CN112846224A - Nano porous metal material and preparation method and application thereof - Google Patents
Nano porous metal material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112846224A CN112846224A CN202110000598.4A CN202110000598A CN112846224A CN 112846224 A CN112846224 A CN 112846224A CN 202110000598 A CN202110000598 A CN 202110000598A CN 112846224 A CN112846224 A CN 112846224A
- Authority
- CN
- China
- Prior art keywords
- follows
- preparation
- stirring
- aqueous solution
- gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007769 metal material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 93
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 239000000499 gel Substances 0.000 claims abstract description 42
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 39
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 27
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 23
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 23
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 20
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000011565 manganese chloride Substances 0.000 claims abstract description 20
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 20
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 20
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 239000011592 zinc chloride Substances 0.000 claims abstract description 19
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 19
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000004964 aerogel Substances 0.000 claims abstract description 11
- 239000000017 hydrogel Substances 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 38
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000003837 high-temperature calcination Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000003990 capacitor Substances 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- 239000002904 solvent Substances 0.000 description 19
- 229910021645 metal ion Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 238000000352 supercritical drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 206010049244 Ankyloglossia congenital Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- -1 yttrium ions Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a nano porous metal material and a preparation method and application thereof, wherein acrylamide, methylene bisacrylamide, palladium powder and gamma-methacryloxypropyl trimethoxy silane are used as raw materials to prepare gel; then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene; then soaking the gel into an aqueous solution, soaking for 2-3 days at room temperature, stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material; calcining at high temperature, and irradiating ions to obtain the final product. The nano-porous metal material prepared by the method has higher porosity and large specific surface area, and has higher specific capacitance when being used as a super capacitor anode material.
Description
Technical Field
The invention relates to the technical field, in particular to a nano porous metal material and a preparation method and application thereof.
Background
The nano porous metal material is a functional structural material which is developed rapidly at present, has the characteristics of metal and other nano materials, and has wide potential application prospects in catalysis, filtration, water dissociation, sensors, chemical synthesis, hydrogen storage, automobile exhaust treatment, drug loading and release, electrochemical energy storage and conversion and the like.
The traditional preparation method of the nano porous metal material is an alloy removing method, and particularly, one or more active components in the alloy are selectively removed by an electrochemical method under a certain corrosion condition by utilizing the difference of chemical properties among different components in the alloy, so that a three-dimensional porous structure is formed by the residual metal components, namely, active components are dissolved or separated out, and relatively stable components are enriched. The dealloying method can obtain a three-dimensional reticular porous structure with high specific surface area, the frenulum and the pore channel are mutually continuous, the porous structure can be dynamically regulated and controlled, and the dealloying method has the advantages of simplicity in operation, low cost, suitability for large-scale production and the like. The dealloying method is an effective method for more conveniently and quickly obtaining the porous metal material with the pore diameter reaching the nanometer size, and realizes the breakthrough of the porous metal material in the pore diameter size.
The dealloying method comprises two processes of selection, preparation and selective corrosion of an alloy matrix. Wherein, the former process usually adopts a high-temperature smelting method and the like, has higher requirements on equipment and temperature and has certain danger in operation; in the latter process, recrystallization inevitably occurs and residues of active components exist; resulting in waste of materials, especially precious metals, and the corrosive liquid is a highly toxic and dangerous solvent.
In addition to the dealloying method, the existing preparation method of the nano porous metal material also comprises a nano powder sintering method, a template method and the like, wherein the nano powder sintering method is a method for obtaining a porous sintered body by filling metal powder with a certain size into a mold for forming and performing pressure sintering. The template method is to deposit a target metal material into pores of a porous template through a physical and chemical method, and then remove the template, so as to obtain the nano porous metal material with the similar or related appearance and size with the template, wherein the subsequent treatment process of the hard template method is complicated, the hard template structure is single, and the appearance change is less; and the nano porous material prepared by the soft template has poor stability and low template efficiency. On the whole, the template method has complex preparation process and higher cost, is not suitable for batch production, and limits the practical application of the nano porous metal material.
