CN112317758B - Preparation method of nano nickel - Google Patents
Preparation method of nano nickel Download PDFInfo
- Publication number
- CN112317758B CN112317758B CN201911044339.0A CN201911044339A CN112317758B CN 112317758 B CN112317758 B CN 112317758B CN 201911044339 A CN201911044339 A CN 201911044339A CN 112317758 B CN112317758 B CN 112317758B
- Authority
- CN
- China
- Prior art keywords
- nickel
- reaction
- heating
- nano
- carbonate
- 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.)
- Active
Links
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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- 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
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a preparation method of nano nickel, which comprises the following steps: s1: carrying out a complex reaction on metallic nickel and an ammonium carbonate solution to generate a nickel-ammonia complex solution; s2: decomposing the nickel ammonia complex to generate nickel carbonate; s3: and step S2, heating the nickel carbonate in a reducing atmosphere step by step, and carrying out thermal decomposition reduction reaction to generate nano nickel. The nano nickel prepared by the method is in a nano-sized strip structure, and is easy to disperse, large in specific surface area and small in resistance.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a preparation method of nano nickel.
Background
Nickel is an important class of metallic materials and is widely used in almost all modern industrial fields. The micro/nano multi-level structure construction technology is combined with the traditional technology, and the properties of the assembly body are more accurately regulated and controlled by regulating the components, size, shape and organization of the structural units from the molecular level, so that the properties of metals in the application fields of catalysis, electrodes, chemical protective coatings, soft magnetic materials, low-temperature superplastic materials and the like can be greatly changed. The methods for preparing the metal ballasted nanostructure have been developed greatly recently, and the synthesized nanostructure comprises nanospheres by a chemical reduction method, nano rings deposited by an electrochemical template, and the like.
The nano nickel material prepared by the prior method has the following problems: 1. easy agglomeration and difficult uniform dispersion in the solution; 2. the nano nickel material is spherical, and the conductivity is required to be improved; 3. the preparation process is complex, the purity is low, and the waste pollutes the environment.
Disclosure of Invention
The technical problem to be solved by the invention is the problem existing in the current nano metal nickel material.
In order to solve the technical problems, the invention provides a preparation method of nano nickel, which comprises the following steps:
s1: carrying out a complex reaction on metallic nickel and an ammonium carbonate solution to generate a nickel-ammonia complex solution;
s2: decomposing the nickel ammonia complex to generate nickel carbonate;
s3: and step S2, heating the nickel carbonate in a reducing atmosphere step by step, and carrying out thermal decomposition reduction reaction to generate nano nickel.
The thermal decomposition reduction adopts a step heating method, and can comprise the following steps: heating the initial temperature to 100-200 ℃, preserving heat for reaction, and heating to 250-800 ℃ to generate nano nickel.
As a preferred embodiment, the thermal decomposition reduction includes:
heating in the first stage: heating to 100-200 ℃ within 3 hours;
and (3) the second-stage heat preservation reaction: the reaction is carried out for more than 8 hours at the temperature of 100-200 ℃;
and in the third stage, heating: heating to 250-800 ℃ within 15 hours.
Further preferably, the thermal decomposition reduction reaction in step S3 includes:
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 100-150 ℃ within 0.5-2 hours;
and (3) the second-stage heat preservation reaction: reacting for 10-20 hours at 100-150 ℃ with heat preservation;
and in the third stage, heating: heating to 300-600 ℃ within 3-8 hours.
Preferably, the nickel ammonia complex solution in the step S2 is stirred at the temperature of 80-180 ℃ and decomposed into nickel carbonate and ammonia gas.
Preferably, step S1 includes:
adding metallic nickel into an ammonium carbonate solution, introducing air or oxygen, and carrying out a complexing reaction to generate a nickel-ammonia complex solution; wherein the method comprises the steps ofThe concentration of nickel ions in the nickel ammonia complex solution is 40-100 g/L, and NH in the ammonium bicarbonate solution 3 The concentration is 80-200 g/L, CO 2 The concentration is 40-200 g/L.
Preferably, after the thermal decomposition reduction reaction in step S3, a cooling step is further included to thermally decompose the reduction product, and naturally cool to room temperature.
