CN1676670B - Method for continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave - Google Patents
Method for continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave Download PDFInfo
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Abstract
This invention refers to the producing field of nano materials, specifically about a kind of method of preparing nano metal powder by organic mediator electrolysis/supersonic wave continuous producing. This method uses membrane to divide the electrolysis bath into two parts. The part with the negative pole is filled with electric conducting organic solution, and the other part with the positive pole is filled with the inorganic electrolysis water solution. Besides, we can fill the same kind of solution into the both parts. The membrane of the electrolysis bath should be positive ion changing film or simple physical isolating film. This invention has wide applicability, as it is suitable for the element both more and less active than hydrogen. The efficiency of the electrolysis is high, and the cost is low. Also, the powder produced can disperse easily and it is stable. What is more, the structure of the device is simple, and it can realize convenient manufacture and continuous producing, so it can be developed to realize commercial process.
Description
Technical field
The present invention relates to field of nano material preparation, specifically be meant a kind of method of continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave.
Background technology
At present, utilize research that the electrolysis/ultrasonic wave method prepares metal-powder as " investigation of materials association symposial proceedings " 1995 both at home and abroad, disclose a kind of impulse ultrasound and pulsed current of on same electrode, adopting simultaneously in 372:75～81 and prepared the method for crystal metal powder." Materials Science and Engineering " 2002,18 (4) and for example: disclose a kind of ultrasonic generator that adopts in 70～74 and combined the method for preparing copper powder with negative electrode.These two kinds of methods all are that electrolysis and ultrasonication are arranged in carrying out in a kind of inorganic electrolyte water solution system, and they all have a common shortcoming: only be applicable to the torpescence metal of the relative hydrogen of preparation or the easy nano metal powder of surface passivation.And being not suitable for for relative hydrogen than active metal such as zinc, iron rule; because; nano metal powder breaks away from after negative electrode enters the aqueous solution, does not have galvanic protection, more active nano metal powder be easy to water or water in oxygen generation chemical reaction and dissolve.Also have " Acta Metallurgica Sinica " 2000,36 (6): disclose a kind of method of using out-phase electrolyte solution electrolytic preparation metal-powder in 659～661, it adopts stratified liquid phase structure up and down, the upper strata is an organic solution, lower floor is the inorganic electrolyte aqueous solution, utilizes the different physical properties of both density to realize going up lower leaf.Cathode cylinder places two liquid phase intersections, among two liquid phases, and constantly rotation.When cathode cylinder is in the inorganic electrolyte aqueous solution, electrochemical reaction takes place, metal is separated out in the above, and cathode cylinder because organic solution is non-conductive, stops so metal is separated out when turning in the organic solution.Use high speed organic liquor stream method to make metal-powder break away from negative electrode then.But in this method; because the influence of other factors such as the gravity of metal-powder itself, high-speed jet; the metal-powder that spins off from negative electrode is as easy as rolling off a log to be reentered in the middle of the inorganic electrolyte aqueous solution; make its be easy to water or water in oxygen generation chemical reaction and dissolve; the metal-powder that generates is actually and is difficult to collect and protects, thereby this method can not have industrial prospect.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, solve common electrolysis/ultrasonic wave pointedly and prepare the torpescence metal that only is applicable to the relative hydrogen of preparation of nanometer powder method existence or the nano metal powder problem of easy surface passivation.Propose a kind of applied widelyly, both be applicable to the torpescence metallic element of relative hydrogen, also be applicable to the method than the continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave of active metal element of relative hydrogen.
The objective of the invention is to realize by following measure:
The method of continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave is separated into two portions with barrier film with electrolyzer, it is characterized in that the electrolyzer that negative electrode is housed adds electroconductibility organic solution; The anodic electrolyzer is housed adds the inorganic electrolyte aqueous solution.Can also be in addition: the electrolyzer of negative electrode is housed and the anodic electrolyzer is housed all adds with a kind of electroconductibility organic solution.
The prescription of the electroconductibility organic solution described in the aforesaid method is as follows: with 1 liter dimethyl sulphoxide solution or/and N, the N dimethyl formamide solution is a benchmark, add anhydrous salt 30～50 grams that contain the metal target element, supporting electrolyte 20～100 grams, additive 0.1～0.8 gram, wherein, the anhydrous salt that contains the metal target element be the metal target element chlorate, nitrate, vitriol wherein any one salt or their composition; Supporting electrolyte be potassium, sodium, lithium nitrate, chlorate, vitriol wherein any one salt or their composition; Additive be gelatin or/and wooden sodium sulfonate or/and thiocarbamide.
The prescription of the inorganic electrolyte aqueous solution in the aforesaid method is as follows: in 1 liter the aqueous solution, add salt 30～60 grams that contain the metal target element, supporting electrolyte 30～85 gram, the salt that wherein contains the metal target element be the chlorate of metal target element, nitrate, vitriol wherein any one salt or their composition.Supporting electrolyte be potassium, sodium, ammonium nitrate, chlorate, vitriol wherein any one salt or their composition.
Metal target element described in the aforesaid method is meant any one in iron, zinc, nickel, aluminium, manganese, cobalt, tin, lead, titanium, vanadium, cadmium, molybdenum, chromium and the copper.
Barrier film described in the aforesaid method is cationic exchange membrane or common physical membrane.
Compare with preparation method of the prior art, the present invention has following major advantage:
1, the present invention is applied widely, both be applicable to the torpescence metallic element of relative hydrogen, also be applicable to relative hydrogen than the active metal element, say in theory, as long as the material of energy electrolytic deposition can adopt present method technology to prepare needed nano metal powder.
2, electrolytic efficiency height of the present invention, because the inefficiency electrolysis does not take place in theory, thereby the electrolytic efficiency of present method is up to more than 85 percent.Solved the deficiency of in the past in a kind of inorganic electrolyte water solution system, carrying out the method for electrolysis and ultrasonication.
3, the present invention utilizes ultrasonic method stripping metal powder to be easy to realize that effect is obvious, has solved the problem of scraping the powder difficulty in the common electrolysis.
4, the present invention adopts ultrasonic vibration, the jet that it produced can make the metal that is deposited on cathode surface hightail cathode surface and with the flow dispersion of solution in whole solution, prevent that particulate from growing up, controlled powder size effectively, so that prepare qualified nano metal powder.
5, the present invention adopts ultrasonic wave can also make metal-powder be easy to disperse in solution, has suppressed the reunion of metal-powder to a certain extent, and the metal-powder particle diameter of generation is even.
6, the present invention adopts electroconductibility organic solution to compare the easier dispersion of nanometer powder and stable with aqueous electrolyte liquid.
7, preparation cost of the present invention is low, particularly for refractory metal, generally needs at present to adopt high energy such as LASER HEAT evaporation technique to prepare nanometer powder, and cost is very high.Adopt present method preparation then can reduce preparation cost greatly, therefore have tangible technical superiority.
8, the apparatus structure that adopts simple, easily manufactured, and can realize continuous production; Be convenient to enlarge to realize suitability for industrialized production.
Embodiment
Embodiment 1
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 1 liter of dimethyl sulphoxide solution is benchmark, adds ferrous or anhydrous Nickel Chloride of anhydrous chlorides of rase or anhydrous cobalt dichloride 40 grams; Anhydrous nitric acid sodium or anhydrous chlorides of rase sodium or anhydrous sodium sulphate 80 grams; Gelatin 0.1 gram, wooden sodium sulfonate's 0.15 gram, thiocarbamide 0.15 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add iron protochloride or Nickel Chloride or cobalt dichloride 50 grams in 1 premium on currency solution; Ammonium chloride or ammonium sulfate or ammonium nitrate 40 grams, SODIUMNITRATE or sodium sulfate or sodium-chlor 15 grams.Anode electrode uses insoluble electrode, and material is a graphite, and cathode electrode selects stainless steel as material.Negative electrode separates with ultrasonic generator, and the distance between them is 18 millimeters.Distance between anode electrode and the cathode electrode is 40 millimeters.Electrolysis power is a D.C. regulated power supply.Electrolysis time is 1 hour 40 minutes.The current density of cathode electrode be 1.83 kilo-amperes/square metre.Room temperature is 25 degrees centigrade, and the temperature of electrolytic solution is 52 degrees centigrade in the electrolytic preparation process.The metallic cation that is equipped with in the anodic electrolyzer enters into the electrolyzer that negative electrode is housed by barrier film under the effect of electrical forces, carry out electrochemical reaction and generate needed metal-powder in the liquid layer of cathode electrode surface or near surface.Above-mentioned metallic cation is to be generated or/and provided by the metal target positively charged ion in the inorganic electrolyte aqueous solution by redox reaction by soluble anode.Ultrasonic generator produces ultrasonic wave simultaneously, the high-pressure spray that under hyperacoustic vibrations and cavatition, produces, make metal powder granulates just be detached cathode surface and dispersion suspension when also not having enough time to grow up in the middle of electroconductibility organic solution, immense pressure or jet that ultrasonic cavitation produces can be pulverized the macrobead in the solution again.The metallic particles that peels off does not out contact with the air in the external world in the middle of being scattered in electroconductibility organic solution, even hydrogen can not react with electroconductibility organic solution than the active metal yet relatively.Ultrasonic wave has suppressed the reunion of metal-powder again effectively, makes it disperse better, be suspended in the middle of the electroconductibility organic solution.The electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know through X-ray diffraction analysis, generate the average crystal grain size and be about cobalt powder 3.32 grams that iron powder 3.61 grams of 68 nanometers or nickel powder 3.45 grams that the average crystal grain size is about 75 nanometers or average crystal grain size are about 72 nanometers, their current efficiency is respectively 92.3%, 89.9% and 88.2%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the mean particle size of iron powder that is generated or nickel powder or cobalt powder is all below 100 nanometers.
Embodiment 2
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 500 milliliters of N, N dimethyl formamide solution and 500 milliliters of dimethyl sulfoxide (DMSO) are benchmark, add anhydrous cupric sulfate 15 grams, anhydrous cupric chloride 20 grams, anhydrous nitric acid copper 15 grams; Anhydrous nitric acid sodium or anhydrous sodium sulphate or anhydrous chlorides of rase sodium 45 grams, anhydrous potassium chloride or anhydrous potassium sulfate or anhydrous nitric acid potassium 55 grams; Wooden sodium sulfonate's 0.3 gram, thiocarbamide 0.1 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add copper sulfate 25 grams in 1 premium on currency solution, cupric chloride 15 grams, cupric nitrate 20 grams; Ammonium chloride or ammonium sulfate or ammonium nitrate 40 grams, Repone K or vitriolate of tartar or saltpetre 45 grams.Anode electrode uses the solubility electrode, and material is a copper.Cathode electrode also selects copper as material.Negative electrode separates with ultrasonic generator, and the distance between them is 20 millimeters.Distance between anode electrode and the cathode electrode is 40 millimeters.Electrolysis power is a D.C. regulated power supply.The current density of cathode electrode be 2.15 kilo-amperes/square metre.Room temperature is 24 degrees centigrade, and the temperature of electrolytic solution is 52 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 40 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate copper powder 3.56 grams that the average crystal grain size is about 70 nanometers, current efficiency is 92.8%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the mean particle size of the copper powder that is generated is below 100 nanometers.
Embodiment 3
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 1 liter of N, the N dimethyl formamide solution is a benchmark, adds Zincomed or anhydrous slufuric acid cadmium 20 grams, anhydrous nitric acid zinc or anhydrous nitric acid cadmium 25 grams; Anhydrous nitric acid sodium or anhydrous sodium sulphate or anhydrous chlorides of rase sodium 40 grams, anhydrous potassium chloride or anhydrous potassium sulfate or anhydrous nitric acid potassium 35 grams, anhydrous nitric acid lithium or anhydrous slufuric acid lithium or Lithium chloride (anhydrous) 15 grams; Gelatin 0.15 gram, thiocarbamide 0.15 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add zinc nitrate or cadmium nitrate 25 grams in 1 premium on currency solution, zinc chloride or Cadmium chloride fine powder 20 grams; Repone K or vitriolate of tartar or saltpetre 30 grams.Anode electrode uses insoluble electrode, and material is a graphite.Cathode electrode selects stainless steel as material.Negative electrode separates with ultrasonic generator, and the distance between them is 18 millimeters.Distance between anode electrode and the cathode electrode is 35 millimeters.Electrolysis power is a D.C. regulated power supply.The current density of cathode electrode be 2.4 kilo-amperes/square metre.Room temperature is 25 degrees centigrade, and the temperature of electrolytic solution is 58 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 45 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate the average crystal grain size and be about zinc powder 4.31 grams of 68 nanometers or cadmium powder 3.83 grams that the average crystal grain size is about 59 nanometers, their current efficiency is respectively 86.4% and 85.2%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the mean particle size of zinc powder that is generated or cadmium powder is all below 100 nanometers.
Embodiment 4
With the General Physics barrier film electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 1 liter of N, the N dimethyl formamide solution is a benchmark, adds anhydrous slufuric acid aluminium 25 grams, Aluminum chloride anhydrous 15 grams; Anhydrous potassium chloride or anhydrous potassium sulfate or anhydrous nitric acid potassium 35 grams, anhydrous nitric acid lithium or anhydrous slufuric acid lithium or Lithium chloride (anhydrous) 45 grams; Gelatin 0.15 gram, wooden sodium sulfonate's 0.2 gram.Be equipped with the anodic electrolyzer add 1 liter with the electrolyzer that negative electrode is housed in identical electroconductibility organic solution.Anode electrode uses the solubility electrode, and material is an aluminium.Cathode electrode selects stainless steel as material.Negative electrode separates with ultrasonic generator, and the distance between them is 18 millimeters.Distance between anode electrode and the cathode electrode is 40 millimeters.Electrolysis power is a D.C. regulated power supply.The current density of cathode electrode be 1.94 kilo-amperes/square metre.Room temperature is 26 degrees centigrade, and the temperature of electrolytic solution is 56 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 40 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate aluminium powder 3.76 grams that the average crystal grain size is about 70 nanometers, current efficiency is 88.3%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the mean particle size of the aluminium powder that is generated is below 100 nanometers.
Embodiment 5
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 400 milliliters of N, N dimethyl formamide solution and 600 milliliters of dimethyl sulfoxide (DMSO) are benchmark, add Manganese chloride anhydrous 20 grams, anhydrous nitric acid manganese 20 grams; Anhydrous nitric acid sodium or anhydrous sodium sulphate or anhydrous chlorides of rase sodium 40 grams, anhydrous nitric acid lithium or anhydrous slufuric acid lithium or Lithium chloride (anhydrous) 25 grams; Wooden sodium sulfonate's 0.25 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add manganous sulfate 35 grams in 1 premium on currency solution, manganous nitrate 20 grams; Ammonium chloride or ammonium sulfate or ammonium nitrate 40 grams, SODIUMNITRATE or sodium sulfate or sodium-chlor 15 grams, Repone K or vitriolate of tartar or saltpetre 15 grams.Anode electrode uses insoluble electrode, and material is a graphite.Cathode electrode selects stainless steel as material.Cathode electrode and ultrasonic generator combine.Distance between anode electrode and the cathode electrode is 35 millimeters.Electrolysis power is a D.C. regulated power supply.The current density of cathode electrode be 2.1 kilo-amperes/square metre.Room temperature is 26 degrees centigrade, and the temperature of electrolytic solution is 54 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 50 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate manganese powder 3.58 grams that the average crystal grain size is about 73 nanometers, current efficiency is 87.5%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the mean particle size of the manganese powder that is generated is below 100 nanometers.
Embodiment 6
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 1 liter of dimethyl sulphoxide solution is benchmark, adds plumbous 30 grams of anhydrous nitric acid tin or anhydrous nitric acid; Anhydrous potassium chloride or anhydrous potassium sulfate or anhydrous nitric acid potassium 85 grams; Thiocarbamide 0.3 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add nitric acid tin or lead nitrate 35 grams in 1 premium on currency solution; SODIUMNITRATE or sodium sulfate or sodium-chlor 40 grams.Anode electrode uses insoluble electrode, and material is a graphite.The material of cathode electrode is selected stainless steel.Negative electrode separates with ultrasonic generator, and the distance between them is 16 millimeters.Distance between anode electrode and the cathode electrode is 40 millimeters.Electrolysis power is a D.C. regulated power supply.The current density of cathode electrode be 2.2 kilo-amperes/square metre.Room temperature is 23 degrees centigrade, and the temperature of electrolytic solution is 55 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 50 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate the average crystal grain size and be about glass putty 3.82 grams of 85 nanometers or lead powder 3.77 grams that the average crystal grain size is about 77 nanometers, their current efficiency is respectively 85.8% and 87.2%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the glass putty that is generated or the mean particle size of lead powder are all below 100 nanometers.
Embodiment 7
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 600 milliliters of N, N dimethyl formamide solution and 400 milliliters of dimethyl sulfoxide (DMSO) are benchmark, add anhydrous slufuric acid titanium or anhydrous slufuric acid vanadium 40 grams; Anhydrous nitric acid lithium or anhydrous slufuric acid lithium or Lithium chloride (anhydrous) 20 grams; Gelatin 0.2 gram, wooden sodium sulfonate's 0.2 gram, thiocarbamide 0.3 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add titanium sulfate or Vanadosulfuric acid 35 grams in 1 premium on currency solution, titanium chloride or vanadium chloride 20 grams; SODIUMNITRATE or sodium sulfate or sodium-chlor 25 grams, Repone K or vitriolate of tartar or saltpetre 25 grams.Anode electrode uses insoluble electrode, and material is a graphite.The material of cathode electrode is selected stainless steel.Negative electrode separates with ultrasonic generator, and the distance between them is 18 millimeters.Distance between anode electrode and the cathode electrode is 35 millimeters.Electrolysis power is the controllable pulse power supply, and frequency is 2 kilohertzs.The current density of cathode electrode be 1.98 kilo-amperes/square metre.Room temperature is 28 degrees centigrade, and the temperature of electrolytic solution is 58 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 45 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate the average crystal grain size and be about titanium valve 3.34 grams of 79 nanometers or vanadium powder 3.45 grams that the average crystal grain size is about 74 nanometers, their current efficiency is respectively 87.1% and 86.9%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the titanium valve that is generated or the mean particle size of vanadium powder are all below 100 nanometers.
Embodiment 8
With Du Pont's 324 perfluor cationic exchange membranes electrolyzer is separated into two portions.In being housed, the electrolyzer of negative electrode adds electroconductibility organic solution.The concrete prescription of electroconductibility organic solution is: with 1 liter of N, the N dimethyl formamide solution is a benchmark, adds anhydrous chromium trichloride or anhydrous chlorides of rase molybdenum 35 grams; Anhydrous nitric acid sodium or anhydrous sodium sulphate or anhydrous chlorides of rase sodium 30 grams, anhydrous potassium chloride or anhydrous potassium sulfate or anhydrous nitric acid potassium 35 grams, anhydrous nitric acid lithium or anhydrous slufuric acid lithium or Lithium chloride (anhydrous) 15 grams; Gelatin 0.3 gram.Add the inorganic electrolyte aqueous solution in the anodic electrolyzer is housed, the concrete prescription of the inorganic electrolyte aqueous solution is: add chromium sulphate or molybdenum trisulfate 30 grams in 1 premium on currency solution; Ammonium chloride or ammonium sulfate or ammonium nitrate 30 grams.Anode electrode uses insoluble electrode, and material is a graphite.Cathode electrode selects stainless steel as material.Negative electrode separates with ultrasonic generator, and the distance between them is 20 millimeters.Distance between anode electrode and the cathode electrode is 35 millimeters.Electrolysis power is a D.C. regulated power supply.The current density of cathode electrode be 2.23 kilo-amperes/square metre.Room temperature is 24 degrees centigrade, and the temperature of electrolytic solution is 54 degrees centigrade in the electrolytic preparation process.Electrolytic detailed process such as embodiment 1.After 1 hour 50 minutes, the electroconductibility organic solution that contains metal-powder is carried out centrifugation, vacuum-drying, repetitive scrubbing has obtained metal-powder.Know that through X-ray diffraction analysis generate the average crystal grain size and be about chromium powder 3.82 grams of 86 nanometers or molybdenum powder 3.63 grams that the average crystal grain size is about 77 nanometers, their current efficiency is respectively 86.6% and 88.2%.Analysis obtains through SA-CP4 centrifugal type particle-size analyzer, and the chromium powder that is generated or the mean particle size of molybdenum powder are all below 100 nanometers.
Claims (5)
1. the method for a continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave, with barrier film electrolyzer is separated into two portions, it is characterized in that: the electrolyzer that negative electrode is housed adds electroconductibility organic solution, the prescription of described electroconductibility organic solution is as follows: with 1 liter dimethyl sulphoxide solution or/and N, the N dimethyl formamide solution is a benchmark, add anhydrous salt 30～50 grams that contain the metal target element, supporting electrolyte 20～100 grams, additive 0.1～0.8 gram; The anodic electrolyzer is housed adds the inorganic electrolyte aqueous solution, the prescription of the described inorganic electrolyte aqueous solution is as follows: in 1 liter the aqueous solution, add salt 30～60 grams that contain the metal target element, supporting electrolyte 30～85 grams; Described diaphragm for electrolytic cell is selected cationic exchange membrane or common physical membrane for use.
2. the method for a continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave, with barrier film electrolyzer is separated into two portions, it is characterized in that: the electrolyzer of negative electrode is housed and the anodic electrolyzer is housed all adds with a kind of electroconductibility organic solution, the prescription of described electroconductibility organic solution is as follows: with 1 liter dimethyl sulphoxide solution or/and N, the N dimethyl formamide solution is a benchmark, add anhydrous salt 30～50 grams that contain the metal target element, supporting electrolyte 20～100 grams, additive 0.1～0.8 gram.
3. the method for a kind of continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave according to claim 1, it is characterized in that: the anhydrous salt of the metal target element that in electroconductibility organic solution, is contained be the chlorate of metal target element, nitrate, vitriol wherein any one salt or their composition, supporting electrolyte be potassium, sodium, lithium nitrate, chlorate, vitriol wherein any one salt or their composition, additive be gelatin or/and wooden sodium sulfonate or/and thiocarbamide; The salt of the metal target element that in the inorganic electrolyte aqueous solution, is contained be the metal target element chlorate, nitrate, vitriol wherein any one salt or their composition, supporting electrolyte be potassium, sodium, ammonium nitrate, chlorate, vitriol wherein any one salt or their composition.
4. the method for a kind of continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave according to claim 2, it is characterized in that: the anhydrous salt of the metal target element that in electroconductibility organic solution, is contained be the chlorate of metal target element, nitrate, vitriol wherein any one salt or their composition, supporting electrolyte be potassium, sodium, lithium nitrate, chlorate, vitriol wherein any one salt or their composition, additive be gelatin or/and wooden sodium sulfonate or/and thiocarbamide.
5. according to the method for claim 3 or 4 described a kind of continuously preparing nano metal powder by organic medium electrolysis/ultrasonic wave, it is characterized in that: described metal target element is meant any one in iron, zinc, nickel, aluminium, manganese, cobalt, tin, lead, titanium, vanadium, cadmium, molybdenum, chromium and the copper.
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| CN102586810A (en) * | 2012-03-17 | 2012-07-18 | 张无量 | Method for preparing magnesium metal powder |
| CN102978666B (en) * | 2012-08-02 | 2015-07-01 | 厦门紫金矿冶技术有限公司 | Nano-gold preparation method |
| CN103122468B (en) * | 2012-10-25 | 2015-04-29 | 扬州双盛锌业有限公司 | Preparation method of flaky zinc powder |
| CN103233246B (en) * | 2013-04-19 | 2016-02-24 | 中南大学 | A kind of electrochemical cathode prepares the method for powder body material |
| CN104014814B (en) * | 2014-06-19 | 2016-03-30 | 江苏凯尚节能科技有限公司 | A kind of preparation method of Nano-Zinc particle |
| CN106283113B (en) * | 2015-06-05 | 2018-03-27 | 张无量 | The method for preparing magnesium metal |
| CN107955952A (en) * | 2017-11-02 | 2018-04-24 | 马鞍山市宝奕金属制品工贸有限公司 | A kind of method using scum production high-purity iron powder |
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