As a self-supporting material, nanoporous metal materials have gained wide attention due to their unique structural features and chemical properties. It has been reported that almost all nanoporous metal structures consist of narrow pores and coarsened ligaments, and the porosity is generally small and the specific surface area is also small, so that the performance is greatly limited.
Patent CN104928518B discloses a superfine nano porous metal and its preparation method, which adopts a common dealloying method, corrodes Mg and Y elements by dealloying with saturated sodium carbonate solution to obtain a porous metal material, which has the inherent defects of dealloying method, metal waste, and further affects the product performance because of unavoidable recrystallization and residue of active components.
Disclosure of Invention
The invention aims to provide a nano porous metal material, a preparation method and application thereof.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of a nano porous metal material comprises the following specific steps:
(1) firstly, preparing gel by taking acrylamide, methylene bisacrylamide, palladium powder and gamma-methacryloxypropyl trimethoxy silane as raw materials;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel into an aqueous solution, soaking for 2-3 days at room temperature (25 ℃), stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material.
Preferably, in the step (1), the mass ratio of acrylamide, methylene bisacrylamide, palladium powder and gamma-methacryloxypropyltrimethoxysilane is 100: 0.04-0.06: 0.01-0.02: 0.08 to 0.1.
Preferably, the specific method of step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, carrying out ultrasonic oscillation for 30-40 minutes, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
Preferably, in the step (1-2), the amounts of ammonium persulfate and N, N' -tetramethyldiethylamine are 0.1% and 0.2% of the weight of acrylamide, respectively, and the amount of deionized water is 3.5-4.5 times of the weight of acrylamide.
Preferably, in the step (1-2), the mixture is stirred, mixed uniformly, kept stand at room temperature for 2-3 hours, and then transferred to a mold.
Further preferably, in the step (1-3), the process conditions of the polymerization reaction are as follows: reacting for 3-5 hours at 40-50 ℃.
Preferably, the specific method of the step (2) is as follows by weight parts: mixing 1-2 parts of sodium citrate, 2-4 parts of boric acid, 0.02-0.03 part of manganese chloride, 0.01-0.02 part of zinc chloride, 0.005-0.008 part of yttrium chloride, 2-4 parts of sodium hypophosphite, 0.1-0.2 part of 3, 4-ethylenedioxythiophene and 100 parts of deionized water to prepare an aqueous solution.
Preferably, in the step (3), the mass ratio of the gel to the aqueous solution is 1: 5 to 8.
Preferably, in the step (3), the specific method of stirring the reaction is as follows: stirring and reacting for 30-40 minutes at 35-40 ℃.
Preferably, in step (3), the electropolymerization process conditions are as follows: the voltage window is controlled to be-0.5-1.2V, the scanning speed is 70-80 mV/s, and the electropolymerization time is 30-50 minutes.
Preferably, in the step (3), before drying, deionized water is used for washing for 2-3 times until no metal ions exist in the cleaning solution, and then acetone is used for solvent exchange until the water content in the acetone after the exchange is lower than 2000ppm, so that the solvent exchange can be completed.
Preferably, in step (3), CO is used2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 5-10 kg/min, and the drying time is 8-12 hours.
Preferably, in the step (4), the high-temperature calcination process conditions are as follows: calcining for 5-8 hours at 350-400 ℃ under the argon atmosphere.
Preferably, in the step (4), the specific method of ion irradiation is: transferring the product obtained by high-temperature calcination to a serial electrostatic accelerator, vacuumizing to 0.00001-0.0001 Pa, injecting metal ions with energy of 3-5 MeV and dosage of 1-2 × 1014ions/cm2The irradiation temperature is 25 ℃, and the irradiation time is 2-3 hours.
Further preferably, the metal ion is selected from any one of gold, silver or copper.