Preferably, the reducing atmosphere is one or a combination of hydrogen and ethanol.
Preferably, the reducing atmosphere is hydrogen: when the nickel carbonate is subjected to thermal decomposition reduction reaction, hydrogen is continuously introduced, and the hydrogen introduction amount is more than 1 time of the nickel carbonate substance. Further preferably, the reducing atmosphere is hydrogen: when the nickel carbonate is subjected to thermal decomposition reduction reaction, hydrogen is continuously introduced, and the introduced amount of the hydrogen is more than 2 times of the amount of the nickel carbonate substance.
The invention also provides the nano nickel prepared by the method, which has a strip structure, the length is below 600nm, and the length-diameter ratio is 2-50:1.
The nano nickel prepared by the preparation method provided by the invention has a strip structure, the length is less than 600nm, and the length-diameter ratio is 2-50:1; the purity is up to 99.8%, the specific surface area is 15-35 m 2 /g, resistance is small by 1X 10 -5 ～2.5×10 -5 Omega cm; and it is uniformly dispersed in the solution and can be cross-linked to increase the conductivity of the solution. The preparation method provided by the invention is environment-friendly and has no waste emission polluting the environment.
Drawings
FIG. 1 is a first electron microscope image of nano-nickel prepared in example 1 of the present invention;
FIG. 2 is a second electron microscope image of nano-nickel prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in the following in connection with specific embodiments. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of nano nickel, wherein nickel carbonate adopts stepped heating in a reducing atmosphere to carry out thermal decomposition reduction, and the preparation method comprises the following steps:
s1: the metal nickel and the ammonium bicarbonate solution are subjected to complexation reaction to generate nickel ammonia complex solution, which comprises the following steps:
adding metallic nickel into an ammonium carbonate solution, introducing air or oxygen, and carrying out a complexing reaction to generate a nickel-ammonia complex solution; wherein the concentration of nickel ions in the nickel-ammonia complex solution is 40-100 g/L, and NH in the ammonium bicarbonate solution 3 The concentration is 80-200 g/L, CO 2 The concentration is 40-200 g/L.
S2: the nickel ammonia complex is decomposed to generate nickel carbonate, which comprises the following steps:
and step S2, stirring the nickel ammine complex solution at the temperature of 80-180 ℃ to decompose nickel carbonate and ammonia gas.
S3: the nickel carbonate obtained in the step S2 is thermally decomposed and reduced in a reducing atmosphere to generate nano nickel; wherein the thermal decomposition reduction adopts stepped temperature rise: heating the initial temperature to 100-200 ℃, preserving heat for reaction, and heating to 250-800 ℃ to generate nano nickel. Under the step heating condition, the nickel carbonate prepared by decomposing the nickel ammonia complex is stably pyrolyzed and reduced, and the step heating and reducing air flow enable the nickel carbonate to be pyrolyzed and reduced to form strip-shaped nano-sized metallic nickel.
The reducing atmosphere can be selected from one or a combination of hydrogen and ethanol. When the reducing atmosphere is hydrogen, the hydrogen is introduced more than 2 times of the nickel carbonate substance, the reduction reaction is complete, the purity of nickel is high, and the formation of strip nano nickel is facilitated. The flow rate of the reducing gas can be set appropriately in combination with the reaction time and the amount of the reducing atmosphere required.
The nickel carbonate prepared by decomposing the nickel ammonia complex is in a nano-sized strip structure, a cross-linked structure can be generated in application, and the conductivity is better than that of granular nano nickel and the performance is better.
Example 1
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) 6kg of metallic nickel was added to the complex reaction apparatus, followed by addition of 110L of an ammonium bicarbonate solution (the concentration of ammonia in the ammonium bicarbonate solution was 100g/L and CO 2 The concentration of (1) is 60 g/L), air is introduced, the reaction is complete, aqueous solution of nickel ammine complex is obtained, and the filtration is carried out;
2) Adding the filtered nickel ammine complex aqueous solution into a decomposition reaction device, reacting completely at the temperature of 100 ℃ to generate nickel carbonate precipitate and ammonia gas, condensing and absorbing the ammonia gas, recycling the ammonia gas, dehydrating and drying nickel carbonate;
3) Adding dehydrated and dried nickel carbonate into a reducing furnace, introducing hydrogen (the hydrogen is continuously introduced in the whole reaction process, the introduced amount of the hydrogen is 2 times of the amount of the nickel carbonate substance),
heating in the first stage: the initial temperature of the reaction is room temperature for 1 hour, and the temperature is raised to 120 ℃;
and (3) the second-stage heat preservation reaction: the reaction is carried out for 12 hours at 120 ℃;
and in the third stage, heating: 3 hours, the temperature was raised to 600 ℃.
