting zinc anode according to claim 1 2 The preparation method of the material is characterized in that the concentration of resorcinol in the mixed solution in the step 2) is 4-5 g/L, and the volume ratio of formaldehyde to the mixed solution is 0.007-0.009.
5. The surface mesoporous SiO for protecting zinc anode according to claim 1 2 The preparation method of the material is characterized in that the reaction temperature of the step 1) and the step 2) is between 20 ℃ and 45 ℃.
6. The surface mesoporous SiO of a zinc anode for protection prepared by the preparation method according to any one of claims 1 to 5 2 A material.
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| CN111463481A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Composite quasi-solid electrolyte, preparation method and full battery |
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| CN101325255A (en) * | 2007-06-15 | 2008-12-17 | 比亚迪股份有限公司 | Zinc cathode, preparation method thereof and zinc secondary battery using zinc cathode |
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