CN106910903B - A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst - Google Patents
A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst Download PDFInfo
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- CN106910903B CN106910903B CN201710099756.XA CN201710099756A CN106910903B CN 106910903 B CN106910903 B CN 106910903B CN 201710099756 A CN201710099756 A CN 201710099756A CN 106910903 B CN106910903 B CN 106910903B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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Abstract
The invention discloses a kind of preparation methods of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst of cell catalyst technical field, it is characterised in that: specific step is as follows: S1 for the preparation method of the nickel cobalt carbon nanotube aerogel zinc and air cell catalyst: ammonium hydroxide is added dropwise and adjusts pH value；S2: while cobalt nitrate solution and ammonium hydroxide is added dropwise and stirs evenly；S3: ammonium hydroxide is added dropwise again and adjusts pH value, generates hydrogel；S4: the water in dehydrated alcohol displacement hydrogel obtains freezing shape alcogel；S5: alcogel is moved into autoclave, and the pressurization that heats up；S6: it by ethanol evaporation, and is purged to obtain catalyst precarsor with nitrogen；S7: crushing and is sieved; catalyst production method of the present invention is simple, can carry out the industrial production of scale, prepared catalyst activity is high, stability is good, granular superfine; premise guarantee is improved for the uniform carbon nanotube of preparation mass, there is very high economic benefit.
Description
Technical field
The present invention relates to cell catalyst technical field, specially a kind of nickel cobalt carbon nanotube aerogel zinc and air cell catalysis
The preparation method of agent.
Background technique
Cobalt acid lithium is battery material most widely used at present, but cobalt resource is increasingly deficient, expensive, and cobalt acid lithium battery
There is security risk in use.Nickle cobalt lithium manganate with relatively inexpensive nickel and manganese instead of in cobalt acid lithium 2/3rds with
On cobalt, advantage is clearly compared with other lithium cell anode material lithium manganates, LiFePO 4 in terms of cost, nickel
Cobalt lithium manganate material and cobalt acid lithium are very close in terms of chemical property and processing performance, so that nickel-cobalt lithium manganate material becomes
New battery material and gradually replace cobalt acid lithium, become the favorite of lithium ion battery material of new generation.
Carbon nanotube is the seamless nanotube curled by single-layer or multi-layer graphite flake, and carbonaceous gas prepares carbon nanotube
Reaction condition is mild, process easily realize and can a large amount of, continuous production, the catalysis of cobalt decomposes preparation carbon nanotube to carbonaceous gas and exists
In most cases, the carbon nanotube morphology of acquisition is not easy to control and diameter is thicker, and wherein the preparation method of catalyst is to carbon nanometer
The reactivity of pipe and the carbon nanotube morphology of acquisition will make a significant impact, and the diameter of carbon nanotube and the particle of catalyst are big
It is small to be consistent substantially.Therefore preparing equally distributed ultrafine metal catalyst is to obtain the carbon that caliber is tiny, form is uniform to receive
The premise of mitron.Based on this, we have proposed a kind of throwings of the preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst
Enter to use, to solve the above problems.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst, with
Solve the problems mentioned above in the background art.
To achieve the above object, the invention provides the following technical scheme: a kind of nickel cobalt carbon nanotube aerogel zinc and air cell
The preparation method of catalyst, specific step is as follows for the nickel cobalt/carbon nanotube aerogel zinc and air cell catalyst preparation method:
S1: in the metal nickel solution that ammonium hydroxide is added drop-wise to 0.2~0.4mol/l in the case where room temperature stirs strongly, until mixed liquor
Stop that ammonium hydroxide is added dropwise when pH value is 7.5；
S2: at the same be added dropwise 0.2~0.4mol/l cobalt nitrate solution and ammonium hydroxide into mixed solution, and stir 15~
20min；
S3: ammonium hydroxide is added dropwise again maintains the pH value of mixed solution between 8.5~9, and is stirred and stands, and mixes molten
Hydrogel is generated in liquid；
S4: using the water in dehydrated alcohol displacement hydrogel, until the water content in filtrate is lower than with gas chromatographic detection
5%, it obtains freezing shape alcogel at this time；
S5: alcogel is moved into autoclave, sealing autoclave after dehydrated alcohol is added, and with certain rate by high pressure
Kettle is warming up to 260~280 DEG C, and the pressure in autoclave reaches 75~78atm at this time, keeps under dehydrated alcohol supercriticality
25~30min；
S6: opening the outlet valve of autoclave, slowly release alcohol vapour, makes pressure in autoclave gradually near normal pressure,
And nitrogen purging autoclave is made into its near room temperature in a nitrogen atmosphere, catalyst precarsor is obtained after opening autoclave；
S7: being crushed catalyst precarsor and be sieved, and ultra-fine nickel-cobalt catalyst is prepared.
Preferably, in the step S1, metal nickel solution uses method of cementation by the impurity in its solution before the reaction
It filters out.
Preferably, in the step S3, stirring and the time stood are respectively 3h.