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared in the embodiment is 99.9%; as shown in fig. 1 and fig. 2, the nano nickel in the embodiment has a strip structure, the length is 50 nm-600 nm, and the length-diameter ratio is 2-50:1; the specific surface area of the nano nickel is 35m 2 And/g. The stab probe method detects the resistance, the resistance is 1 multiplied by 10 -5 Ω·cm。
Dispersion experiments: 0.5kg of nickel powder, 2kg of nickel balls with a diameter of 1mm are added into a container with a diameter of 200mm, and the mixture is ground for 1min at a speed of 100 revolutions per minute in an alcohol medium. The observation shows that the dispersion is good and no agglomeration phenomenon exists.
Example 2
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) 6kg of metallic nickel was added to the complex reaction apparatus, followed by addition of 110L of an ammonium bicarbonate solution (the concentration of ammonia in the ammonium bicarbonate solution was 100g/L and CO 2 The concentration of (1) is 60 g/L), air is introduced, the reaction is complete, the nickel ammine complex aqueous solution is obtained,filtering;
2) Adding the filtered nickel ammine complex aqueous solution into a decomposition reaction device, heating to 180 ℃ under a pressure environment, completely reacting to generate nickel carbonate precipitate and ammonia gas, condensing and absorbing the ammonia gas, recycling the ammonia gas, dehydrating and drying the nickel carbonate;
3) Adding dehydrated and dried nickel carbonate into a reducing furnace, introducing hydrogen (the hydrogen is continuously introduced in the whole reaction process, the introduced amount of the hydrogen is 2 times of the amount of the nickel carbonate substance),
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 100 ℃ within 0.5 hour;
and (3) the second-stage heat preservation reaction: the reaction is carried out for 20 hours at 100 ℃;
and in the third stage, heating: the temperature was raised to 300℃over 3 hours.
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared by the method is 99.8%; the nano nickel of the embodiment is in a strip structure, the length is 50 nm-400 nm, and the length-diameter ratio is 2-50:1; the specific surface area of the nano nickel is 23m 2 And/g. The stab probe method detects the resistance, the resistance is 1.4X10 -5 Ω·cm。
Dispersion experiments: as observed in example 1, the dispersion was good and no agglomeration was observed.
Example 3
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) 6kg of metallic nickel was added to the complex reaction apparatus, followed by addition of 110L of an ammonium bicarbonate solution (the concentration of ammonia in the ammonium bicarbonate solution was 100g/L and CO 2 The concentration of (1) is 60 g/L), air is introduced, the reaction is complete, aqueous solution of nickel ammine complex is obtained, and the filtration is carried out;
2) Adding the filtered nickel ammine complex aqueous solution into a decomposition reaction device, completely reacting in a pressure environment at 120 ℃ to generate nickel carbonate precipitate and ammonia gas, condensing and absorbing the ammonia gas, recycling the ammonia gas, dehydrating and drying the nickel carbonate;
3) Adding dehydrated and dried nickel carbonate into a reducing furnace, introducing hydrogen (the hydrogen is continuously introduced in the whole reaction process, the introduced amount of the hydrogen is 2 times of the amount of the nickel carbonate substance),
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 150 ℃ within 2 hours;
and (3) the second-stage heat preservation reaction: the reaction is carried out for 8 hours at 150 ℃;
and in the third stage, heating: the temperature was raised to 600℃over 8 hours.
