CN114613933A - Porous CeO2Zinc cathode coating design and aqueous zinc ion battery - Google Patents
Porous CeO2Zinc cathode coating design and aqueous zinc ion battery Download PDFInfo
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims description 29
- 238000000576 coating method Methods 0.000 title claims description 29
- 238000013461 design Methods 0.000 title claims description 4
- 239000011701 zinc Substances 0.000 claims abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 66
- 239000011148 porous material Substances 0.000 claims abstract description 51
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000011056 performance test Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract 4
- 238000010325 electrochemical charging Methods 0.000 abstract 1
- 238000010326 electrochemical discharging Methods 0.000 abstract 1
- 239000011253 protective coating Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 49
- 239000012621 metal-organic framework Substances 0.000 description 45
- 239000010936 titanium Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 210000001787 dendrite Anatomy 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003365 glass fiber Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 description 3
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating 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
- 230000010361 irregular oscillation Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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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
- 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
-
- 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
- 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
Abstract
The invention relates to the technical field of zinc ion batteries, in particular to CeO2A preparation method and application of a zinc cathode modified by a porous material. The preparation method comprises the following steps: mixing formic acid, DMF and water in a certain proportion to form a reaction solvent, and stirring to uniformly mix the reaction solvent; sequentially adding a certain amount of ammonium ceric nitrate and trimesic acid into a reaction solvent, and stirring until the ammonium ceric nitrate and the trimesic acid are completely dissolved to obtain a mixed solution; stirring and reacting for 10-30min at the temperature of 90-120 ℃, naturally cooling to room temperature, and washing and drying to obtain a precursor Ce-MOF-808; heat treatment at 600 ℃ with 400-2A porous material. CeO prepared by the invention2The porous electrode material inherits the porous structure of the MOF precursor, and after the electrode material is mixed with the binder, the electrode material is coated on the surface of the zinc cathode to form the electrode material with a specific thicknessThe protective coating effectively solves the problems of easy corrosion and uncontrollable growth of dendritic crystals of the zinc cathode in the electrochemical charging and discharging process, and remarkably improves the problem of poor cycle stability of the zinc ion battery caused by corrosion of the zinc cathode and growth of the dendritic crystals.
Description
Technical Field
The invention relates to the technical field of water-based zinc ion batteries, in particular to CeO2Preparation method of zinc cathode modified by porous material and MOF-derived porous CeO2The material preparation and the application of the zinc cathode coating.
Background
The energy crisis is aggravated by the heavy use of fossil fuels, so that the environmental pollution problem is more serious, and the development and utilization of renewable energy sources (wind energy, solar energy and the like) are urgently needed. However, the use of renewable energy sources has problems of discontinuity, instability, and the like, and thus an efficient and safe electric energy storage system becomes a research hotspot. Important criteria for developing large-scale electrical energy storage systems are low cost, high reliability, good safety, environmental friendliness, high energy efficiency, long cycle life, and high energy and power density. Among various energy storage devices, lithium ion batteries widely used in electronic devices and electric vehicles undoubtedly dominate the major market for rechargeable batteries.
Zinc ion batteries based on water-based electrolytes have extremely competitive price, performance and safety and are a very promising alternative to energy storage systems. However, during the battery cycle process, the problems of corrosion, dendrite growth and the like of the zinc negative electrode occur, and the service life of the battery is influenced. Therefore, zinc electrode surface modification is an interesting issue.
The zinc negative electrode protective layer needs to have a suitable pore structure and pore size distribution. The well-designed porous structure channel is beneficial to the transmission of ions in the redox reaction of the battery from the electrolyte to the electrochemical active substance, and the smooth electron transmission can also minimize voltage polarization and ensure the uniform reaction, thereby inhibiting the growth of dendritic crystals and the occurrence of side reactions. The MOF is used as a porous inorganic/organic hybrid material, has a high specific surface area and porosity, a controllable crystal structure and a crystalline porous network material with adjustable pore size, and the crystal morphology and pore channels of the MOF can be regulated and controlled by adjusting metal ions and organic ligands. However, MOFs have low structural stability and are therefore often used as precursors for the preparation of porous materials, which are heatedThe solution yields a more stable material. In addition, through the control of the MOF derivation process conditions, the porous structure of the MOF precursor can be effectively reserved, and the MOF precursor can have larger specific surface area and porosity. At the same time, MOF-derived CeO2Has good affinity to zinc, and can provide uniform nucleation sites for the deposition of zinc, thereby inhibiting the generation of zinc dendrites.