Preferably, in the step S5, the rate of heat addition of autoclave is 25~35 DEG C/min, the critical-temperature of dehydrated alcohol
It is 243 DEG C, critical pressure 6.4MPa.
Compared with prior art, the beneficial effects of the present invention are: catalyst production method of the present invention is simple, scale can be carried out
The industrial production of change, prepared catalyst activity is high, stability is good, granular superfine, receives for the uniform carbon of preparation mass
Mitron improves premise guarantee, has very high economic benefit.
Detailed description of the invention
Fig. 1 is work flow diagram of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment one
A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst, the nickel cobalt/carbon nanotube aerogel
Specific step is as follows for the preparation method of zinc and air cell catalyst:
S1: in the metal nickel solution that ammonium hydroxide is added drop-wise to 0.2mol/l in the case where room temperature stirs strongly, until the pH value of mixed liquor
Stop that ammonium hydroxide is added dropwise when being 7.5, metal nickel solution uses method of cementation to filter out the impurity in its solution before the reaction；
S2: while the cobalt nitrate solution and ammonium hydroxide that 0.2mol/l is added dropwise be into mixed solution, and stirs 15min；
S3: ammonium hydroxide is added dropwise again maintains the pH value of mixed solution between 8.5, and is stirred and stands, mixed solution
Middle generation hydrogel, stirring and the time stood are respectively 3h；
S4: using the water in dehydrated alcohol displacement hydrogel, until the water content in filtrate is lower than with gas chromatographic detection
5%, it obtains freezing shape alcogel at this time；
S5: alcogel is moved into autoclave, sealing autoclave after dehydrated alcohol is added, and with certain rate by high pressure
Kettle is warming up to 260 DEG C, and the pressure in autoclave reaches 75atm at this time, and 25min is kept under dehydrated alcohol supercriticality, high
The rate of heat addition for pressing kettle is 25 DEG C/min, and the critical-temperature of dehydrated alcohol is 243 DEG C, critical pressure 6.4MPa；
S6: opening the outlet valve of autoclave, slowly release alcohol vapour, makes pressure in autoclave gradually near normal pressure,
And nitrogen purging autoclave is made into its near room temperature in a nitrogen atmosphere, catalyst precarsor is obtained after opening autoclave；
S7: being crushed catalyst precarsor and be sieved, and ultra-fine nickel-cobalt catalyst is prepared.
Embodiment two
A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst, the nickel cobalt/carbon nanotube aerogel
Specific step is as follows for the preparation method of zinc and air cell catalyst:
S1: in the metal nickel solution that ammonium hydroxide is added drop-wise to 0.4mol/l in the case where room temperature stirs strongly, until the pH value of mixed liquor
Stop that ammonium hydroxide is added dropwise when being 7.5, metal nickel solution uses method of cementation to filter out the impurity in its solution before the reaction；
S2: while the cobalt nitrate solution and ammonium hydroxide that 0.4mol/l is added dropwise be into mixed solution, and stirs 20min；
S3: ammonium hydroxide is added dropwise again maintains the pH value of mixed solution between 9, and is stirred and stands, in mixed solution
Hydrogel is generated, stirring and the time stood are respectively 3h；
S4: using the water in dehydrated alcohol displacement hydrogel, until the water content in filtrate is lower than with gas chromatographic detection
5%, it obtains freezing shape alcogel at this time；
S5: alcogel is moved into autoclave, sealing autoclave after dehydrated alcohol is added, and with certain rate by high pressure
Kettle is warming up to 280 DEG C, and the pressure in autoclave reaches 8atm at this time, and 30min, high pressure are kept under dehydrated alcohol supercriticality
The rate of heat addition of kettle is 35 DEG C/min, and the critical-temperature of dehydrated alcohol is 243 DEG C, critical pressure 6.4MPa；
S6: opening the outlet valve of autoclave, slowly release alcohol vapour, makes pressure in autoclave gradually near normal pressure,
And nitrogen purging autoclave is made into its near room temperature in a nitrogen atmosphere, catalyst precarsor is obtained after opening autoclave；
S7: being crushed catalyst precarsor and be sieved, and ultra-fine nickel-cobalt catalyst is prepared.