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared by the method is 99.8%; the nano nickel of the embodiment is in a strip structure, the length is 50 nm-400 nm, and the length-diameter ratio is 2-50:1; the specific surface area of the nano nickel is 25m 2 And/g. The stab probe method detects the resistance, the resistance is 1.3 multiplied by 10 -5 Ω·cm。
Dispersion experiments: as observed in example 1, the dispersion was good and no agglomeration was observed.
Example 4
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) 6kg of metallic nickel was added to the complexing reaction apparatus, followed by addition of 60L of an ammonium bicarbonate solution (the concentration of ammonia in the ammonium bicarbonate solution was 180g/L and CO 2 The concentration of (2) is 200 g/L), air is introduced, the reaction is complete, aqueous solution of nickel ammine complex is obtained, and the filtration is carried out;
2) Adding the filtered nickel ammine complex aqueous solution into a decomposition reaction device, reacting completely at the temperature of 80 ℃ to generate nickel carbonate precipitate and ammonia gas, condensing and absorbing the ammonia gas, recycling the ammonia gas, dehydrating and drying nickel carbonate;
3) Adding dehydrated and dried nickel carbonate into a reducing furnace, introducing hydrogen (the hydrogen is continuously introduced in the whole reaction process, the introduced amount of the hydrogen is 2 times of the amount of the nickel carbonate substance),
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 200 ℃ within 3 hours;
and (3) the second-stage heat preservation reaction: the reaction is carried out for 8 hours at 200 ℃;
and in the third stage, heating: the temperature was raised to 250℃over 2 hours.
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared by the method is 99.9%; the nano nickel of the embodiment is in a strip structure, the length is 50 nm-400 nm, and the length-diameter ratio is 2-50:1; the specific surface area of the nano nickel is 25m 2 And/g. The stab probe method detects the resistance, the resistance is 1.8X10 -5 Ω·cm。
Dispersion experiments: as observed in example 1, the dispersion was good and no agglomeration was observed.
Example 5
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) 6kg of metallic nickel was added to the complex reaction apparatus, followed by addition of 110L of an ammonium bicarbonate solution (the concentration of ammonia in the ammonium bicarbonate solution was 100g/L and CO 2 The concentration of (1) is 60 g/L), air is introduced, the reaction is complete, aqueous solution of nickel ammine complex is obtained, and the filtration is carried out;
2) Adding the filtered nickel ammine complex aqueous solution into a decomposition reaction device, reacting completely at the temperature of 100 ℃ to generate nickel carbonate precipitate and ammonia gas, condensing and absorbing the ammonia gas, recycling the ammonia gas, dehydrating and drying nickel carbonate;
3) Adding dehydrated and dried nickel carbonate into a reducing furnace, introducing hydrogen (the hydrogen is continuously introduced in the whole reaction process, the introduced amount of the hydrogen is 2 times of the amount of the nickel carbonate substance),
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 120 ℃ within 1 hour;
and (3) the second-stage heat preservation reaction: the reaction is carried out for 10 hours at 120 ℃;
and in the third stage, heating: for 15 hours, the temperature was raised to 800 ℃.
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared in the embodiment is 99.9%; as shown in FIG. 1, the nano nickel in the embodiment has a strip structure, the length is 50 nm-400 nm, and the length-diameter ratio is 2-50:1; the specific surface area of the nano nickel is 28m 2 And/g. The stab probe method detects the resistance, the resistance is 1 multiplied by 10 -5 Ω·cm。
Dispersion experiments: as observed in example 1, the dispersion was good and no agglomeration was observed.
Comparative example 1
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) Taking 12kg of commercial nickel carbonate for drying;
3) Adding the dried nickel carbonate into a reduction furnace, introducing hydrogen,
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 120 ℃ for 1 hour;
and (3) the second-stage heat preservation reaction: the reaction is carried out for 12 hours at 120 ℃;
and in the third stage, heating: for 6 hours, the temperature was raised to 600 ℃.
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared by the method is 99.7%; the nano nickel of the embodiment is granular, and the grain diameter is 400-500 nm; the specific surface area of the nano nickel is 15m 2 And/g. The stab probe method detects the resistance, the resistance is 1 multiplied by 10 -4 Ω·cm。
Dispersion experiments: as in example 1, the agglomeration phenomenon was observed.