In addition, the invention also claims a nano porous metal material obtained by the preparation method and application of the nano porous metal material as a super capacitor anode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention firstly takes acrylamide, methylene bisacrylamide, palladium powder and gamma-methacryloxypropyl trimethoxy silane as raw materials to prepare gel; then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene; then soaking the gel into an aqueous solution, soaking for 2-3 days at room temperature, stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material; high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material which has higher porosity, large specific surface area and excellent performance;
(2) in order to improve the uniform distribution of the palladium powder in a system, the invention firstly utilizes gamma-methacryloxypropyl trimethoxysilane for modification, during the subsequent gelation process, double bonds brought by the gamma-methacryloxypropyl trimethoxysilane can be polymerized with acrylamide and methylene bisacrylamide to form a larger network structure, more pores are formed, and the porosity and specific surface area of a product are improved, so that the performance of the product is improved;
(3) according to the invention, the gel is immersed in the aqueous solution, manganese ions, zinc ions, yttrium ions and 3, 4-ethylenedioxythiophene contained in the aqueous solution are uniformly adsorbed in pores of the gel and are electropolymerized to generate polythiophene which is modified on the metal surface, so that the high-temperature-resistant polythiophene is not decomposed during high-temperature calcination, the porosity and the specific surface area of the product are further improved, and ion irradiation is carried out after the high-temperature calcination is finished, so that the pore surface is further roughened, and the specific surface area of the product is further improved.
(4) The nano porous metal material obtained by the invention has higher porosity and specific surface, more activation sites are formed on the surface of the pores, the electrolyte ions can enter and exit, and the nano porous metal material is used as the positive electrode material of the super capacitor and has higher specific capacitance.
Drawings
FIG. 1 is a scanning electron microscope image of the nanoporous metal material obtained in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing gel from 100g of acrylamide, 0.04g of methylene bisacrylamide, 0.02g of palladium powder and 0.08g of gamma-methacryloxypropyltrimethoxysilane serving as raw materials;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel in the aqueous solution for 3 days at room temperature (25 ℃), stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) calcining at high temperature, and irradiating ions to obtain the nano porous metal material (shown in a scanning electron microscope picture in figure 1).
The specific method of the step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, carrying out ultrasonic oscillation for 30 minutes, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
In the step (1-2), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 4.5 times of the weight of acrylamide.
And (3) in the step (1-2), stirring and uniformly mixing, standing at room temperature for 2 hours, and transferring into a mold.
In the step (1-3), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 3 hours.
The specific method of the step (2) is as follows: 2g of sodium citrate, 2g of boric acid, 0.03g of manganese chloride, 0.01g of zinc chloride, 0.008g of yttrium chloride, 2g of sodium hypophosphite, 0.2g of 3, 4-ethylenedioxythiophene and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 5.
in the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 40 ℃ for 30 minutes.
In the step (3), the electropolymerization process conditions are as follows: the voltage window was controlled at 1.2V, the scan rate was 70mV/s, and the electropolymerization time was 50 minutes.
In the step (3), before drying, washing for 2 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 10kg/min, and the drying time is 8 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 400 ℃ for 5 hours under an argon atmosphere.
In the step (4), the specific method of ion irradiation is as follows: transferring the product obtained by high-temperature calcination to a serial electrostatic accelerator, vacuumizing to 0.0001Pa, and injecting metal ions (gold) with energy of 3MeV and dosage of 2 × 1014ions/cm2The irradiation temperature was 25 ℃ and the irradiation time was 2 hours.
Example 2
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing gel from 100g of acrylamide, 0.06g of methylene bisacrylamide, 0.01g of palladium powder and 0.1g of gamma-methacryloxypropyltrimethoxysilane as raw materials;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel in water solution at room temperature (25 ℃) for 2 days, stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material.
The specific method of the step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, oscillating for 40 minutes by ultrasonic waves, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
In the step (1-2), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 3.5 times of the weight of acrylamide.
And (3) in the step (1-2), stirring and uniformly mixing, standing at room temperature for 3 hours, and transferring into a mold.
In the step (1-3), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 40 ℃ for 5 hours.
The specific method of the step (2) is as follows: 1g of sodium citrate, 4g of boric acid, 0.02g of manganese chloride, 0.02g of zinc chloride, 0.005g of yttrium chloride, 4g of sodium hypophosphite, 0.1g of 3, 4-ethylenedioxythiophene and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 8.
In the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 35 ℃ for 40 minutes.
In the step (3), the electropolymerization process conditions are as follows: the voltage window was controlled at-0.5V, the scan rate was 80mV/s, and the electropolymerization time was 30 minutes.
In the step (3), before drying, washing for 3 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 5kg/min, and the drying time is 12 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 350 ℃ for 8 hours under an argon atmosphere.
In the step (4), the specific method of ion irradiation is as follows: transferring the product obtained by high-temperature calcination to a tandem electrostatic accelerator, vacuumizing to 0.00001Pa, and injecting metal ions (silver) with energy of 5MeV and dosage of 1 × 1014ions/cm2The irradiation temperature was 25 ℃ and the irradiation time was 3 hours.
Example 3
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing 100g of acrylamide, 0.05g of methylene bisacrylamide, 0.015g of palladium powder and 0.09g of gamma-methacryloxypropyl trimethoxysilane into gel;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel in the aqueous solution for 3 days at room temperature (25 ℃), stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material.
The specific method of the step (1) is as follows:
(1-1) adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, oscillating for 35 minutes by ultrasonic waves, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
In the step (1-2), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 4 times of the weight of acrylamide.
In the step (1-2), the mixture is stirred, mixed uniformly, kept stand at room temperature for 2.5 hours and then transferred into a mold.
In the step (1-3), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 45 ℃ for 4 hours.
The specific method of the step (2) is as follows: 1.5g of sodium citrate, 3g of boric acid, 0.025g of manganese chloride, 0.015g of zinc chloride, 0.007g of yttrium chloride, 3g of sodium hypophosphite, 0.15g of 3, 4-ethylenedioxythiophene and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 6.
in the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 38 ℃ for 35 minutes.
In the step (3), the electropolymerization process conditions are as follows: the voltage window was controlled at 1V, the scan rate was 75mV/s, and the electropolymerization time was 40 minutes.
In the step (3), before drying, washing for 2 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 8kg/min, and the drying time is 10 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 380 deg.C for 7 hr under argon atmosphere.
In the step (4), the specific method of ion irradiation is as follows: transferring the product obtained by high-temperature calcination to a tandem electrostatic accelerator, vacuumizing to 0.00008Pa, and injecting metal ions (copper) with energy of 4MeV and dosage of 1.5 × 1014ions/cm2The irradiation temperature was 25 ℃ and the irradiation time was 2.5 hours.
Comparative example 1
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing gel by using 100g of acrylamide, 0.04g of methylene bisacrylamide and 0.02g of palladium powder as raw materials;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel in the aqueous solution for 3 days at room temperature (25 ℃), stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material.
The specific method of the step (1) is as follows:
(1-1) adding acrylamide, methylene bisacrylamide and ammonium persulfate into a mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and palladium powder, stirring uniformly, and transferring into a mold;
(1-2) carrying out polymerization reaction to obtain the gel.
In the step (1-1), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 4.5 times of the weight of acrylamide.
In the step (1-1), the mixture is stirred, mixed uniformly, kept stand at room temperature for 2 hours and then transferred into a mold.
In the step (1-2), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 3 hours.
The specific method of the step (2) is as follows: 2g of sodium citrate, 2g of boric acid, 0.03g of manganese chloride, 0.01g of zinc chloride, 0.008g of yttrium chloride, 2g of sodium hypophosphite, 0.2g of 3, 4-ethylenedioxythiophene and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 5.
in the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 40 ℃ for 30 minutes.
In the step (3), the electropolymerization process conditions are as follows: the voltage window was controlled at 1.2V, the scan rate was 70mV/s, and the electropolymerization time was 50 minutes.
In the step (3), before drying, washing for 2 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 10kg/min, and the drying time is 8 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 400 ℃ for 5 hours under an argon atmosphere.
In the step (4), the specific method of ion irradiation is as follows: transferring the product obtained by high-temperature calcination to a serial electrostatic accelerator, vacuumizing to 0.0001Pa, and injecting metal ions (Gold), energy of 3MeV, dose of 2X 1014ions/cm2The irradiation temperature was 25 ℃ and the irradiation time was 2 hours.
Comparative example 2
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing gel from 100g of acrylamide, 0.04g of methylene bisacrylamide, 0.02g of palladium powder and 0.08g of gamma-methacryloxypropyltrimethoxysilane serving as raw materials;
(2) then preparing an aqueous solution containing manganese chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel in the aqueous solution for 3 days at room temperature (25 ℃), stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material.
The specific method of the step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, carrying out ultrasonic oscillation for 30 minutes, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
In the step (1-2), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 4.5 times of the weight of acrylamide.
And (3) in the step (1-2), stirring and uniformly mixing, standing at room temperature for 2 hours, and transferring into a mold.
In the step (1-3), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 3 hours.
The specific method of the step (2) is as follows: 2g of sodium citrate, 2g of boric acid, 0.03g of manganese chloride, 2g of sodium hypophosphite, 0.2g of 3, 4-ethylenedioxythiophene and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 5.
in the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 40 ℃ for 30 minutes.
In the step (3), the electropolymerization process conditions are as follows: the voltage window was controlled at 1.2V, the scan rate was 70mV/s, and the electropolymerization time was 50 minutes.
In the step (3), before drying, washing for 2 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 10kg/min, and the drying time is 8 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 400 ℃ for 5 hours under an argon atmosphere.
In the step (4), the specific method of ion irradiation is as follows: transferring the product obtained by high-temperature calcination to a serial electrostatic accelerator, vacuumizing to 0.0001Pa, and injecting metal ions (gold) with energy of 3MeV and dosage of 2 × 1014ions/cm2The irradiation temperature was 25 ℃ and the irradiation time was 2 hours.
Comparative example 3
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing gel from 100g of acrylamide, 0.04g of methylene bisacrylamide, 0.02g of palladium powder and 0.08g of gamma-methacryloxypropyltrimethoxysilane serving as raw materials;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride and yttrium chloride;
(3) then soaking the gel in the aqueous solution for 3 days at room temperature (25 ℃), stirring for reaction to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) high-temperature calcination and ion irradiation are carried out to obtain the nano porous metal material.
The specific method of the step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, carrying out ultrasonic oscillation for 30 minutes, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
In the step (1-2), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 4.5 times of the weight of acrylamide.
And (3) in the step (1-2), stirring and uniformly mixing, standing at room temperature for 2 hours, and transferring into a mold.
In the step (1-3), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 3 hours.
The specific method of the step (2) is as follows: 2g of sodium citrate, 2g of boric acid, 0.03g of manganese chloride, 0.01g of zinc chloride, 0.008g of yttrium chloride, 2g of sodium hypophosphite and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 5.
in the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 40 ℃ for 30 minutes.
In the step (3), before drying, washing for 2 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 10kg/min, and the drying time is 8 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 400 ℃ for 5 hours under an argon atmosphere.
In the step (4), the specific method of ion irradiation is as follows: transferring the product obtained by high-temperature calcination to a serial electrostatic accelerator, vacuumizing to 0.0001Pa, and injecting metal ions (gold) with energy of 3MeV and dosage of 2 × 1014ions/cm2The irradiation temperature was 25 ℃ and the irradiation time was 2 hours.
Comparative example 4
A preparation method of a nano porous metal material comprises the following specific steps:
(1) preparing gel from 100g of acrylamide, 0.04g of methylene bisacrylamide, 0.02g of palladium powder and 0.08g of gamma-methacryloxypropyltrimethoxysilane serving as raw materials;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene;
(3) then soaking the gel in the aqueous solution for 3 days at room temperature (25 ℃), stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) and (3) calcining at high temperature to obtain the nano porous metal material.
The specific method of the step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, carrying out ultrasonic oscillation for 30 minutes, and filtering to obtain modified palladium powder;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into the mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring and uniformly mixing, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
In the step (1-2), the dosage of ammonium persulfate and N, N, N ', N' -tetramethyl diethylamine are respectively 0.1% and 0.2% of the weight of acrylamide, and the dosage of deionized water is 4.5 times of the weight of acrylamide.
And (3) in the step (1-2), stirring and uniformly mixing, standing at room temperature for 2 hours, and transferring into a mold.
In the step (1-3), the process conditions of the polymerization reaction are as follows: the reaction was carried out at 50 ℃ for 3 hours.
The specific method of the step (2) is as follows: 2g of sodium citrate, 2g of boric acid, 0.03g of manganese chloride, 0.01g of zinc chloride, 0.008g of yttrium chloride, 2g of sodium hypophosphite, 0.2g of 3, 4-ethylenedioxythiophene and 100g of deionized water are mixed to prepare an aqueous solution.
In the step (3), the mass ratio of the gel to the aqueous solution is 1: 5.
in the step (3), the specific method of stirring reaction is as follows: the reaction was stirred at 40 ℃ for 30 minutes.
In the step (3), the electropolymerization process conditions are as follows: the voltage window was controlled at 1.2V, the scan rate was 70mV/s, and the electropolymerization time was 50 minutes.
In the step (3), before drying, washing for 2 times by using deionized water until no metal ions exist in the cleaning solution, and then performing solvent exchange by using acetone until the water content in the acetone after the exchange is lower than 2000ppm, thereby completing the solvent exchange.
In the step (3), CO is adopted2Supercritical drying, wherein the specific process conditions are as follows: the pressure is 10Mpa, the temperature is 40 ℃, the flow rate is 10kg/min, and the drying time is 8 hours.
In the step (4), the process conditions of high-temperature calcination are as follows: calcining at 400 ℃ for 5 hours under an argon atmosphere.
Test examples
The porosity and the specific surface area of the nano-porous metal materials obtained in the examples 1-3 and the comparative examples 1-4 are detected, the porosity is referred to GB/T21650.2-2008, and the specific surface area is determined by a nitrogen adsorption method. The results are shown in Table 1.
TABLE 1 porosity and specific surface area test results
The nano-porous metal materials obtained in examples 1-3 and comparative examples 1-4 are used as positive electrode materials to construct a super capacitor, and the super capacitor comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte comprises electrolyte and a solvent, the concentration of the electrolyte is 1.2mol/L, the electrolyte is LiPF, and the solvent is ethylene carbonate, and the volume ratio of ethyl methyl carbonate to dimethyl carbonate is 1.2: 1: 1. The negative electrode takes active carbon as a negative electrode material, and the diaphragm is a ceramic diaphragm.
The specific capacity was tested using RST5200E electrochemical workstation (Zheng Zhou Shi instruments science and technology Co., Ltd.), and the results are shown in Table 2.
TABLE 2 specific capacitance examination results
As can be seen from tables 1 and 2, the products obtained in examples 1 to 3 have high porosity, large specific surface area and excellent electrical properties, and are suitable for being used as the positive electrode material of the supercapacitor.
Comparative example 1 in step (1), the gamma-methacryloxypropyltrimethoxysilane is omitted, on one hand, the uniform dispersion of palladium powder in a system is influenced, on the other hand, the degree of polymerization and branching is not enough, and the porosity and the specific surface area of a product are directly influenced, so that the electrical property is influenced; in the comparative example 2, zinc chloride and yttrium chloride are omitted in the step (2), the porosity and the specific surface area of the product are also obviously reduced, which shows that the adjustment of electron cloud distribution among different metal ions, the activation sites and the like can also influence the surface performance of the product, and further influence the electrical performance; comparative example 3, 4-ethylenedioxythiophene was omitted in step (2), and the formation of polythiophene was absent, resulting in a decrease in porosity and specific surface area of the product, and a significant deterioration in electrical properties; comparative example 4 the electron irradiation was omitted in step (4), and the specific surface area of the product was significantly reduced, thereby affecting the electrical properties.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a nano porous metal material is characterized by comprising the following specific steps:
(1) preparing acrylamide, methylene bisacrylamide, palladium powder and gamma-methacryloxypropyl trimethoxysilane into gel for later use;
(2) then preparing an aqueous solution containing manganese chloride, zinc chloride, yttrium chloride and 3, 4-ethylenedioxythiophene for later use;
(3) soaking the gel in the step (1) into the aqueous solution in the step (2) at room temperature for 2-3 days, stirring for reaction, performing electropolymerization to obtain a metal-hydrogel composite material, and drying to obtain a metal-aerogel composite material;
(4) and (4) calcining the composite material obtained in the step (3) at high temperature, and irradiating ions to obtain the nano porous metal material.
2. The preparation method according to claim 1, wherein in the step (1), the mass ratio of acrylamide, methylene bisacrylamide, palladium powder and gamma-methacryloxypropyltrimethoxysilane is 100: 0.04-0.06: 0.01-0.02: 0.08 to 0.1.
3. The production method according to any one of claims 1 to 2, wherein the specific method of step (1) is as follows:
(1-1) firstly adding palladium powder into gamma-methacryloxypropyltrimethoxysilane, carrying out ultrasonic oscillation for 30-40 minutes, and filtering to obtain modified palladium powder for later use;
(1-2) adding acrylamide, methylene bisacrylamide and ammonium persulfate into a mixing kettle, continuously adding deionized water, stirring to completely dissolve the solid, adding N, N, N ', N' -tetramethyldiethylamine and modified palladium powder, stirring uniformly, and transferring into a mold;
(1-3) carrying out polymerization reaction to obtain the gel.
4. The preparation method according to claim 1, wherein the specific method of step (2) is as follows, in parts by weight: mixing 1-2 parts of sodium citrate, 2-4 parts of boric acid, 0.02-0.03 part of manganese chloride, 0.01-0.02 part of zinc chloride, 0.005-0.008 part of yttrium chloride, 2-4 parts of sodium hypophosphite, 0.1-0.2 part of 3, 4-ethylenedioxythiophene and 100 parts of deionized water to prepare an aqueous solution.
5. The method according to claim 1, wherein in the step (3), the mass ratio of the gel to the aqueous solution is 1: 5 to 8.
6. The preparation method according to claim 1, wherein in the step (3), the stirring reaction is carried out by a specific method comprising: stirring and reacting for 30-40 minutes at 35-40 ℃.
7. The preparation method according to claim 1, wherein in step (3), the electropolymerization process conditions are as follows: the voltage window is controlled to be-0.5-1.2V, the scanning speed is 70-80 mV/s, and the electropolymerization time is 30-50 minutes.
8. The preparation method according to claim 1, wherein in the step (4), the process conditions of the high-temperature calcination are as follows: calcining for 5-8 hours at 350-400 ℃ under the argon atmosphere.
9. A nano-porous metal material prepared by the preparation method of claims 1-8.
10. Use of the nanoporous metallic material of claim 9 as a supercapacitor positive electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110000598.4A CN112846224A (en) | 2021-01-04 | 2021-01-04 | Nano porous metal material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110000598.4A CN112846224A (en) | 2021-01-04 | 2021-01-04 | Nano porous metal material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112846224A true CN112846224A (en) | 2021-05-28 |
Family
ID=76001056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110000598.4A Pending CN112846224A (en) | 2021-01-04 | 2021-01-04 | Nano porous metal material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112846224A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012035507A2 (en) * | 2010-09-16 | 2012-03-22 | Ulusal Bor Arastirma Enstitusu | Production method of hydrogel-metal composite |
| CN103993299A (en) * | 2014-04-22 | 2014-08-20 | 中国工程物理研究院激光聚变研究中心 | Preparation method for nano porous metal materials |
| CN105540672A (en) * | 2016-01-29 | 2016-05-04 | 卓达新材料科技集团有限公司 | Preparation method for germanium oxide and manganese oxide hybrid aerogel composite material |
-
2021
- 2021-01-04 CN CN202110000598.4A patent/CN112846224A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012035507A2 (en) * | 2010-09-16 | 2012-03-22 | Ulusal Bor Arastirma Enstitusu | Production method of hydrogel-metal composite |
| CN103993299A (en) * | 2014-04-22 | 2014-08-20 | 中国工程物理研究院激光聚变研究中心 | Preparation method for nano porous metal materials |
| CN105540672A (en) * | 2016-01-29 | 2016-05-04 | 卓达新材料科技集团有限公司 | Preparation method for germanium oxide and manganese oxide hybrid aerogel composite material |
Non-Patent Citations (2)
| Title |
|---|
| 曹凤等: "多孔金属材料的化学制备方法及性能研究进展", 《材料导报》 * |
| 王聪聪等: "凝胶注模成形制备铜锡多孔材料的研究", 《粉末冶金技术》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bendi et al. | Metal Organic Framework-Derived Metal Phosphates as Electrode Materials for Supercapacitors. | |
| CN108122690B (en) | Preparation method of sulfur-nitrogen co-doped carbon nanosphere electrode material | |
| CN109422263B (en) | Cellulose porous activated carbon and preparation method and application thereof | |
| CN103508442B (en) | The preparation method of Graphene | |
| CN105719852A (en) | Preparation method for three-dimensional nano-porous graphene/manganese dioxide composite electrode material | |
| CN105668552A (en) | Preparation method of easy-to-disperse nitrogen-doped graphene powder | |
| CN107394214A (en) | The preparation and application of the nitrogen co-doped porous carbon microsphere material of cobalt | |
| CN111318306A (en) | Novel bifunctional electrochemical high-efficiency catalyst composite material and preparation method thereof | |
| CN109913887A (en) | A kind of flexible electrode catalyst and its preparation method and application of the nitrogen-doped carbon cladding Pt nanoparticle based on electrostatic spinning technique | |
| CN110610820A (en) | Preparation method of porous carbon flexible self-supporting electrode based on melamine foam and metal organic framework material | |
| CN107572517A (en) | Alginic acid alkali three-dimensional network layered activated carbon and one step charing preparation method | |
| CN113403629A (en) | Catalyst for water electrolysis hydrogen production system and preparation method thereof | |
| CN1827266A (en) | Process for preparing nano nickel powder | |
| CN113782731A (en) | Cathode material for water-based zinc secondary battery and preparation method thereof | |
| CN112846224A (en) | Nano porous metal material and preparation method and application thereof | |
| CN102610793A (en) | Nitride substituted graphene oxide electrode and preparation method thereof | |
| CN111790446B (en) | Iron/tungsten bimetal organic framework anode oxygen evolution composite material and preparation method thereof | |
| CN115036152B (en) | Hollow spherical boron-carbon-nitrogen material and preparation method thereof | |
| CN105977477A (en) | Preparation method of silicon carbon electrode material with micro-nano structure | |
| Meng et al. | Nickel/porous carbon composite derived from bimetallic MOFs for electrical double-layer supercapacitor application | |
| CN116445955A (en) | Cobalt phosphide electrolytic water catalyst and preparation method thereof | |
| CN114171740B (en) | Preparation method of nano lithium iron phosphate positive electrode material and lithium ion battery | |
| CN114852997A (en) | Three-dimensional carbon nanotube-mesoporous carbon composite sponge, and preparation method and application thereof | |
| CN108063252A (en) | A kind of activation method of cathode material for high capacity lithium ion battery | |
| CN109192550B (en) | Self-supporting film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210528 |