CN117613508A - Preparation method and application of BETA molecular sieve membrane based on ruthenium-loaded nanocluster - Google Patents
Preparation method and application of BETA molecular sieve membrane based on ruthenium-loaded nanocluster Download PDFInfo
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- CN117613508A CN117613508A CN202311624491.2A CN202311624491A CN117613508A CN 117613508 A CN117613508 A CN 117613508A CN 202311624491 A CN202311624491 A CN 202311624491A CN 117613508 A CN117613508 A CN 117613508A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 57
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000012528 membrane Substances 0.000 title claims abstract description 35
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000002033 PVDF binder Substances 0.000 claims abstract description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 230000008021 deposition Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 3
- 238000005520 cutting process Methods 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 6
- 150000003303 ruthenium Chemical class 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000003071 parasitic effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a BETA molecular sieve membrane based on ruthenium-loaded nanoclusters, which comprises the following steps: s1, calcining a commercial BETA molecular sieve in a muffle furnace; s2, impregnating the calcined BETA molecular sieve with RuCl 3 The solution is stirred vigorously to obtain a BETA molecular sieve loaded with ruthenium nanoclusters; s3, uniformly mixing the obtained BETA molecular sieve loaded with ruthenium nanoclusters with PVDF, adding NMP solution, grinding for 30min, and usingPressing the ground slurry into a membrane by a tablet press, finally cutting the molecular sieve membrane into a membrane sheet, and soaking in 1 mol ZnSO 4 Obtaining a BETA molecular sieve membrane loaded with ruthenium nanoclusters after 3 days in the solution; the invention provides a method for preparing a water-based zinc metal battery diaphragm by using a BETA molecular sieve loaded ruthenium nanocluster to regulate zinc deposition behavior for the first time, and improves the solid-liquid interface stability of the zinc battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method and application of a BETA molecular sieve membrane based on ruthenium-loaded nanoclusters.
Background
Rechargeable battery technology is considered an excellent candidate for renewable energy storage due to its low geographic requirements, high flexibility, scalable manufacturing, and ease of installation. The explosive demand for energy storage applications has accelerated the development of cost effective and high energy/power density rechargeable batteries. Currently, the most advanced lithium ion batteries based on intercalation theory almost reach their theoretical energy density. Furthermore, inflammable organic electrolytes lead to a high risk of safety accidents in lithium batteries due to thermal runaway caused by the reactivity of the electrode material with the electrolyte. The zinc battery compatible with water becomes a good substitute, and zinc resources are rich, so that the zinc battery has great attraction. In addition, the aqueous zinc battery has low toxicity and high theoretical capacity (820 mAh g -1 Or 5855mAh cm -3 ) And the advantages of high ion conductivity and the like, and lead to extensive researches. However, many challenges have hindered the practical use of aqueous zinc cells. Major problems include corrosion, dendrite growth, and parasitic side reactions faced by zinc metal anodes. Most of the current research is mainly focused on three aspects: and constructing an artificial interface layer by an in-situ or ex-situ method, modifying the electrolyte, and optimizing the zinc cathode. However, artificial interfacial layers often require cumbersome processes, resulting in increased costs in commercial applications; electrolyte additives are often accompanied by uncontrolled chemical and electrochemical processes, which in turn trigger undesirable parasitic side reactions; the preparation process for improving the zinc cathode is complex, has high cost and is not easy to expand in large scale. The diaphragm is used as an indispensable component in a battery system, diaphragm modification is also an important means for regulating zinc deposition behavior and improving the stability of a solid-liquid interface of a zinc battery, but the diaphragm of the zinc battery is notable in that little research is performed at present. The diaphragm is positioned between the anode and the cathode, is the only way for ion diffusion, and plays an important role in the mass transfer process at the interface of the anode and the cathode. In fact, glass Fiber (GF) has many drawbacks as the most widely used separator material for aqueous zinc ion batteries, such as: filling with sufficient electrolyte is required, resulting in many SOs 4 2- And H + Reaching the zinc cathodeSurface and parasitic side reactions are initiated, the pore structure is uneven, the mechanical strength is lower, and zinc dendrites are continuously developed and penetrate through the membrane. Thus, separator modification is of great importance to achieve stable zinc cell operation.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides a preparation material using a BETA molecular sieve carrier loaded ruthenium cluster as a diaphragm and an application thereof in a water-based zinc metal battery system.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a preparation method of BETA molecular sieve membrane based on ruthenium-loaded nanocluster comprises the following steps:
s1, calcining a commercial BETA molecular sieve in a muffle furnace, heating from room temperature to 350 ℃ at 1 ℃/min, preserving heat for 2 hours, heating from 350 ℃ to 550 ℃ at 2 ℃/min, preserving heat for 4 hours, and naturally cooling;
s2, impregnating the calcined BETA molecular sieve with RuCl 3 The solution was then vigorously stirred to allow RuCl 3 Absorbing the solution into BETA molecular sieve, drying the obtained solid in oven at 80deg.C overnight, and then adding H 2 Heating to 400 deg.C under atmosphere, continuously reducing for 2 hr, and maintaining the temperature for 2 hr to obtain BETA molecular sieve loaded with ruthenium nanoclusters;
s3, uniformly mixing the obtained BETA molecular sieve loaded with ruthenium nanoclusters with PVDF according to the mass ratio of 9:1, adding NMP solution, grinding for 30min, wherein the mass ratio of PVDF to NMP solution is 1:4, pressing the ground slurry into a membrane with the thickness of 300 mu m by using a tablet press, and placing the membrane in a vacuum oven to be dried for 12h at 80 ℃; finally, the molecular sieve membrane is cut into membrane sheets and soaked in 1 mol ZnSO 4 And (3) standing in the solution for 3 days to obtain the BETA molecular sieve membrane loaded with ruthenium nanoclusters.
The BETA molecular sieve membrane based on the ruthenium-loaded nanocluster can be applied to a water-based zinc metal battery.
The principle and the beneficial effects of the invention are as follows: firstly, BETA molecular sieve has 0.56-0.7nm microporous nano-pore, and can remove part of water molecules by size effect to form concentrated solutionThe agent structure can effectively inhibit side reactions related to water, thereby limiting Zn 2+ And the transmission of water molecules in the ionic solvent structure is favorable for inhibiting the corrosion of the water molecules to the zinc cathode. Second, there are a large number of Si-O and Al-O bonds in the molecular sieve, where O atoms can form hydrogen bonds with water molecules, so that free water is reduced and zinc metal anode corrosion is reduced. In addition, the ordered channels of the BETA molecular sieve can guide zinc ions to be uniformly distributed and transported, which is beneficial to inhibiting dendrite. Finally, the ruthenium sites with delocalized electron structures in the ruthenium clusters have stronger adsorption capacity to-OH, the original hydrogen bond network is destroyed, and H is influenced by + 、OH - And the mass transfer rate of the anode can effectively inhibit anode corrosion. The invention provides a method for preparing a water-based zinc metal battery diaphragm by using a BETA molecular sieve loaded ruthenium nanocluster to regulate zinc deposition behavior for the first time, and improves the solid-liquid interface stability of the zinc battery. The invention brings new revelation for the design of the high-efficiency water system zinc battery diaphragm.
Drawings
FIG. 1 is a commercial BETA molecular sieve scanning electron microscope picture.
FIG. 2 is a TEM image of BETA molecular sieve loaded with 1wt% ruthenium nanoclusters.
FIG. 3 is a graph comparing the cycling performance of zinc symmetric cells using glass fiber membrane (GF) and BETA molecular sieve membrane loaded with ruthenium nanoclusters at a 1mA rate and a 1mAh capacity.
FIG. 4 is a graph of CA contrast curves for BETA molecular sieve membranes using glass fiber membranes (GF) and using different amounts of ruthenium cluster loading.
Figure 5 is an XRD pattern for a symmetrical cell using a glass fiber membrane (GF) and a 1wt% ruthenium cluster loaded BETA molecular sieve membrane after various cycles.
Fig. 6 is a CV curve for zinc symmetric cells using glass fiber separators (GF) and BETA molecular sieve separators loaded with different amounts of ruthenium clusters.
Fig. 7 is a graph of corrosion current measurements for Zn Ti cells using glass fiber separator (GF) and using BETA molecular sieve separator.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments should not be construed as limiting the present invention.
The embodiment is based on heterojunction ZnSe/CoSe of positive and negative electrode protection of lithium-sulfur full battery 2 The preparation method of the universal carrier comprises the following specific steps:
synthesis of Ru/BETA molecular sieves: calcining BETA molecular sieve (commercial) in muffle furnace (specifically, heating to 350deg.C from room temperature at 1deg.C/min, maintaining for 2 hr, heating to 550deg.C from 350deg.C at 2deg.C/min, maintaining for 4 hr, and naturally cooling) before synthesis, and soaking the calcined BETA molecular sieve in RuCl 3 The solution was then vigorously stirred to allow RuCl 3 Absorbing the solution into BETA molecular sieve (the weight ratio of three ruthenium clusters in the BETA molecular sieve is 0wt%, 0.5wt%, 1wt%, respectively denoted as B0, B0.5, and B1) to obtain solid, drying overnight in oven at 80deg.C, and H 2 The atmosphere is heated to 400 ℃, continuously reduced for 2 hours and kept for 2 hours.
Preparation of a water-based zinc battery separator: after 1.8g of molecular sieve was mixed uniformly with 0.2g of PVDF (molecular sieve: PVDF=9:1), 0.8mL of NMP solution was added and milled for 30min (1.8 g of molecular sieve: 0.2g PVDF:0.8mL NMP). The ground slurry was pressed into a 300 μm thick film using a tablet press and dried in a vacuum oven at 80℃for 12 hours. Cutting molecular sieve membrane into membrane sheet with diameter of 17mm, soaking in 1M ZnSO 4 And (3) putting the mixture into the solution for 3 days to obtain the water-based zinc metal battery diaphragm.
Zn symmetric cells using commercial GF separator and molecular sieve separator loaded with ruthenium clusters at 1mA cm -2 Current density and 1mAh cm -2 The cycle performance at area capacity is shown in figure 3. It can be seen from fig. 3 that the symmetrical cell using GF separator suddenly short-circuited the voltage after about 200 hours of cycling, due to dendrite overgrowth. While cells using molecular sieve separators loaded with 1wt% ruthenium clusters remained stable in circulation after 1200 hours.
The dendrite growth inhibition test of the aqueous zinc metal battery diaphragm prepared in the embodiment is shown in figures 4 and 5, in which the current density is increased uncontrollably in 600s of commercial GF diaphragm charging, illustrating Zn 2+ Maintains continuous two-dimensional diffusion and Zn in the process 2+ Dendrites continue to grow along the (101) crystal plane. In contrast, the molecular sieve membrane loaded with ruthenium nanoclusters rapidly enters stable three-dimensional diffusion after being subjected to transient two-dimensional diffusion, and Zn 2+ And depositing along the (002) crystal face and horizontally extending to finally realize the smooth and flat zinc cathode surface.
Regulating zinc deposition and improving solid-liquid interface stability of zinc battery: modified diaphragm regulating Zn 2+ The deposition behavior is characterized as shown in fig. 6. The CV curve is at the end of the reduction peak at about 0mA cm -2 The potential of the inflection point is nucleation overpotential, the size of the nucleation overpotential means the difficulty of nucleation, the nucleation overpotential of the modified diaphragm is obviously smaller than that of a commercial diaphragm, and the modified diaphragm is favorable for Zn 2+ Ion transport kinetics. In addition, the area of the redox peak of the molecular sieve membrane loaded with 1wt% of ruthenium clusters is far larger than that of a commercial membrane, which indicates that the electrode surface participates in more reactive substances and Zn in the process of the redox reaction of the anode 2+ The transmission kinetics are faster.
Corrosion of zinc metal negative electrode is reduced: the corrosion resistance test of the molecular sieve membrane is shown in fig. 7. The commercial diaphragm shows larger corrosion current and more negative corrosion potential, and compared with the commercial diaphragm, the corrosion current of the molecular sieve diaphragm is far smaller than that of the commercial diaphragm, so that the corrosion reaction rate of the zinc cathode is greatly reduced, and the desolvation of the molecular sieve pore canal enables the corrosion of the surface of the zinc cathode to be obviously inhibited.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (2)
1. A preparation method of BETA molecular sieve membrane based on ruthenium-loaded nanocluster is characterized in that: the preparation method comprises the following steps:
s1, calcining a commercial BETA molecular sieve in a muffle furnace, heating from room temperature to 350 ℃ at 1 ℃/min, preserving heat for 2 hours, heating from 350 ℃ to 550 ℃ at 2 ℃/min, preserving heat for 4 hours, and naturally cooling;
s2, impregnating the calcined BETA molecular sieve with RuCl 3 The solution was then vigorously stirred to allow RuCl 3 Absorbing the solution into BETA molecular sieve, drying the obtained solid in oven at 80deg.C overnight, and then adding H 2 Heating to 400 deg.C under atmosphere, continuously reducing for 2 hr, and maintaining the temperature for 2 hr to obtain BETA molecular sieve loaded with ruthenium nanoclusters;
s3, uniformly mixing the obtained BETA molecular sieve loaded with ruthenium nanoclusters with PVDF according to the mass ratio of 9:1, adding NMP solution, grinding for 30min, wherein the mass ratio of PVDF to NMP solution is 1:4, pressing the ground slurry into a membrane with the thickness of 300 mu m by using a tablet press, and placing the membrane in a vacuum oven to be dried for 12h at 80 ℃; finally, the molecular sieve membrane is cut into membrane sheets and soaked in 1 mol ZnSO 4 And (3) standing in the solution for 3 days to obtain the BETA molecular sieve membrane loaded with ruthenium nanoclusters.
2. Use of the BETA molecular sieve membrane based on ruthenium-loaded nanoclusters according to claim 1 in aqueous zinc metal batteries.
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