Comparative example 2
The preparation method of the nano nickel in the embodiment comprises the following steps:
1) 6kg of metallic nickel was added to the complex reaction apparatus, followed by addition of 110L of an ammonium bicarbonate solution (the concentration of ammonia in the ammonium bicarbonate solution was 100g/L and CO 2 The concentration of (1) is 60 g/L), air is introduced, the reaction is complete, aqueous solution of nickel ammine complex is obtained, and the filtration is carried out;
2) Adding the filtered nickel ammine complex aqueous solution into a decomposition reaction device, reacting completely at the temperature of 100 ℃ to generate nickel carbonate precipitate and ammonia gas, condensing and absorbing the ammonia gas, recycling the ammonia gas, dehydrating and drying nickel carbonate;
3) Adding dehydrated and dried nickel carbonate into a reduction furnace, introducing hydrogen, heating to 600 ℃ for 8 hours at the initial reaction temperature, and preserving heat for 10 hours;
4) Cooling to room temperature to prepare the nano nickel.
Through detection, the purity of the nano nickel prepared by the method is 99.8%; the nano nickel of the embodiment is in a mixed structure of a strip structure and particles, has the agglomeration phenomenon,the length of the strip structure is 50 nm-400 nm, the length-diameter ratio is 2-50:1, and the particle size of the granular structure is about 100 nm; specific surface area of 10m 2 Per g, melting point 401 ℃. The stab probe method detects the resistance, the resistance is 4 multiplied by 10 -5 Ω·cm。
Dispersion experiments: as in example 1, some agglomeration was observed.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises the element.
The foregoing is merely exemplary of the present invention and is not intended to limit the present invention. Various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are to be included in the scope of the claims of the present invention.
Claims (5)
1. The preparation method of the nano nickel is characterized by comprising the following steps:
s1: adding metallic nickel into an ammonium carbonate solution, introducing air or oxygen, and carrying out a complexing reaction to generate a nickel-ammonia complex solution; wherein the concentration of nickel ions in the nickel-ammonia complex solution is 40-100 g/L, and NH in the ammonium bicarbonate solution 3 The concentration is 80-200 g/L, CO 2 The concentration is 40-200 g/L;
s2: decomposing the nickel ammonia complex to generate nickel carbonate;
s3: step S2, heating nickel carbonate in a reducing atmosphere step by step, and carrying out thermal decomposition reduction reaction to generate nano nickel; the step temperature rise of the thermal decomposition reduction reaction comprises: heating in the first stage: heating to 100-200 ℃ within 3 hours; and (3) the second-stage heat preservation reaction: the reaction is carried out for more than 8 hours at the temperature of 100-200 ℃; and in the third stage, heating: heating to 250-800 ℃ within 15 hours; the reducing atmosphere is hydrogen: when the nickel carbonate is subjected to thermal decomposition reduction reaction, hydrogen is continuously introduced, and the hydrogen introduction amount is more than 1 time of the nickel carbonate substance.
2. The method of preparing nano-nickel according to claim 1, wherein the step-wise heating of the thermal decomposition reduction reaction in step S3 comprises:
heating in the first stage: the initial temperature of the reaction is room temperature, and the temperature is raised to 100-150 ℃ within 0.5-2 hours;
and (3) the second-stage heat preservation reaction: performing heat preservation reaction for 10-20 hours at 100-150 ℃;
and in the third stage, heating: heating to 300-600 ℃ within 3-8 hours.
3. The method for preparing nano nickel according to claim 1, wherein the step S2 nickel ammonia complex solution is stirred at a temperature of 80-180 ℃ and decomposed into nickel carbonate and ammonia gas.
4. The method for preparing nano-nickel according to claim 1, wherein after the thermal decomposition reduction reaction in step S3, a cooling step is further included, and the thermal decomposition reduction reaction product is naturally cooled to room temperature, so as to obtain nano-nickel.