Disclosure of Invention
The technical problem to be solved by the invention is to provide CeO2A preparation method of a zinc cathode modified by a porous material. The problems of corrosion, dendritic crystal growth and the like of the zinc cathode in the battery cycle are solved. Adopts a simple and controllable one-step solvothermal method and a heat treatment process, and MOF and CeO derived by pyrolysis thereof are prepared by the method2The process is safe, pollution-free, simple and easy to operate. Prepared MOF-derived CeO2After the porous material is mixed with the binder, the coating effectively solves the problems of easy corrosion and uncontrollable growth of dendritic crystals of the zinc cathode in the electrochemical charge and discharge process, and prolongs the service life of the battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
MOF-derived CeO2The preparation method of the zinc cathode modified by the porous material comprises the following steps:
(1) mixing formic acid, DMF and water in a certain proportion to form a reaction solvent, and stirring to uniformly mix the reaction solvent;
(2) sequentially adding a certain amount of ammonium ceric nitrate and trimesic acid into the reaction solvent obtained in the step (1), and stirring until the ammonium ceric nitrate and the trimesic acid are completely dissolved to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into a reactor, stirring and reacting at the temperature of 90-120 ℃ for 10-30min, naturally cooling to room temperature, washing and drying to obtain the CeO derived from the MOF2A porous material precursor Ce-MOF-808;
(4) placing the precursor Ce-MOF-808 obtained in the step (3) in a tube furnace, carrying out heat treatment for 1-5h in the air atmosphere of 400-600 ℃, and naturally cooling to room temperature to obtain CeO derived from MOF2A porous material;
(5) mixing the porous material obtained in the step (4) with a binder according to a certain proportion, coating the mixture on the surface of zinc, and drying the zinc surface in vacuum to obtain the CeO derived from the MOF2A zinc cathode modified by a porous material.
Further, the preparation method as described above, in step (1), the volume ratio of formic acid, DMF and water is 0.4-0.6:2: 1.
Further, in the preparation method, in the step (1), the stirring is performed at a rotation speed of 450-; in the step (2), stirring for 5-10 min; the rotation speed of the stirring in the step (3) is 350-450 r/min.
Further, according to the above production method, in the step (2), the molar ratio of the cerium ammonium nitrate to the trimesic acid is 3.6: 1.
Further, in the preparation method as described above, in the step (3), the drying is performed in a vacuum drying oven, the drying temperature is 60 ℃, and the drying time is 2 hours; in the step (5), the vacuum drying temperature is 60 ℃, and the drying time is 24 h.
Further, according to the preparation method, in the step (4), the heating rate of the heat treatment is 5 ℃/min, the temperature is increased to 500 ℃, and the temperature is maintained for 3 hours.
Further, in the above production method, step (5), the binder is PVDF 5130.
Further, according to the preparation method, in the step (5), the mass ratio of the porous material to the binder is 9: 1.
Further, the preparation method is as described above, and in the step (5), the coating mode is knife coating, spin coating and dripping coating.
MOF-derived CeO2The preparation method of the zinc cathode modified by the porous material is prepared according to the preparation method.
The invention has the beneficial effects that:
1. the invention carries out coating modification on the surface of a zinc cathode and coats CeO derived from MOF2The zinc cathode modified by the coating is uniformly electroplated and stripped under the coating after charging and discharging, so that the phenomenon that electricity is generated due to the fact that a diaphragm is pierced is avoidedThe short circuit of the battery promotes the coulomb efficiency and the cycle performance, and prolongs the service life of the battery.
2. The invention relates to CeO derived from MOF2The porous material is dispersed and dissolved in NMP (N-methyl pyrrolidone), PVDF is added, the porous material is coated on the surface of the metal zinc and dried to form a coating, and the close adhesion of the coating and CeO are utilized2The zinc-based electrolyte has good affinity to zinc, and can provide uniform nucleation sites for the deposition of zinc, thereby inhibiting the generation of zinc dendrites and inhibiting the side reaction of metal zinc and electrolyte.
3. The invention provides a preparation method, MOF derived CeO2The preparation of the porous material and the application to drying of the porous material not only have very simple process, but also have very great superiority in time cost, and have great application prospect and research value in the actual application field of the zinc ion battery.
Description of the drawings:
FIG. 1: the MOF-derived CeO provided by the invention2Scanning electron micrographs of the porous material;
FIG. 2: the MOF-derived CeO provided by the invention2XRD pattern of porous material;
FIG. 3: the MOF-derived CeO provided by the invention2Nitrogen adsorption-desorption curves for porous materials;
FIG. 4: the CeO provided by the invention2@ Zn negative electrode at a current density of 0.5mA cm-2The surface capacity is 0.5mA h cm-2Next, a charge-discharge curve chart of the water system zinc ion symmetrical battery;
FIG. 5: the CeO provided by the invention2@ Zn// Ti asymmetric cell at a current density of 2mA cm-2Surface capacity of 1mA h cm-2A charging and discharging curve diagram is drawn;
FIG. 6: the CeO provided by the invention2A charging and discharging curve chart of the water system zinc ion full battery under the condition that the current density is 1A/g is @ Zn// MnVO;
FIG. 7: according to the bare zinc cathode provided by the invention, under the condition that the current density is 1A/g, a zinc cathode plane is scanned by an electron microscope after the charge-discharge cycle of a water system zinc ion full battery;
FIG. 8: according to the bare zinc cathode provided by the invention, under the condition that the current density is 1A/g, the cross section of the zinc cathode is scanned by an electron microscope after the charge-discharge cycle of a water system zinc ion full battery;
FIG. 9: the CeO provided by the invention2A @ Zn zinc negative electrode, in which the current density is 1A/g, the charge-discharge cycle of the water system zinc ion full cell is followed by a planar scanning electron microscope image;
FIG. 10: the CeO provided by the invention2A @ Zn zinc negative electrode, under the condition of current density of 1A/g, a cross-sectional scanning electron microscope image is obtained after the charge-discharge cycle of the water system zinc ion full battery;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the related reagents and raw materials are all conventional reagents and raw materials sold in the market if not specified; the related detection, test and preparation methods are all conventional methods if no special description is provided.
EXAMPLE 1 Zinc Anode coating Material-A MOF-derived CeO2Preparation of porous Material
The preparation method comprises the following steps:
14g of ammonium ceric nitrate and 1.79g of trimesic acid were weighed out and dispersed in a mixture of 96ml of DMF and 20.56ml of formic acid, and stirred on a magnetic stirring table for 10 min. The mixture was charged into a round bottom flask and heated and stirred for 15min under 100 ℃ oil bath. Naturally cooling to room temperature after the reaction is finished, respectively carrying out centrifugal washing twice on reactants by using DMF (dimethyl formamide) and absolute ethyl alcohol, collecting washed products, placing the products in a vacuum drying oven, and carrying out vacuum drying for 2h at the temperature of 60 ℃ to obtain the CeO derived from the MOF2A porous material precursor Ce-MOF-808. Then the precursor is placed in a tube furnace, and the temperature rise rate is 5 ℃/min under the atmosphere of airCalcining at 500 ℃ for 3h, and naturally cooling to room temperature to obtain the CeO derived from the MOF2A porous material.
The present example employs a one-step solvothermal method and a simple heat treatment process. And washing and drying the obtained yellow precipitate, and then further performing heat treatment to obtain a target product, wherein the experimental steps are simple, the repeatability is high, and the controllability is good. Obtained MOF-derived CeO2The porous material has good dispersibility, stable structure and uniform appearance (figure 1). MOF-derived porous CeO2As can be seen from FIG. 2, CeO2The crystal diffraction peaks of the powder were all observed, demonstrating that CeO with a complete crystal structure2The powder was successfully prepared. MOF-derived CeO2The nitrogen adsorption-desorption curve of the porous material (figure 3), and the MOF-derived CeO can be known from figure 32The porous material is of a mesoporous structure, the porous structure channel is beneficial to the transmission of ions in the redox reaction of the battery from electrolyte to an electrochemical active substance, the smooth electron transmission can also minimize voltage polarization, and the uniform reaction is ensured, so that the growth of dendritic crystals and the occurrence of side reactions are inhibited.
Example 2: MOF-derived CeO2Application of porous material modified zinc cathode in zinc ion battery
The zinc foil used in this example was 0.2mm thick and 12mm in diameter.
The button cell used in this example is CR 2032.
(I) MOF-derived CeO2Preparation of zinc cathode modified by porous material
MOF-derived CeO prepared from example 12Uniformly mixing a porous material and PVDF according to a weight ratio of 9:1, adding a proper amount of NMP (N-methyl pyrrolidone) and acetone, stirring for 30min on a magnetic stirring table, placing the mixed system in an ultrasonic water tank for ultrasonic treatment for 30min to accelerate the uniform dispersion of the material, transferring the uniformly mixed material to a water bath kettle, stirring and heating at a water bath temperature of 60 ℃ to remove an acetone solution, finally obtaining uniform slurry without granular sensation, uniformly coating the slurry on a zinc foil wafer, and performing vacuum drying at the temperature of 60 ℃ for 12h to obtain the MOF-derived CeO2A zinc cathode modified by a porous material.
(II) symmetrical Battery Assembly
The assembling method comprises the following steps: the MOF-derived CeO prepared in (a)2The zinc cathode modified by the porous material is simultaneously used as a positive pole piece and a negative pole piece of the button cell. Putting a zinc negative pole piece into a negative pole shell, ensuring that one surface with a coating is contacted with a diaphragm, then putting a glass fiber diaphragm, dripping 120 mu L of 3mol/L zinc trifluoromethanesulfonate electrolyte, then putting another zinc negative pole piece above the diaphragm, also making one surface with the coating be contacted with the diaphragm, then sequentially putting a gasket and a spring plate, finally buckling the positive pole shell, and packaging the battery by using a battery packaging machine to obtain a CeO containing MOF (metal organic framework) derivatives2Zinc cathode water system zinc ion symmetrical button cell decorated by porous material and marked as CeO2@Zn//CeO2@ Zn symmetrical button cell.
Comparative example 1-aqueous zinc ion symmetric button cell for pure zinc electrode: the assembly method is the same as above, except that pure zinc foils are used for the positive and negative plates, and the pure zinc foils are marked as Zn// Zn symmetrical button cells.
(III) asymmetric Battery Assembly
The assembling method comprises the following steps: using titanium foil as a positive pole piece of a button cell, and carrying out MOF (metal organic framework) derived CeO (CeO) preparation2And the zinc negative pole piece modified by the porous material is used as a negative pole piece of the button cell. Putting a negative pole piece into a negative pole shell, enabling one surface with a coating to be in contact with a diaphragm, then putting a glass fiber diaphragm, dripping 120 mu L of 3mol/L zinc trifluoromethanesulfonate electrolyte, then putting a titanium foil above the diaphragm, then sequentially putting a gasket and an elastic sheet, finally buckling the positive pole shell, and packaging the battery by using a battery packaging machine to obtain a battery containing the MOF-derived CeO2The water system zinc ion asymmetric button battery composed of the zinc cathode pole piece modified by the porous material and the titanium foil anode pole piece is marked as CeO2@ Zn// Ti asymmetric button cell.
Comparative example 2-aqueous zinc ion asymmetric button cell of pure zinc titanium electrode: the assembly method is the same as the above, except that the positive pole piece uses titanium foil, the negative pole piece uses pure zinc foil, and the battery is marked as a Zn/Ti asymmetric button battery.
(IV) full cell assembly
The assembling method comprises the following steps: coating MnVO and PTFE on a titanium foil according to a certain proportion, marking as MnVO @ Ti, taking the MnVO @ Ti as a positive pole piece of the button cell, and carrying out MOF-derived CeO preparation2And the zinc negative pole piece modified by the porous material is used as a negative pole piece of the button cell. Putting a negative pole piece into a negative pole shell, enabling one side with a coating to be in contact with a diaphragm, then putting a glass fiber diaphragm, dropping 120 mu L of 3mol/L zinc trifluoromethanesulfonate electrolyte, then putting MnVO @ Ti above the diaphragm, enabling one side with the coating to be in contact with the diaphragm, then sequentially putting a gasket and an elastic sheet, finally buckling the positive pole shell, and packaging the battery by using a battery packaging machine to obtain a piece of CeO containing MOF derivative2A water system zinc ion full-cell button cell composed of a zinc cathode pole piece modified by a porous material and a MnVO @ Ti anode pole piece is marked as CeO2The @ Zn// MnVO @ Ti full cell button cell is provided.
Comparative example 3-aqueous zinc ion full cell button cell with bare zinc electrode: the assembly method is the same as above, except that the cathode pole piece uses pure zinc foil and is marked as Zn// MnVO @ Ti full cell button cell.
(V) Battery Performance test
And performing constant current charge and discharge tests on the water-system zinc ion symmetric button cell, the water-system zinc ion asymmetric button cell and the water-system zinc ion full cell.
1. At a current density of 0.5mA cm-2Surface capacity of 0.5mAh cm-2Next, a constant current charge and discharge test was performed on the water-based zinc ion symmetric button cell, and the result is shown in fig. 4. The Zn// Zn symmetrical button cell has a short circuit phenomenon after being cycled for about 40h, and then voltage polarization is continuously and unstably changed, which means that the cell has serious side reactions such as corrosion and the like during the cycle, so that the zinc is unevenly plated/stripped, the dendritic crystal of the zinc grows rapidly, and the short circuit phenomenon of the cell is caused after the short cycle time. And CeO2@Zn//CeO2The @ Zn symmetrical coin cell can last for 1000h all the time, and CeO is used during circulation2@Zn//CeO2The voltage polarization of the @ Zn symmetrical button battery is always lower than that of Zn// Zn symmetrical coin cell, indicating MOF-derived CeO2The zinc cathode modified by the porous material inhibits side reactions occurring in the battery cycle period to a great extent, ensures uniform deposition/dissolution of zinc, and improves the cycle stability of the battery. Further, CeO2@Zn//CeO2The initial nucleation overpotential of the @ Zn symmetrical button cell is also lower than the nucleation overpotential of the Zn// Zn symmetrical button cell, which shows that the modification layer is more beneficial to the uniform nucleation of zinc ions on the surface of the negative electrode.
2. At a current density of 2mA cm-2Surface capacity of 1mAh cm-2Next, a constant current charge and discharge test was performed on the water-based zinc ion asymmetric button cell, and the result is shown in fig. 5. Comparing Zn// Ti asymmetric button cell with CeO2Improved CeO after charge-discharge cycle of @ Zn// Ti asymmetric button cell coulombic efficiency Curve (CE)2The CE of the @ Zn// Ti asymmetric button cell is more stable than that of the Zn// Ti asymmetric button cell, the Zn// Ti asymmetric button cell generates irregular oscillation after 50 cycles of circulation, and CeO2The @ Zn// Ti asymmetric coin cell was able to cycle stably for 400 cycles with a CE as high as 99.5%, indicating that MOF-derived CeO2The zinc cathode modified by the porous material is beneficial to reversible electroplating/stripping of the zinc cathode, so that the cycling stability of the water system zinc ion battery is further improved.
3. The result of constant current charge and discharge test of the aqueous zinc ion full cell button cell at a current density of 1A/g is shown in fig. 6. Comparing Zn// MnVO @ Ti full cell button cell with CeO2The capacitor-cycle curve of the @ Zn// MnVO @ Ti full cell button cell is that the capacity retention ratio of the Zn// MnVO @ Ti full cell is only 26.3 percent after 600 cycles, and the CeO2The capacity retention rate of the @ Zn// MnVO @ Ti full cell is as high as 85.1% after 600 cycles. This indicates MOF-derived CeO2The zinc cathode modified by the porous material can keep the capacity stability of the zinc ion battery in the circulating process. The Zn// MnVO @ Ti full cell showed a lot of non-uniform dendrites after cycling (FIGS. 7, 8), CeO2The coating after the full battery of @ Zn// MnVO @ Ti cycles has smooth appearance and no dendritic crystal (figure 9), and zinc is generated in CeO2Uniform under the coating of porous materialElectroplating and stripping (FIG. 10), indicating MOF-derived CeO2The porous material can promote uniform nucleation of zinc during cycling, thereby inhibiting the generation of zinc dendrites.
In summary, MOF-derived CeO2The zinc cathode modified by the porous material is simple in preparation method, and can enable the water system zinc ion battery to show excellent electrochemical performance.
Claims (7)
1. Porous CeO2Zinc cathode coating design, water system zinc ion battery. Especially MOF derived CeO2The preparation method of the zinc cathode modified by the porous material is characterized by comprising the following steps:
(1) mixing formic acid, DMF and water in a certain proportion to form a reaction solvent, and stirring to uniformly mix the reaction solvent;
(2) sequentially adding a certain amount of ammonium ceric nitrate and trimesic acid into the reaction solvent obtained in the step (1), and stirring until the ammonium ceric nitrate and the trimesic acid are completely dissolved to obtain a mixed solution;
(3) putting the mixed solution obtained in the step (2) into a reactor, stirring and reacting at the temperature of 90-120 ℃ for 10-30min, naturally cooling to room temperature, washing and drying to obtain the CeO derived from the MOF2A porous material precursor Ce-MOF-808;
(4) placing the precursor Ce-MOF-808 obtained in the step (3) in a tube furnace, carrying out heat treatment for 1-5h in the air atmosphere of 400-600 ℃, and naturally cooling to room temperature to obtain CeO derived from MOF2A porous material;
(5) mixing the porous material obtained in the step (4) with a binder according to a certain proportion, coating the mixture on the surface of zinc, and drying the zinc surface in vacuum to obtain the CeO derived from the MOF2A zinc cathode modified by a porous material. And assembling the zinc ion battery into a water system zinc ion battery for electrochemical performance test.
2. The method of claim 1, wherein: in the step (1), the volume ratio of the formic acid to the DMF to the water is 0.4-0.6:2: 1. The stirring is carried out at the rotating speed of 450-500r/min, and the stirring time is 20-30 min.
3. The method of claim 1, wherein: in the step (2), stirring for 5-10 min; the stirring speed is 350-450 r/min; the molar ratio of the ammonium ceric nitrate to the trimesic acid is 3.6: 1.
4. The method of claim 1, wherein: in the step (3), the drying is carried out in a vacuum drying oven, the drying temperature is 60 ℃, and the drying time is 2 hours.
5. The method of claim 1, wherein: in the step (4), the heating rate of the heat treatment is 5 ℃/min, the temperature is increased to 500 ℃, and the temperature is kept for 3 h.
6. The method of claim 1, wherein: in the step (5), the binder is PVDF 5130; the ratio of the porous material to the binder is 9: 1; the vacuum drying temperature is 60 ℃, and the drying time is 12 h; the coating modes comprise blade coating, spin coating and drop coating.
7. Porous CeO2The design of the zinc cathode coating is used for protecting the cathode of the water-based zinc ion battery, the preparation method of the cathode coating as claimed in any one of claims 1-6 is adopted, and the application of the cathode coating in the water-based zinc ion battery is realized.
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| CN114864913A (en) * | 2022-06-15 | 2022-08-05 | 中原工学院 | PEG-CeF 3 @ Zn corrosion-resistant composite metal cathode and preparation method and application thereof |
| CN115172647A (en) * | 2022-09-02 | 2022-10-11 | 中南大学 | Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113258070A (en) * | 2021-05-31 | 2021-08-13 | 哈尔滨工业大学 | Metal zinc cathode interface modification method for water-based zinc ion battery |
| CN114171711A (en) * | 2021-11-12 | 2022-03-11 | 西南民族大学 | Electrode preparation method of water-based zinc ion battery, electrode and battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113258070A (en) * | 2021-05-31 | 2021-08-13 | 哈尔滨工业大学 | Metal zinc cathode interface modification method for water-based zinc ion battery |
| CN114171711A (en) * | 2021-11-12 | 2022-03-11 | 西南民族大学 | Electrode preparation method of water-based zinc ion battery, electrode and battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114864913A (en) * | 2022-06-15 | 2022-08-05 | 中原工学院 | PEG-CeF 3 @ Zn corrosion-resistant composite metal cathode and preparation method and application thereof |
| CN114864913B (en) * | 2022-06-15 | 2023-12-22 | 中原工学院 | PEG-CeF 3 Corrosion-resistant composite metal anode of @ Zn, and preparation method and application thereof |
| CN115172647A (en) * | 2022-09-02 | 2022-10-11 | 中南大学 | Fatty acid zinc modified zinc metal negative electrode and preparation method and application thereof |
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