Embodiment three
A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst, the nickel cobalt/carbon nanotube aerogel
Specific step is as follows for the preparation method of zinc and air cell catalyst:
S1: in the metal nickel solution that ammonium hydroxide is added drop-wise to 0.3mol/l in the case where room temperature stirs strongly, until the pH value of mixed liquor
Stop that ammonium hydroxide is added dropwise when being 7.5, metal nickel solution uses method of cementation to filter out the impurity in its solution before the reaction；
S2: while the cobalt nitrate solution and ammonium hydroxide that 0.3mol/l is added dropwise be into mixed solution, and stirs 18min；
S3: ammonium hydroxide is added dropwise again maintains the pH value of mixed solution between 8.7, and is stirred and stands, mixed solution
Middle generation hydrogel, stirring and the time stood are respectively 3h；
S4: using the water in dehydrated alcohol displacement hydrogel, until the water content in filtrate is lower than with gas chromatographic detection
5%, it obtains freezing shape alcogel at this time；
S5: alcogel is moved into autoclave, sealing autoclave after dehydrated alcohol is added, and with certain rate by high pressure
Kettle is warming up to 270 DEG C, and the pressure in autoclave reaches 76atm at this time, and 28min is kept under dehydrated alcohol supercriticality, high
The rate of heat addition for pressing kettle is 30 DEG C/min, and the critical-temperature of dehydrated alcohol is 243 DEG C, critical pressure 6.4MPa；
S6: opening the outlet valve of autoclave, slowly release alcohol vapour, makes pressure in autoclave gradually near normal pressure,
And nitrogen purging autoclave is made into its near room temperature in a nitrogen atmosphere, catalyst precarsor is obtained after opening autoclave；
S7: being crushed catalyst precarsor and be sieved, and ultra-fine nickel-cobalt catalyst is prepared.
In summary described in embodiment, highly preferred embodiment of the present invention is embodiment three, the catalyst granules prepared
Homogenous superfine provides premise for the uniform carbon nanotube of preparation mass, while preparation method is simple, efficient, prepares
Catalyst activity it is high, stability is good.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (3)
1. a kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst, it is characterised in that: the nickel cobalt/carbon nanometer
Specific step is as follows for the preparation method of pipe aeroge zinc and air cell catalyst:
S1: in the metal nickel solution that ammonium hydroxide is added drop-wise to 0.2~0.4mol/L in the case where room temperature stirs strongly, until the pH value of mixed liquor
Stop that ammonium hydroxide is added dropwise when being 7.5；
S2: at the same be added dropwise 0.2~0.4mol/L cobalt nitrate solution and ammonium hydroxide into mixed solution, and stir 15~20min；
S3: ammonium hydroxide is added dropwise again maintains the pH value of mixed solution between 8.5~9, and is stirred and stands, in mixed solution
Generate hydrogel；
S4: using the water in dehydrated alcohol displacement hydrogel, until the water content in filtrate is lower than 5% with gas chromatographic detection, this
When obtain freeze shape alcogel；
S5: alcogel is moved into autoclave, sealing autoclave after dehydrated alcohol is added, and with certain rate by autoclave liter
Temperature is to 260~280 DEG C, and the pressure in autoclave reaches 75~78atm at this time, under dehydrated alcohol supercriticality keep 25~
30min, the rate of heat addition of autoclave are 25~35 DEG C/min, and the critical-temperature of dehydrated alcohol is 243 DEG C, and critical pressure is
6.4MPa；
S6: opening the outlet valve of autoclave, slowly release alcohol vapour, so that the pressure in autoclave is gradually down to normal pressure, and will
Nitrogen purging autoclave makes it be down to room temperature in a nitrogen atmosphere, obtains catalyst precarsor after opening autoclave；
S7: being crushed catalyst precarsor and be sieved, and ultra-fine nickel-cobalt catalyst is prepared.
2. a kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst according to claim 1, special
Sign is: in the step S1, metal nickel solution uses method of cementation to filter out the impurity in its solution before the reaction.
3. a kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst according to claim 1, special
Sign is: in the step S3, stirring and the time stood are respectively 3h.
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| CN109755600B (en) * | 2019-01-29 | 2022-08-05 | 天津大学 | Carbon cloth loaded nickel-cobalt-oxygen nanosheet composite material, preparation method thereof and application of electrode |
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| CN104993159A (en) * | 2015-06-09 | 2015-10-21 | 东华大学 | Dual-function catalyst and preparation thereof and application in metal-air battery |
| CN105289617A (en) * | 2015-11-11 | 2016-02-03 | 东华大学 | Nickel cobalt oxide/carbon nanotube composite catalyst, preparation and application thereof |
| CN105609791A (en) * | 2015-12-18 | 2016-05-25 | 东华大学 | La-Co-Mn and carbon nanotube dual-functional composite catalyst and preparation and application thereof |
| CN105609790A (en) * | 2015-12-14 | 2016-05-25 | 青岛大学 | Preparation method for Ni-Co/carbon nanotube aerogel catalyst of zinc-air battery |
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| CN103041755A (en) * | 2011-10-13 | 2013-04-17 | 林志予 | Preparation method of nanocomposite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104993159A (en) * | 2015-06-09 | 2015-10-21 | 东华大学 | Dual-function catalyst and preparation thereof and application in metal-air battery |
| CN105289617A (en) * | 2015-11-11 | 2016-02-03 | 东华大学 | Nickel cobalt oxide/carbon nanotube composite catalyst, preparation and application thereof |
| CN105609790A (en) * | 2015-12-14 | 2016-05-25 | 青岛大学 | Preparation method for Ni-Co/carbon nanotube aerogel catalyst of zinc-air battery |
| CN105609791A (en) * | 2015-12-18 | 2016-05-25 | 东华大学 | La-Co-Mn and carbon nanotube dual-functional composite catalyst and preparation and application thereof |
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