5. The nano nickel prepared by the preparation method of any one of claims 1-4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2019107163483 | 2019-08-05 | ||
| CN201910716348 | 2019-08-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112317758A CN112317758A (en) | 2021-02-05 |
| CN112317758B true CN112317758B (en) | 2023-05-19 |
Family
ID=74319603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911044339.0A Active CN112317758B (en) | 2019-08-05 | 2019-10-30 | Preparation method of nano nickel |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112317758B (en) |
| WO (1) | WO2021022801A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113003618A (en) * | 2021-03-01 | 2021-06-22 | 杭州申柯新材料有限公司 | Production line for producing high-purity nickel protoxide by direct oxidation method of metallic nickel and production process thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1381036A (en) * | 1971-09-14 | 1975-01-22 | Nickel Le | Method for producing high-purity nickel powder with predetermined physical characteristics |
| US4089676A (en) * | 1976-05-24 | 1978-05-16 | Williams Gold Refining Company Incorporated | Method for producing nickel metal powder |
| CN1344190A (en) * | 1999-11-19 | 2002-04-10 | 堺化学工业株式会社 | Method for producing fine powder of metallic nickel comprised of fine spherical particles |
| CN1765549A (en) * | 2005-11-25 | 2006-05-03 | 北京科技大学 | Method for preparing nano nickel powder by precipitation-hydrogen reduction process |
| CN101007356A (en) * | 2007-01-24 | 2007-08-01 | 深圳市格林美高新技术有限公司 | Environmental friendly nickel board and processing technology and device thereof |
| JP2007191772A (en) * | 2006-01-20 | 2007-08-02 | Sakai Chem Ind Co Ltd | Method for producing nickel fine particle |
| CN102489718A (en) * | 2011-12-14 | 2012-06-13 | 丹阳市博高新材料技术有限公司 | Method for preparing submicron flaky superfine nickel powder |
| CN104625082A (en) * | 2015-02-12 | 2015-05-20 | 湖南微科新材料有限公司 | Nanometer nickel powder preparation method |
| JP2015140480A (en) * | 2014-01-30 | 2015-08-03 | 国立大学法人高知大学 | Method for manufacturing nickel powder |
| CN107073586A (en) * | 2014-07-02 | 2017-08-18 | 因温斯特技术公司 | Nickel metallic is manufactured |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647423A (en) * | 1969-10-27 | 1972-03-07 | Floyd Acoveno | Production of copper, nickel oxide and zinc oxide |
| EP0388808B1 (en) * | 1989-03-20 | 1994-06-15 | Inco Limited | Nickel hydroxide |
| JP4341119B2 (en) * | 1999-09-24 | 2009-10-07 | 堺化学工業株式会社 | Method for producing spherical nickel powder |
| AUPR917701A0 (en) * | 2001-11-29 | 2001-12-20 | QNI Technology Limited | Integrated ammoniacal solvent extraction and hydrogen reduction of nickel |
| EP1986804B1 (en) * | 2006-02-16 | 2011-12-28 | Brigham Young University | Preparation of uniform nanoparticles of ultra-high purity metal oxides, mixed metal oxides, metals, and metal alloys |
| US7758668B1 (en) * | 2006-04-18 | 2010-07-20 | Chemnano, Inc. | Process of manufacturing metallic nano-scale powders |
| CN102091789A (en) * | 2010-12-21 | 2011-06-15 | 丹阳市求精合金钢有限公司 | Method for preparing submicron hammer ball superfine nickel powder |
| CN104708008B (en) * | 2013-12-13 | 2017-02-01 | 格林美股份有限公司 | Making method for cobalt-nickel alloy powder |
| CN109689257A (en) * | 2016-09-27 | 2019-04-26 | 住友金属矿山株式会社 | The manufacturing method of nickel powder |
| CN106861701B (en) * | 2017-02-28 | 2020-01-03 | 山西大学 | Preparation method and application of nano-powder nickel catalyst |
-
2019
- 2019-10-30 CN CN201911044339.0A patent/CN112317758B/en active Active
-
2020
- 2020-02-13 WO PCT/CN2020/074981 patent/WO2021022801A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1381036A (en) * | 1971-09-14 | 1975-01-22 | Nickel Le | Method for producing high-purity nickel powder with predetermined physical characteristics |
| US4089676A (en) * | 1976-05-24 | 1978-05-16 | Williams Gold Refining Company Incorporated | Method for producing nickel metal powder |
