CN115678023B - Conductive metal organic framework material, preparation method and application thereof, anode of germanium air battery and germanium air battery - Google Patents
Conductive metal organic framework material, preparation method and application thereof, anode of germanium air battery and germanium air battery Download PDFInfo
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- CN115678023B CN115678023B CN202211266389.5A CN202211266389A CN115678023B CN 115678023 B CN115678023 B CN 115678023B CN 202211266389 A CN202211266389 A CN 202211266389A CN 115678023 B CN115678023 B CN 115678023B
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 79
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000013299 conductive metal organic framework Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000011245 gel electrolyte Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- 238000002161 passivation Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 2
- 239000003446 ligand Substances 0.000 description 5
- 239000012621 metal-organic framework Substances 0.000 description 5
- PUXBEKLSMBVFNW-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexamine hexahydrochloride Chemical compound Cl.Cl.Cl.Cl.Cl.Cl.NC1=CC=2C3=CC(=C(C=C3C3=CC(=C(C=C3C2C=C1N)N)N)N)N PUXBEKLSMBVFNW-UHFFFAOYSA-N 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000001632 homeopathic effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a conductive metal organic framework material, a preparation method and application thereof, a germanium air battery anode and a germanium air battery. Wherein, the preparation of the conductive metal organic framework material comprises the following steps: dispersing 2,3,6,7,10, 11-hexaaminotrityl hexahydrochloride in an aqueous solution to obtain a solution I; dispersing nickel chloride hexahydrate in an aqueous solution to obtain a solution II; mixing the solution I with the solution II for reaction; and after the reaction is completed, dropwise adding ammonia water into the mixed solution to continue the reaction, and finally obtaining the conductive metal organic framework material. The invention adoptsFilm coating method, conductive MOF material Ni 2 (HITP) 3 The thin film is composited with the germanium anode, and the thin film separates the germanium anode from the electrolyte without affecting charge transfer, so that passivation of the anode surface is reduced to improve the battery performance.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a conductive metal organic framework material, a preparation method and application thereof, a germanium air battery anode and a germanium air battery.
Background
Germanium air cells have their particular advantages over germanium air cells and other air cells. Germanium air cells have better discharge kinetics resulting in higher actual power density and actual specific energy density, which is almost 3 times that of RTIL-based silicon air cells, about 100 times that of alkaline silicon air cells, and two and three times that of commercial zinc air cells and aluminum air cells, respectively (Phys. Chem. Phys.,2014, 16:22487-22494; chem electric chem,2016, 3:242-246). Under alkaline conditions, the surface of the germanium anode inevitably undergoes passivation reactions, which render the remaining anode unusable. Thus, anodizing germanium to reduce surface passivation is a viable solution that can improve cell performance.
Metal-organic frameworks (MOFs) are a type of crystal porous material, and consist of Metal cluster nodes and organic ligands, and have the structural advantages of high porosity, high specific surface area, adjustable pore structure and the like. However, most MOFs materials, due to their own insulating properties, have limited their application in electrochemical directions to a large extent.
Therefore, how to apply the metal organic framework material on the anode of the germanium air battery to reduce the passivation of the surface of the germanium anode is a problem to be solved at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a conductive metal organic framework material, a preparation method and application thereof, a germanium air battery anode and a germanium air battery.
A preparation method of a conductive metal organic framework material comprises the following steps:
dispersing 2,3,6,7,10, 11-hexaaminotrityl hexahydrochloride in an aqueous solution to obtain a solution I;
dispersing nickel chloride hexahydrate in an aqueous solution to obtain a solution II;
mixing the solution I with the solution II for reaction;
and after the reaction is completed, dropwise adding ammonia water into the mixed solution to continue the reaction, and finally obtaining the conductive metal organic framework material.
Further, according to the preparation method of the conductive metal organic framework material, the volume ratio of the solution I to the solution II is 1:1.
Further, according to the preparation method of the conductive metal organic framework material, the concentration of the solution I is 1.5x10 -3 M-7.5×10 -3 M, the concentration of the solution II is 1.0X10 -3 M-5.0×10 -3 M, the concentration ratio of the two aqueous solutions is 1.4-1.6:1.
Further, the preparation method of the conductive metal organic framework material comprises the step of reacting the solution I and the solution II for 20-40min at the temperature of 55-70 ℃.
Further, according to the preparation method of the conductive metal organic framework material, the concentration of ammonia water is 14M, and the volume ratio of the ammonia water to the mixed solution is 200:1-3.
The conductive metal organic framework material prepared by any one of the above methods.
The application of the conductive metal organic framework material in preparing the anode of the germanium air battery.
Applications as described above, including:
the film-shaped conductive metal organic framework material is adoptedThe film-forming method is attached to the surface of the germanium sheet to form a composite material formed by the germanium sheet and the conductive metal-organic framework material;
naturally airing the obtained composite material for 12 hours, soaking the composite material in absolute ethyl alcohol for 24 hours, and finally drying the composite material, wherein the dried composite material is used as a raw material of the anode of the germanium air battery.
The germanium air battery anode prepared by the method is provided.
The germanium air battery anode and the germanium air battery prepared by the gel electrolyte and the air cathode are provided.
The beneficial effects are that:
1. since most MOFs materials have their own insulating properties, their application in electrochemical direction is limited to a large extent, whereas Ni prepared according to the present invention 2 (HITP) 3 Is composed of stacked pi-conjugated two-dimensional layers in which adjacent ligands are closely packed and have suitable orbital overlap, and charge transfer paths can be formed through such non-covalent interactions, thereby improving cell performance.
2. The invention adoptsFilm coating method, conductive MOF material Ni 2 (HITP) 3 The film is combined with the germanium anode, due to Ni 2 (HITP) 3 Having a one-dimensional cylindrical channel with a diameter of about 1.5nm, OH - Can enter the channel to react with the anode to generate charges and transfer out, while the macromolecules can not enter the channel, so that the film can make the germanium anodeSpaced from the electrolyte but not affecting charge transfer, thereby reducing passivation of the anode surface to enhance cell performance.
3. The thickness of the film can be controlled by controlling the concentration of the solution and the reaction time.
4. By usingThe film is transferred by a film hanging method, so that the film can be uniformly covered on the surface of the germanium sheet and is tightly contacted with the germanium sheet and is not easy to fall off.
5. The method provided by the invention has simple and reliable process and is suitable for large-scale industrial production.
Drawings
FIG. 1 (a) Ni obtained in example 1 2 (HITP) 3 FIG. 1 (b) A plan view of a Ge composite material, ni obtained in example 1 2 (HITP) 3 Cross-section electron microscopy of @ Ge composite.
Fig. 2 is a schematic structural diagram of a germanium air battery prepared in example 4.
FIG. 3 (a) shows the result when the current density is 170. Mu.A/cm 2 And a discharge time comparison diagram of the composite germanium air battery and the blank germanium air battery.
FIG. 3 (b) shows a current density of 225. Mu.A/cm 2 And a discharge time comparison diagram of the composite germanium air battery and the blank germanium air battery.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. 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.
The invention provides Ni 2 (HITP) 3 The preparation method of the @ Ge composite material comprises the following steps:
1) 2,3,6,7,10, 11-hexaaminotrityl hexahydrochloride (HATP.6HCl) and nickel chloride hexahydrateNiCl 2 ·6H 2 O) respectively dispersing in the aqueous solution, mixing the two solutions according to the volume ratio of 1:1 for reaction, wherein the reaction condition is that the reaction is carried out for 20-40min at 55-70 ℃; the concentration of the HATP 6HCl aqueous solution is 1.5X10 -3 M～7.5×10 -3 M, the NiCl 2 ·6H 2 The concentration of the O aqueous solution was 1.0X10 -3 M～5.0×10 -3 M, the concentration ratio of the two aqueous solutions is 1.4-1.6:1.
2) Placing the germanium sheet into absolute ethyl alcohol for ultrasonic cleaning so as to remove impurities on the surface of the germanium sheet;
3) Dropwise adding ammonia water into the mixed solution obtained in the step 1) to react for 0.5-60 min at the temperature of 55-70 ℃, and forming a layer of film on the surface of the solution visible to naked eyes; the ammonia water concentration is 14M, and the volume ratio of the ammonia water to the mixed solution is 200:1 to 3.
4) By Langmuir-The film hanging method transfers the film to the surface of the germanium sheet, and comprises the following specific operations: fixing the germanium sheet obtained in the step 2) by using tweezers, obliquely inserting the germanium sheet into the mixed solution from the wall of the beaker, transferring the mixed solution to the position right below the complete continuous film, enabling the germanium sheet to be parallel to the film, slowly lifting the film upwards, and depositing the film on the surface of the germanium sheet in a homeopathic manner;
5) Naturally airing the composite material obtained in the step 4) for 12 hours, soaking the composite material in absolute ethyl alcohol for 24 hours to dissolve redundant ligands and metal ions in the film, and finally drying the composite material at 80 ℃ for 24 hours to obtain Ni 2 (HITP) 3 @ Ge composite.
The Ni provided by the invention 2 (HITP) 3 The preparation method of the composite with germanium sheet can also be used for silicon wafers, zinc sheets, aluminum sheets, iron sheets and the like.
Example 1
And (3) placing the germanium sheet into absolute ethyl alcohol for ultrasonic cleaning so as to remove impurities on the surface of the germanium sheet. 5.2mg of 2,3,6,7,10, 11-hexaaminotrityl hexahydrohydrochloride (HATP. 6 HCl) and 3.4mg of nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) was dispersed in 10ml of the aqueous solution, and the two solutions were stirred and mixed to react at 65℃for 20 minutes. To the mixed solution, 0.2ml was added dropwiseAmmonia water with the concentration of 14M reacts for 1min, and a layer of film is formed on the surface of the solution visible to naked eyes. Fixing the cleaned germanium sheet by using tweezers, obliquely inserting the germanium sheet into the mixed solution from the wall of the beaker, transferring the germanium sheet to the position right below the complete continuous film, enabling the germanium sheet to be parallel to the film, slowly lifting the film upwards, and depositing the film on the surface of the germanium sheet in a homeopathic manner. Naturally airing for 12h, soaking in absolute ethanol for 24h to dissolve redundant ligand and metal ions in the film, and finally drying at 80 ℃ for 24h to obtain Ni 2 (HITP) 3 @ Ge composite.
FIG. 1 (a) Ni obtained in example 1 2 (HITP) 3 FIG. 1 (b) A plan view of a Ge composite material, ni obtained in example 1 2 (HITP) 3 Cross-section electron microscope images of @ Ge composite material as shown in FIG. 1 (a) and FIG. 1 (b), ni was observed by SEM 2 (HITP) 3 The micro-morphology of the surface and the section of the@Ge composite material can find Ni 2 (HITP) 3 Films have been successfully combined with germanium sheets to form battery anodes.
Example 2:
and (3) placing the germanium sheet into absolute ethyl alcohol for ultrasonic cleaning so as to remove impurities on the surface of the germanium sheet. 5.2mg of 2,3,6,7,10, 11-hexaaminotrityl hexahydrohydrochloride (HATP. 6 HCl) and 3.4mg of nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) was dispersed in 10ml of the aqueous solution, and the two solutions were stirred and mixed and reacted at 70℃for 40min. And (3) dropwise adding 0.2ml of ammonia water with the concentration of 14M into the mixed solution, reacting for 60min, and forming a layer of film on the surface of the solution visible to naked eyes. Fixing the cleaned germanium sheet by using tweezers, obliquely inserting the germanium sheet into the mixed solution from the wall of the beaker, transferring the germanium sheet to the position right below the complete continuous film, enabling the germanium sheet to be parallel to the film, slowly lifting the film upwards, and depositing the film on the surface of the germanium sheet in a homeopathic manner. Naturally airing for 12h, soaking in absolute ethanol for 24h to dissolve redundant ligand and metal ions in the film, and finally drying at 80 ℃ for 24h to obtain Ni 2 (HITP) 3 @ Ge composite.
Example 3:
and (3) placing the germanium sheet into absolute ethyl alcohol for ultrasonic cleaning so as to remove impurities on the surface of the germanium sheet. Taking 5.2mg of 2,3,6,7,10, 11-hexaaminotrityl hexahydro hydrochloride (HATP.6HCl) and 34mg of Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) was dispersed in 10ml of the aqueous solution, and the two solutions were mixed with stirring and reacted at 60℃for 30 minutes. And (3) dropwise adding 0.2ml of ammonia water with the concentration of 14M into the mixed solution, reacting for 1min, and forming a layer of film on the surface of the solution visible to naked eyes. Fixing the cleaned germanium sheet by using tweezers, obliquely inserting the germanium sheet into the mixed solution from the wall of the beaker, transferring the germanium sheet to the position right below the complete continuous film, enabling the germanium sheet to be parallel to the film, slowly lifting the film upwards, and depositing the film on the surface of the germanium sheet in a homeopathic manner. Naturally airing for 12h, soaking in absolute ethanol for 24h to dissolve redundant ligand and metal ions in the film, and finally drying at 80 ℃ for 24h to obtain Ni 2 (HITP) 3 @ Ge composite.
Example 4:
the gel KOH electrolyte with 15wt% CMC content of sodium carboxymethylcellulose was prepared by taking 4.25mL of 6M KOH solution and 0.75g of CMC powder and mixing the two uniformly. Then 2.8mg of Pt/C catalyst is placed in a beaker, 700 mu LNafion solution and 300 mu L isopropanol are sequentially added into the beaker, the mixed solution is dispersed for 30min by ultrasonic to prepare slurry, and then the slurry is smeared on the surface of carbon cloth of an air electrode for natural airing, so that the air cathode is prepared. Ni is added with 2 (HITP) 3 The @ Ge composite material, the gel electrolyte and the air cathode are sequentially placed into a button air battery mold for assembly, and are packaged by a packaging machine, so that the button germanium air battery is constructed (figure 2).
FIG. 3 (a) shows the result when the current density is 170. Mu.A/cm 2 In this case, the discharge time of the composite germanium air cell and the blank germanium air cell are compared with each other, and as shown in FIG. 3 (a), the discharge time is 170. Mu.A/cm 2 Constant current discharge under current density, compared with air battery assembled by blank germanium sheet, the novel Ni 2 (HITP) 3 The discharge voltage of the @ Ge air battery is not changed obviously, and the discharge time is increased by nearly one time (33 h-59 h). FIG. 3 (b) shows a current density of 225. Mu.A/cm 2 In this case, the discharge time of the composite germanium air cell and the blank germanium air cell are compared with each other, as shown in FIG. 3 (b), at 225. Mu.A/cm 2 Constant current discharge under current density, compared with air battery assembled by blank germanium sheet, the novel Ni 2 (HITP) 3 The discharge voltage of the @ Ge air battery is not changed obviously, and the discharge time is increased by nearly one time (18 h-39 h).
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (6)
1. An application of conductive metal organic framework material in preparing anode of germanium air battery is characterized in that,
the preparation of the conductive metal organic framework material comprises the following steps:
dispersing 2,3,6,7,10, 11-hexaaminotrityl hexahydrochloride in an aqueous solution to obtain a solution I;
dispersing nickel chloride hexahydrate in an aqueous solution to obtain a solution II;
mixing the solution I with the solution II for reaction;
after the reaction is completed, dropwise adding ammonia water into the mixed solution to continue the reaction, and finally preparing the conductive metal organic framework material;
the volume ratio of the solution I to the solution II is 1:1;
the concentration of the solution I is 1.5X10 -3 M-7.5×10 -3 M, the concentration of the solution II is 1.0X10 -3 M-5.0×10 -3 M, the concentration ratio of the two aqueous solutions is 1.4-1.6:1.
2. The use according to claim 1, wherein the reaction conditions of solution I and solution II are 55-70 ℃ for 20-40min.
3. The use according to claim 1, wherein the ammonia concentration is 14M.
4. The use according to claim 1, characterized in that it comprises:
the film-shaped conductive metal organic framework material is adoptedThe film-forming method is attached to the surface of the germanium sheet to form a composite material formed by the germanium sheet and the conductive metal-organic framework material;
naturally airing the obtained composite material for 12 hours, soaking the composite material in absolute ethyl alcohol for 24 hours, and finally drying the composite material, wherein the dried composite material is used as a raw material of the anode of the germanium air battery.
5. The germanium air battery anode prepared by the application of claim 4.
6. A germanium air battery prepared using the germanium air battery anode of claim 5, a gel electrolyte, and an air cathode.
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| CN113470984A (en) * | 2021-06-29 | 2021-10-01 | 太原理工大学 | Ni3(HITP)2Graphene-based composite aerogel and preparation method and application thereof |
| CN113937274A (en) * | 2021-11-22 | 2022-01-14 | 江苏科技大学 | Metal organic framework composite material and preparation method and application thereof |
| CN114199957A (en) * | 2021-11-22 | 2022-03-18 | 中科检测技术服务(广州)股份有限公司 | High-conductivity MOFs (metal-organic frameworks) base material with ultralow detection limit on chloramphenicol, and preparation method and application thereof |
| CN114204165A (en) * | 2021-12-02 | 2022-03-18 | 昆明学院 | Preparation method of button-type germanium air battery |
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