| CN1344190A (en) * | 1999-11-19 | 2002-04-10 | 堺化学工业株式会社 | Method for producing fine powder of metallic nickel comprised of fine spherical particles |
| CN1765549A (en) * | 2005-11-25 | 2006-05-03 | 北京科技大学 | Method for preparing nano nickel powder by precipitation-hydrogen reduction process |
| JP2007191772A (en) * | 2006-01-20 | 2007-08-02 | Sakai Chem Ind Co Ltd | Method for producing nickel fine particle |
| CN101007356A (en) * | 2007-01-24 | 2007-08-01 | 深圳市格林美高新技术有限公司 | Environmental friendly nickel board and processing technology and device thereof |
| CN102489718A (en) * | 2011-12-14 | 2012-06-13 | 丹阳市博高新材料技术有限公司 | Method for preparing submicron flaky superfine nickel powder |
| JP2015140480A (en) * | 2014-01-30 | 2015-08-03 | 国立大学法人高知大学 | Method for manufacturing nickel powder |
| CN106413952A (en) * | 2014-01-30 | 2017-02-15 | 国立大学法人高知大学 | Manufacturing method for nickel powder |
| CN107073586A (en) * | 2014-07-02 | 2017-08-18 | 因温斯特技术公司 | Nickel metallic is manufactured |
| CN104625082A (en) * | 2015-02-12 | 2015-05-20 | 湖南微科新材料有限公司 | Nanometer nickel powder preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 金属镍纳米材料研究进展;张磊等;材料导报;第14卷(第2期);第57-58页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112317758A (en) | 2021-02-05 |
| WO2021022801A1 (en) | 2021-02-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018120067A1 (en) | Waste biomass-derived metal-free catalysts for oxygen reduction reaction | |
| CN109745984A (en) | A kind of preparation method of the monatomic doped carbon nanometer pipe of metal | |
| CN109824044B (en) | Preparation method of metal monoatomic-doped graphene | |
| CN104291385A (en) | Nickel cobalt oxide mesoporous microsphere and preparation method thereof | |
| WO2007011397A2 (en) | Molybdenum metal powder and production thereof | |
| CN111483999B (en) | Preparation method of nitrogen-doped carbon nanotube, nitrogen-doped carbon nanotube and application of nitrogen-doped carbon nanotube | |
| CN106825597A (en) | A kind of preparation method of cobalt powder | |
| EP3216757A1 (en) | Method for preparing graphene by molten state inorganic salt reaction bed | |
| CN112317758B (en) | Preparation method of nano nickel | |
| CN104625082B (en) | Nanometer nickel powder preparation method | |
| CN112830468B (en) | Preparation method and application of carbon material rich in topological defects obtained by high-temperature ammonia treatment | |
| CN105883805B (en) | A kind of preparation method of the high-specific surface area carbosphere based on tea seed shell base | |
| CN105084344A (en) | Graphene preparation method and graphene prepared through graphene preparation method | |
| CN103880000A (en) | Preparation method of ultralight graphene powder | |
| CN105964260A (en) | Preparation method for metal catalyst and preparation method for carbon nano tube prepared by metal catalyst | |
| CN113117719B (en) | Nickel-based metal nano material with unconventional crystalline phase and preparation method and application thereof | |
| CN103920874A (en) | Preparation method of hollow composite nano-particles | |
| CN104096836A (en) | Graphene-coated magnetic nickel nanoparticle and preparation method thereof | |
| CN104607224B (en) | Nitrogen-doped graphitization carbon encapsulation iron nanoparticle preparation method | |
| CN107746057B (en) | Preparation method of superfine molybdenum carbide | |
| CN113088988B (en) | Cobalt-doped foam carbon pyrolysis derived carbon material and preparation method thereof | |
| CN104117356A (en) | Preparation method of non-noble metal catalyst used for oxygen reduction reaction | |
| CN105945277B (en) | Onion-like fullerene cladding Metal Palladium core-shell structure nanometer particle and preparation method thereof | |
| CN106111030B (en) | A kind of gold/carbon complex microsphere and preparation method thereof | |
| CN101544365A (en) | Method for preparing hollow carbon nano-cage through iodized thermal treatment |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |