CN101077476A - Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel - Google Patents
Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel Download PDFInfo
- Publication number
- CN101077476A CN101077476A CN 200610078405 CN200610078405A CN101077476A CN 101077476 A CN101077476 A CN 101077476A CN 200610078405 CN200610078405 CN 200610078405 CN 200610078405 A CN200610078405 A CN 200610078405A CN 101077476 A CN101077476 A CN 101077476A
- Authority
- CN
- China
- Prior art keywords
- nickel
- complexing agent
- surfactant
- aqueous solution
- precipitating reagent
- 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.)
- Granted
Links
Images
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to spherical nickel powder precursor preparing process. The process includes mixing the reaction material containing surfactant to react through stirring. The process is simple, clean and pollution-free, and can prepare spherical nickel powder of 0.1-2 micron diameter. The prepared nickel powder may be used widely in catalysis, powder metallurgy, cell, magnetic material and other industry.
Description
Technical field
The preparation method who the present invention relates to a kind of preparation method of globular powdered nickel presoma and use the globular powdered nickel of this presoma.
Background technology
Particle diameter has excellent physical chemistry less than 5 microns superfine metal powder material, occupies important position in new material industry, is important material base and the guide of development high-tech industry.Extra-fine nickel powder because it has great skin effect and bulk effect, has all obtained comparatively extensive use in many fields such as chemical industry catalysis, powder metallurgy, battery, magnetic materials as a kind of metal powder material.At present, the preparation method of extra-fine nickel powder is a lot, mainly contains electrolysis, carbonyl nickel thermal decomposition method, water slurry pressurized hydrogen reducing process and evaporation-condensation method etc.These methods all have its advantage separately, but also have certain limitation simultaneously.The powder size that makes as electrolysis is bigger and wayward, carbonyl nickel thermal decomposition rule exists serious pollution problem, the pressurized hydrogen reducing process needs autoclave, and the apparatus expensive of evaporation-condensation method, investment are big, and the electronation rule is owing to use carcinogenic raw material such as hydrazine hydrate to cause very big injury and can't be widely used human body.
CN 1491762A discloses a kind of preparation method of fibrous nickel powder, this method comprise with soluble nickel salting liquid and compound precipitants (comprising complexing agent and precipitating reagent) solution through the spraying feeding device respectively from different containers and stream add in the reaction vessel, at Ni
2+-NH
3-NH
4+-Cl
--C
2O
4 2--H
2Carry out the composite precipitation conversion in the O system, the control temperature is 55-85 ℃, and pH is 7.0-9.0, initial Ni in the feed liquid
2+Concentration is the 0.4-1.2 mol; The composite precipitation thing that obtains after then reaction being finished is through washing, filter and be drying to obtain powdered nickel precursor body; And then powdered nickel precursor body is inserted in the electric furnace of PID adjusting, the control temperature is 350-600 ℃, and at (H
2+ N
2) atmosphere regulation and control under carry out thermal decomposition; Nickel powder after again thermal decomposition being finished cools off immediately with surface anti-oxidation to be handled to room temperature, promptly makes fibrous nano level Special Nickel Powder.
CN 1600480A discloses a kind of preparation method of fibrous nickel powder, and this method comprises at first and adding in the reaction vessel, at Ni with certain feed way through feeding device with the soluble nickel salting liquid and by stoichiometric composite precipitation agent solution
2+-NH
3-NH
4+-SG
N--C
2O
4 2--H
2O (SG
N-Represent acid group Cl
-, SO
4-, CH
3COO
-Perhaps NO
3 -) carry out the composite precipitation conversion in the system, the control temperature is 55-85 ℃, pH is 7.0-9.0, initial Ni in the feed liquid
2+Concentration is the 0.4-1.2 mol; The composite precipitation thing that obtains after then reaction being finished is powdered nickel precursor body through washing, filtration and drying; And then powdered nickel precursor body is inserted in the electric furnace of PID adjusting, the control temperature is 350-650 ℃, and under the non-oxidizing atmosphere regulation and control, carrying out thermal decomposition, the nickel powder after thermal decomposition is finished cools off immediately with surface anti-oxidation to be handled to room temperature, promptly makes fibrous nano level Special Nickel Powder.
Although said method can make the nanoscale Special Nickel Powder, because products therefrom is fibrous, operating difficulties in washing, filtration and drying course, reaction condition is wayward, is difficult to avoid agglomeration, thereby can only obtain the bulky grain nickel powder usually.In addition, the described method of CN 1491762A needs sprayer unit, and sprayer unit causes obstruction easily, is unfavorable for amplifying producing; In addition, this method uses hydrogen that potential safety hazard is arranged in the presoma roasting process.Although and CN 1600480A does not clearly limit feeding device and feed way, by comparing and can find with the described method of CN 1491762A, this method need use spray-drying installation to feed in raw material equally.
And spherical nickel powder can overcome the shortcoming that above-mentioned fibrous nickel powder is easily reunited, make nickel powder in filtration, drying and washing process, operate easily, the specific surface and the tap density of material can also be provided simultaneously, thereby can improve specific capacity, cycle performance and the Stability Analysis of Structures of battery, be more satisfactory positive electrode.For this reason, CN 1516301A discloses a kind of preparation method who contains the ball-shape nickel hydroxide of nanoscale ball nickel, it is characterized in that this method comprises the following three kinds of materials of preparation earlier: material A: get nickelous sulfate, cobaltous sulfate, zinc sulfate and be mixed with the mixed sulfate solution that molar concentration is respectively 0.5-2.0 mol, 0-0.1 mol and 0-0.2 mol; Material B: density is the concentrated ammonia liquor of 0.88-0.92 grams per milliliter; Material C: concentration is the caustic solution of 6-10 mol; Then with above-mentioned three kinds of materials simultaneously continuously implantation temperature be 40-60 ℃ special reactor E and temperature be 60-100 ℃ another special reactor F in, react continuously simultaneously in two reactors and continuous overflow in aging tank, after filtration, obtain containing the high-density ball-shape nickel hydroxide powder of nanoscale ball nickel after the washing, oven dry.Although emphasize in this application can make the ball-shape nickel hydroxide powder with this method, and the structure of unexposed wherein said special reactor E and F and how to obtain above-mentioned reactor, and above-mentioned reactor is the key point that realizes said method.Therefore, according to the disclosure, people still can not obtain globular powdered nickel.
Because nickel powder can be inherited the shape of presoma at roasting process, the shape of powdered nickel precursor body directly determines the shape of nickel powder product.Therefore, in order to obtain globular powdered nickel, at first should obtain the globular powdered nickel presoma.
Summary of the invention
The objective of the invention is to reunite easily for the powdered nickel precursor body that overcomes prior art for preparing causes operating difficulties or to the demanding shortcoming of equipment, provides a kind of powdered nickel precursor body of preparation to be not easy to reunite and the preparation method of globular powdered nickel presoma low for equipment requirements.
The preparation method of globular powdered nickel presoma provided by the invention comprises reaction mass is mixed contact under stirring condition, and described reaction mass contains nickel salt, precipitating reagent and complexing agent, and wherein, described reaction mass also contains surfactant.
The preparation method of globular powdered nickel provided by the invention comprises preparation globular powdered nickel presoma, then presoma is carried out roasting, and wherein, the preparation method of described globular powdered nickel presoma is the preparation method of globular powdered nickel presoma provided by the invention.
The preparation method of globular powdered nickel presoma provided by the invention is by setting about preparing the globular powdered nickel presoma from reaction raw materials.Owing to contain surfactant in the reaction raw materials, make and adopt traditional reaction unit, simple process condition, can make the globular powdered nickel presoma, and the powdered nickel precursor body that makes is by the CO in gentleness
2Or roasting can make globular powdered nickel in the nitrogen atmosphere.Because the presoma that makes is a spheric granules, makes that separation, washing, the drying process of presoma are very smooth and easy, thereby enhances productivity greatly.Because do not use poisonous reducing agents such as hydrazine hydrate in course of reaction, roasting process need not use flammable explosive gas such as hydrogen, makes that whole nickel powder preparation technology is more safe and reliable, has realized the green production of globular powdered nickel.Can make the globular powdered nickel of 0.1-2 micron with method provided by the invention, the gained nickel powder can be used for various uses, as the positive electrode of nickel-based battery, as conducting resinl.
Description of drawings
Fig. 1 is SEM (SEM) photo of the globular powdered nickel presoma that adopts the inventive method and make;
Fig. 2 is the SEM SEM photo of the globular powdered nickel that adopts the inventive method and make;
Fig. 3 is the SEM photo of the powdered nickel precursor body that adopts prior art and make;
Fig. 4 is the SEM photo of the nickel powder that adopts prior art and make.
The specific embodiment
According to method provided by the invention, although a spot of surfactant can prevent the reunion of powdered nickel precursor body, obtain the globular powdered nickel presoma, but under the preferable case, the addition of described surfactant is the 0.5-20 weight % of nickel salt, precipitating reagent and complexing agent total amount, be preferably 1-15 weight %, more preferably 2-10 weight %.
Among the present invention, described surfactant can be cationic surfactant, anion surfactant and non-ionic surface active agent.Described cationic surfactant comprises amine and quaternary ammonium salt, the example of anion emulsifier comprises fatty acid soaps, alkylsulfonate, alkyl sulfate-base and phosphate are as the serial emulsifying agent of condensation product (OP) of alkylphenol and oxirane, the serial emulsifying agent of NPE (NP), iso-octyl sulfate, sulfosuccinic acid two cyclohexyl sodium, sulfosuccinic acid two cyclohexyl potassium, dodecyl benzyl dimethyl ammonium chloride, softex kw, OTAC, fatty acid polyglycol oxirane ester, the triacetamide oleate, in the stearoyl lactate one or more.Examples of nonionic surfactants comprises the fatty acid ester and the polyvinyl alcohol of polyoxyethylene-type, oxirane and propylene oxide block polymer, polyalcohol.The present invention is preferably anion surfactant.The inventor finds that also one or more in the lauryl sodium sulfate in the anion surfactant, benzene sulfonic acid sodium salt, softex kw, the OTAC especially are suitable for preparing the globular powdered nickel that particle diameter is the 0.1-2 micron.Therefore the more preferably described surfactant of the present invention is one or more in lauryl sodium sulfate, benzene sulfonic acid sodium salt, softex kw, the OTAC.
Because the present invention mainly relates to increase surfactant with acquisition globular powdered nickel presoma in reaction mass, thereby does not have special requirement to nickel salt, complexing agent and precipitating reagent, satisfy conventional powdered nickel precursor body preparation and require to get final product.Described nickel salt can be various water soluble nickel salt, as in nickel nitrate, nickelous sulfate, the nickel chloride one or more.Described complexing agent can be various can with the reagent of nickel generation complex reaction, the preferred described complexing agent of the present invention is one or more in ammonia, ethylenediamine, propane diamine, formic acid, acetate and the acetylacetone,2,4-pentanedione.Described precipitating reagent can be one or more in this area various nickel salt precipitating reagents commonly used such as alkali, carbonate, oxalic acid, the oxalates.Can be in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus, ammonium carbonate, carbonic hydroammonium, oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate one or more particularly, the present invention be preferably one or more in oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate.
The addition of described nickel salt, precipitating reagent, complexing agent be preferably the mol ratio that makes precipitating reagent and nickel salt for the 0.95-1.25 of stoichiometric proportion between them doubly, the mol ratio of complexing agent and nickel salt is 0.1-5.For example, when described precipitating reagent was NaOH, potassium hydroxide, the addition of described precipitating reagent and nickel salt made OH
-With Ni
2+Mol ratio be 1.9-2.5; When described precipitating reagent was oxalic acid and/or oxalates, the addition of described nickel salt, precipitating reagent, complexing agent made C
2O
4 2-With Ni
2+Mol ratio be 0.95-1.25.In order to control the granular size of powdered nickel precursor body better, preferably satisfying under the prerequisite of aforementioned proportion, nickel concentration is the 0.1-3 mol in the system, more preferably the 0.5-1.5 mol; Surfactant concentrations is preferably the 5-100 grams per liter, more preferably the 15-80 grams per liter.
There is no particular limitation for the condition that the present invention contacts described mixing, and for example, the temperature of mixing contact is preferably 40-100 ℃, more preferably 50-85 ℃; The time of mixing contact is preferably 0.5-10 hour, more preferably 2-5 hour.
The present invention has no particular limits the feed way and the charging sequence of above-mentioned various reaction masses, can be under stirring condition, is injected in the container continuously nickel salt aqueous solution, the precipitating reagent aqueous solution, complexing agent aqueous solution and aqueous surfactant solution respectively; Also the various materials that can will not react each other under stirring condition are pre-mixed, contact with other mixing of materials again behind the formation solution and react, for example, under the prerequisite that complexing agent and surfactant do not react, in advance complexing agent and surfactant are mixed, and then mixing contacts with precipitant solution with nickel salt; Nickel salt not with the prerequisite of complexing agent and/or surfactant reaction under, can earlier nickel salt be mixed with complexing agent and/or surfactant, formation contains the mixed solution of nickel salt, complexing agent and/or surfactant, and then mixes to contact with precipitating reagent, complexing agent and/or surfactant and react; Precipitating reagent not with the prerequisite of complexing agent and/or surfactant reaction under, also can earlier precipitating reagent be mixed with complexing agent and/or surfactant, formation contains the mixed solution of precipitating reagent, complexing agent and/or surfactant, and then mixes to contact with nickel salt, complexing agent and/or surfactant and react; Precipitating reagent and nickel salt all not with the prerequisite of complexing agent and/or surfactant reaction under, also can be earlier with complexing agent and/or surfactant separated into two parts, a part forms solution with precipitant mix in advance, another part is mixed formation solution with nickel salt, and then above-mentioned two kinds of solution are mixed contact react.
The present invention is preferably at nickel salt, under the prerequisite that surfactant and complexing agent and precipitating reagent and surfactant and complexing agent directly do not react, the mode that described reaction mass mixes contact for will contain in nickel salt and surfactant and the complexing agent at least a water solution A with contain precipitating reagent and surfactant and contact with alternative at least aqueous solution B mixing in the complexing agent, the concentration of nickel salt is the 0.1-3 mol in the water solution A, be preferably the 0.5-1.5 mol, the concentration of complexing agent is the 0-3 mol, be preferably the 0.5-1.5 mol, surfactant concentrations is the 0-100 grams per liter, is preferably 5-100 grams per liter 15-80 grams per liter more preferably; The concentration of precipitating reagent is the 0.1-3 mol among the aqueous solution B, be preferably the 0.5-1.5 mol, surfactant concentrations is the 0-100 grams per liter, is preferably the 5-100 grams per liter, more preferably the 15-80 grams per liter, the concentration of complexing agent is the 0-3 mol, be preferably the 0.5-1.5 mol, and the total concentration of complexing agent is the 0.1-3 mol among water solution A and the aqueous solution B, is preferably the 0.5-1.5 mol, the total concentration of surfactant is the 5-100 grams per liter, is preferably the 15-80 grams per liter.Specifically, for example, between nickel salt, surfactant and complexing agent, all directly do not react, when all directly not reacting between precipitating reagent, surfactant and the complexing agent yet, earlier with nickel salt and part surface activating agent and the mixed water solution A that gets of part complexing agent, with the mixed aqueous solution B that gets of precipitating reagent, remaining surfactant and remaining complexing agent, water solution A is mixed contacting then with aqueous solution B; When nickel salt does not directly react with surfactant and precipitating reagent when directly not reacting with complexing agent, earlier with nickel salt and the mixed mixed aqueous solution A that gets of surfactant, with precipitating reagent and the mixed mixed aqueous solution B that gets of complexing agent, water solution A is mixed contacting then with aqueous solution B; When nickel salt does not directly react with complexing agent and precipitating reagent when directly not reacting with surfactant, earlier with nickel salt and the mixed mixed aqueous solution A that gets of complexing agent, with precipitating reagent and the mixed mixed aqueous solution B that gets of surfactant, water solution A is mixed contacting then with aqueous solution B; When not reacting between surfactant and the complexing agent, earlier surfactant and complexing agent are mixed, and then be mixed together with nickel salt, precipitating reagent and contact.By above-mentioned premixed mode, can make reinforced program simplification and be easy to the ratio of each reaction mass in the hierarchy of control, tiny, the even particle size distribution of gained reactant particle.For granular size and the pattern of controlling powdered nickel precursor body better, the concentration of nickel salt, complexing agent, precipitating reagent equates in the preferred reaction solution, more preferably is the 0.1-3 mol, more preferably the 0.5-1.5 mol.
Wherein, the addition of described nickel salt, precipitating reagent, complexing agent be preferably the mol ratio that makes precipitating reagent and nickel salt for the 0.95-1.25 of stoichiometric proportion between them doubly, the mol ratio of complexing agent and nickel salt is 0.1-5, surfactant is the 0.5-20 weight % of nickel salt, precipitating reagent and complexing agent gross weight.More preferably the adding speed of nickel salt aqueous solution, the precipitating reagent aqueous solution, complexing agent aqueous solution and aqueous surfactant solution makes be preferably 0.5-10 hour, more preferably 2-5 hour the mixing time of contact (i.e. retention time in reactor) of reaction mass.Described reactor is preferably the reactor that the overflow of precipitated product nature is discharged.For adopting above-mentioned pouring-in reaction, can control the time of mixing contact by the adding speed of control reaction mass, for the above-mentioned reaction unit that the 10-50 of routine rises, the injection rate of preferably controlling reaction mass is respectively in 10-100 ml/min scope.
According to the present invention, the described method for preparing the globular powdered nickel presoma also comprises the gained reaction system separated and obtains the solid spherical powdered nickel precursor body, because gained powdered nickel precursor body of the present invention is a form of spherical particles, thereby adopt conventional equipment for separating liquid from solid such as funnel can be easy to realize separating purpose, not only reduce requirement to equipment, and separating rate is fast, has shortened the operating time greatly.
The preparation method of globular powdered nickel presoma provided by the invention preferably also comprise with gained solid powdered nickel precursor body wash, dry step.Described washing adopts conventional deionized water or distilled water washing to get final product for 2 times, more preferably re-uses alcohol washing 1 time under the situation after spending ion-cleaning.Described drying was preferably descended dry 1-2 hour at 80-120 ℃.Adopt conventional drying equipment such as air dry oven to get final product.
The present invention has no particular limits the described method for preparing globular powdered nickel by the roasting of globular powdered nickel presoma, for the method for roasting of conventional batteries positive electrode gets final product, for example comprise that the globular powdered nickel presoma is put into Muffle furnace carries out roasting, the temperature of described roasting is preferably 200-800 ℃, and the time of roasting is preferably 0.5-10 hour.Because described globular powdered nickel presoma is for adopting the globular powdered nickel presoma of method preparation provided by the invention, thereby described roasting can be carried out under carbon dioxide, nitrogen atmosphere, and do not need under reducing atmospheres such as hydrogen, to carry out, improved production security thus greatly.
The following examples will the present invention is further illustrated.Various precipitating reagents all can be used for realizing purpose of the present invention, only as the situation of precipitating reagent the present invention is described below with oxalic acid and/or oxalates, adopt method that other precipitating reagent prepares globular powdered nickel presoma and globular powdered nickel similarly, those skilled in the art need not promptly can realize through creative work by reading the present invention.
Embodiment 1
Present embodiment is used to illustrate the preparation method of globular powdered nickel presoma provided by the invention and globular powdered nickel.
Preparation contains the mixed aqueous solution A of 3 mol nickelous sulfates, 15 grams per liter benzene sulfonic acid sodium salts, preparation contains the mixed aqueous solution B of 1 mol sodium oxalate, 15 grams per liter benzene sulfonate aqueous solutions, then the ethylenediamine solution of above-mentioned water solution A, aqueous solution B and 1 mol being continuously pumped into the volume that installs 2 liters of deionized waters in advance with plunger displacement pump is in 20 liters the stirring reactor, the speed that pumps into is respectively: water solution A is that 15 ml/min, aqueous solution B are 45 ml/min, ethylenediamine solution 30 ml/min, makes C in the reaction system
2O
4 2-With Ni
2+Mol ratio be 1.0, complexing agent and Ni
2+Mol ratio be 1.5, the control reaction temperature is 60 ℃, continuous stirring is reacted the about 2.5 hours solidliquid mixtures in the post-reactor and is begun the nature overflow, stop feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, the gained solid spends deionised water, 100 ℃ of oven dry, promptly gets the globular powdered nickel presoma then.The SEM photo of this presoma as shown in Figure 1.
Gained globular powdered nickel presoma is fed CO at 550 ℃
2Roasting is 4 hours in the Muffle furnace of gas, after the cooling, obtains globular powdered nickel naturally.The SEM photo of gained globular powdered nickel as shown in Figure 2.As can be seen from Figure 2, the epigranular of gained globular powdered nickel has good sphericity, and grain size analysis shows the median particle diameter D of this product
50It is 0.5 micron.
Embodiment 2
Present embodiment is used to illustrate the preparation method of globular powdered nickel presoma provided by the invention and globular powdered nickel.
Preparation contains the mixed aqueous solution A of 1 mol nickel nitrate and 10 grams per liter lauryl sodium sulfate, and preparation contains the mixed aqueous solution B of lauryl sodium sulfate of ammonia spirit, 15 grams per liters of the ammonium oxalate aqueous solution, 2 mol of 1 mol.It is in 20 liters the stirring reactor that above-mentioned two kinds of solution are continuously pumped into the volume that installs 3 liters of deionized waters in advance with the identical speed of 20 ml/min with plunger displacement pump, C in the reaction system
2O
4 2-With Ni
2+Mol ratio be 1.0, complexing agent and Ni
2+Mol ratio be 2.0, the control reaction temperature is 70 ℃, the adding speed of control reaction mass makes the solidliquid mixture in 3 hours post-reactors of continuous feed begin the nature overflow, stop feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, the gained solid spends deionised water, and 105 ℃ of oven dry promptly get the globular powdered nickel presoma then.
With the roasting 3 hours in 450 ℃ of Muffle furnaces that feed nitrogen gas of gained powdered nickel precursor body, after cooling off naturally, obtain globular powdered nickel.Sem analysis shows, the epigranular of gained globular powdered nickel has good sphericity, and grain size analysis shows the median particle diameter D of products obtained therefrom
50It is 1.0 microns.
Present embodiment is used to illustrate the preparation method of globular powdered nickel presoma provided by the invention and globular powdered nickel.
Preparation contains the mixed aqueous solution A of 1.2 mol nickelous sulfates and 5 grams per liter softex kws, preparation contains the mixed aqueous solution B of ethylenediamine solution of the sodium oxalate aqueous solution, 1 mol of 1 mol, then above-mentioned two kinds of solution being continuously pumped into the volume that installs 2 liters of deionized waters in advance with plunger displacement pump is that the speed that pumps into makes C in the reaction system in 20 liters the stirring reactor
2O
4 2-With Ni
2+Mol ratio be 1.2, complexing agent and Ni
2+Mol ratio be 5, retention time is 2.5 hours, the control reaction temperature is 60 ℃, stop feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, the gained solid spends deionised water, 80 ℃ of oven dry, promptly get the globular powdered nickel presoma then.
With the roasting 4 hours in 550 ℃ of electric furnaces that feed nitrogen gas of gained globular powdered nickel presoma, after cooling off naturally, obtain globular powdered nickel.Sem analysis shows, the epigranular of gained globular powdered nickel has good sphericity, and grain size analysis shows the median particle diameter D of this product
50It is 1.0 microns.
Embodiment 4
Present embodiment is used to illustrate the preparation method of globular powdered nickel presoma provided by the invention and globular powdered nickel.
Preparation contains the mixed aqueous solution A of the ethylenediamine of 1.5 mol nickel chlorides, 15 grams per liter OTACs and 0.5 mol, preparation contains the mixed aqueous solution B of the ethylenediamine of 1 mol sodium oxalate, 45 grams per liter benzene sulfonic acid sodium salts and 2.5 mol, then above-mentioned water solution A, aqueous solution B being continuously pumped into the volume that installs 2 liters of deionized waters in advance with plunger displacement pump is that the speed that pumps into makes C in the reaction system in 20 liters the stirring reactor
2O
4 2-With Ni
2+Mol ratio be 1.0, complexing agent and Ni
2+Mol ratio be 2.8, retention time is 2.5 hours, the control reaction temperature is 60 ℃, stop feed liquor after 10 hours, continue to stir heavyization 1 hour, collect the solidliquid mixture of reaction gained, carry out Separation of Solid and Liquid, the gained solid spends deionised water, 120 ℃ of oven dry, promptly get the globular powdered nickel presoma then.
With the roasting 1 hour in 700 ℃ of electric furnaces that feed nitrogen gas of gained globular powdered nickel presoma, after cooling off naturally, obtain globular powdered nickel.Sem analysis shows, the epigranular of gained globular powdered nickel has good sphericity, and grain size analysis shows the median particle diameter D of this product
50It is 1.0 microns.
Embodiment 5
Step according to embodiment 1 prepares globular powdered nickel presoma and globular powdered nickel, and different is, nickelous sulfate, benzene sulfonic acid sodium salt, sodium oxalate react in the injecting reactor simultaneously with separately aqueous solution form and ethylenediamine solution respectively.Sem analysis shows that the granularity of gained globular powdered nickel is not as the epigranular of embodiment 1-4 gained nickel powder, and grain size analysis shows the median particle diameter D of this product
50It is 2.0 microns.
Embodiment 6
Step according to embodiment 1 prepares globular powdered nickel presoma and globular powdered nickel, and different is that used surfactant is the triacetamide oleate.Sem analysis shows, the epigranular of gained globular powdered nickel has good sphericity, and grain size analysis shows the median particle diameter D of this product
50It is 1.8 microns.
Comparative Examples 1
Prepare powdered nickel precursor body and nickel powder by CN 1600480A embodiment 2 described methods, the SEM of gained powdered nickel precursor body and nickel powder product distinguishes as shown in Figure 3 and Figure 4, and grain size analysis shows the median particle diameter D of this nickel powder product
50It is 9.0 microns.Just obtain 50 gram powdered nickel precursor bodies through 120 minutes suction filtrations.
The chemical property analysis of globular powdered nickel
The nickel powder that makes with the foregoing description 1-6 and Comparative Examples 1 is made nickel secondary batteries as positive active material respectively, then above-mentioned battery is carried out specific capacity test and cycle life test respectively, and measurement result is as shown in table 1.
Table 1
| Project | Embodiment 1 | Embodiment 2 | | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 1 |
| Specific capacity (milliampere/gram) | 197 | 197 | 196 | 196 | 192 | 193 | 188 |
| 500 capacity surplus ratios (%) circulate | 86％ | 85％ | 85％ | 84％ | 80％ | 80％ | 76％ |
From the result of last table 1 as can be seen, the globular powdered nickel that makes with method provided by the invention can improve the specific capacity and the cycle life of battery greatly, especially adopts lauryl sodium sulfate, benzene sulfonic acid sodium salt, softex kw, OTAC obviously to be better than other surfactants as the effect of surfactant.
Claims (12)
1, a kind of preparation method of globular powdered nickel presoma, this method comprise reaction mass is mixed contact under stirring condition, and described reaction mass contains the precipitating reagent and the complexing agent of nickel salt, nickel salt, it is characterized in that, described reaction mass also contains surfactant.
2, method according to claim 1, wherein, the addition of described surfactant is the 0.5-20 weight % of nickel salt, precipitating reagent and complexing agent gross weight.
3, method according to claim 1, wherein, described surfactant is one or more in lauryl sodium sulfate, benzene sulfonic acid sodium salt, softex kw, the OTAC.
4, method according to claim 1, wherein, described nickel salt is one or more in nickel nitrate, nickel chloride, nickelous sulfate, the nickel acetate, and described precipitating reagent is one or more in NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, potash, saleratus, ammonium carbonate, carbonic hydroammonium, oxalic acid, sodium oxalate, potassium oxalate, the ammonium oxalate; Described complexing agent is one or more in ammonia, ethylenediamine, acetate, the acetylacetone,2,4-pentanedione.
5, method according to claim 1, wherein, the mol ratio that the addition of described nickel salt, precipitating reagent, complexing agent makes precipitating reagent and nickel salt for the 0.95-1.25 of stoichiometric proportion between them doubly, the mol ratio of complexing agent and nickel salt is 0.1-5.
6, method according to claim 1, wherein, the temperature of described mixing contact is 50-85 ℃, the time of mixing contact is 0.5-10 hour.
7, method according to claim 1, wherein, the mode that described reaction mass mixes contact is under stirring condition, be injected in the container continuously nickel salt aqueous solution, the precipitating reagent aqueous solution, complexing agent aqueous solution and aqueous surfactant solution respectively, the concentration of described nickel salt aqueous solution is the 0.1-3 mol, the concentration of the precipitating reagent aqueous solution is the 0.1-3 mol, described precipitating reagent is oxalic acid and/or oxalates, the concentration of complexing agent aqueous solution is the 0.1-3 mol, and the concentration of aqueous surfactant solution is the 5-100 grams per liter.
8, method according to claim 1, wherein, the mode that described reaction mass mixes contact is under stirring condition, at least a water solution A that will contain in nickel salt, surfactant and the complexing agent is injected in the container respectively with at least a aqueous solution B that contains in precipitating reagent, surfactant and the complexing agent continuously, the concentration of nickel salt is the 0.1-3 mol in the water solution A, the concentration of complexing agent is the 0-3 mol, and surfactant concentrations is the 0-100 grams per liter; The concentration of precipitating reagent is the 0.1-3 mol among the aqueous solution B, surfactant concentrations is the 0-100 grams per liter, the concentration of complexing agent is the 0-3 mol, and the total concentration of complexing agent is the 0.1-3 mol among water solution A and the aqueous solution B, and the total concentration of surfactant is the 5-100 grams per liter.
9, according to claim 7 or 8 described methods, wherein, described precipitating reagent is oxalic acid and/or oxalates, the mol ratio that the adding speed of nickel salt aqueous solution, the precipitating reagent aqueous solution, complexing agent aqueous solution and aqueous surfactant solution makes precipitating reagent and nickel salt for the 0.95-1.25 of stoichiometric proportion between them doubly, the mol ratio of complexing agent and nickel salt is 0.1-5, surfactant is the 0.5-20 weight % of nickel salt, precipitating reagent and complexing agent gross weight.
10, according to claim 7 or 8 described methods, wherein, it is 0.5-10 hour that the adding speed of nickel salt aqueous solution, the precipitating reagent aqueous solution, complexing agent aqueous solution and aqueous surfactant solution makes mixing time of contact of reaction mass.
11, a kind of preparation method of globular powdered nickel, this method comprise preparation globular powdered nickel presoma, then presoma are carried out roasting, and wherein, the preparation method of described globular powdered nickel presoma is any described method among the claim 1-8.
12, method according to claim 11, wherein, the temperature of described roasting is 200-800 ℃, the time of roasting is 0.5-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610078405A CN100588453C (en) | 2006-05-24 | 2006-05-24 | Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610078405A CN100588453C (en) | 2006-05-24 | 2006-05-24 | Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101077476A true CN101077476A (en) | 2007-11-28 |
| CN100588453C CN100588453C (en) | 2010-02-10 |
Family
ID=38905239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200610078405A Expired - Fee Related CN100588453C (en) | 2006-05-24 | 2006-05-24 | Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100588453C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102699338A (en) * | 2012-05-18 | 2012-10-03 | 宁夏东方钽业股份有限公司 | Method for preparing spherical nickel powder |
| CN103433501A (en) * | 2013-08-08 | 2013-12-11 | 淮阴师范学院 | Preparation method of uniform-grain-size spherical nano cobalt |
| CN104170023A (en) * | 2012-03-06 | 2014-11-26 | 东洋油墨Sc控股株式会社 | Conductive fine particles, method for manufacturing same, conductive resin composition, conductive sheet, and electromagnetic shielding sheet |
| CN106623961A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Preparation method of nickel powder with small FSSS |
| CN106670489A (en) * | 2016-11-28 | 2017-05-17 | 荆门市格林美新材料有限公司 | Preparing method for spherical high-purity nickel powder |
| CN108778578A (en) * | 2016-03-04 | 2018-11-09 | 住友金属矿山株式会社 | The manufacturing method of nickel powder |
| CN108907229A (en) * | 2018-07-24 | 2018-11-30 | 安徽工业大学 | A kind of preparation method of ellipsoid porous hollow nickel powder |
| CN110983142A (en) * | 2019-11-25 | 2020-04-10 | 河海大学 | Preparation method of tungsten carbide-nickel hard alloy |
| CN114059356A (en) * | 2021-11-19 | 2022-02-18 | 福建中裕新材料技术有限公司 | Preparation method of slurry for high-performance TPR synthetic leather |
| CN114455642A (en) * | 2021-12-31 | 2022-05-10 | 宜宾光原锂电材料有限公司 | Preparation method of nano-pore precursor |
-
2006
- 2006-05-24 CN CN200610078405A patent/CN100588453C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104170023A (en) * | 2012-03-06 | 2014-11-26 | 东洋油墨Sc控股株式会社 | Conductive fine particles, method for manufacturing same, conductive resin composition, conductive sheet, and electromagnetic shielding sheet |
| CN104170023B (en) * | 2012-03-06 | 2016-12-28 | 东洋油墨Sc控股株式会社 | Electrically conductive microparticle and manufacture method, electroconductive resin constituent, conductive sheet and electromagnetic shielding sheet |
| CN102699338A (en) * | 2012-05-18 | 2012-10-03 | 宁夏东方钽业股份有限公司 | Method for preparing spherical nickel powder |
| CN102699338B (en) * | 2012-05-18 | 2014-06-04 | 国家钽铌特种金属材料工程技术研究中心 | Method for preparing spherical nickel powder |
| CN103433501A (en) * | 2013-08-08 | 2013-12-11 | 淮阴师范学院 | Preparation method of uniform-grain-size spherical nano cobalt |
| CN108778578A (en) * | 2016-03-04 | 2018-11-09 | 住友金属矿山株式会社 | The manufacturing method of nickel powder |
| CN106670489A (en) * | 2016-11-28 | 2017-05-17 | 荆门市格林美新材料有限公司 | Preparing method for spherical high-purity nickel powder |
| CN106623961A (en) * | 2016-11-28 | 2017-05-10 | 荆门市格林美新材料有限公司 | Preparation method of nickel powder with small FSSS |
| CN108907229A (en) * | 2018-07-24 | 2018-11-30 | 安徽工业大学 | A kind of preparation method of ellipsoid porous hollow nickel powder |
| CN108907229B (en) * | 2018-07-24 | 2021-08-27 | 安徽工业大学 | Preparation method of ellipsoidal porous hollow nickel powder |
| CN110983142A (en) * | 2019-11-25 | 2020-04-10 | 河海大学 | Preparation method of tungsten carbide-nickel hard alloy |
| CN110983142B (en) * | 2019-11-25 | 2021-10-19 | 河海大学 | Preparation method of tungsten carbide-nickel hard alloy |
| CN114059356A (en) * | 2021-11-19 | 2022-02-18 | 福建中裕新材料技术有限公司 | Preparation method of slurry for high-performance TPR synthetic leather |
| CN114455642A (en) * | 2021-12-31 | 2022-05-10 | 宜宾光原锂电材料有限公司 | Preparation method of nano-pore precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100588453C (en) | 2010-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100588453C (en) | Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel | |
| CN101897061B (en) | Cathode material precursors doped homogeneously with nanoparticle core | |
| CN108373175A (en) | Aluminium doped cobaltic-cobaltous oxide and its preparation method and application | |
| CN104353472A (en) | Preparation method of BiOBr/RGO nanometer composite and application thereof in reaction of degrading rhodamine | |
| CN108946827A (en) | A kind of ultra-small grain size nickel cobalt manganese hydroxide and preparation method thereof | |
| CN110745784B (en) | Metal oxide nano-particles and preparation method and application thereof | |
| CN108517537A (en) | Double scale transition metal phosphides of a kind of nitrogen-doped carbon load and its preparation method and application | |
| CN104084599A (en) | Method for producing ultrafine spherical silver powder for conductive silver paste | |
| CN109817901A (en) | A kind of preparation method of the spherical precursor of nickel cobalt aluminium doping | |
| CN108160071B (en) | Nano palladium catalyst with high-activity crystal face and biological reduction preparation method thereof | |
| CN110817976B (en) | Positive electrode material precursor and preparation method and application thereof | |
| CN111111652B (en) | Self-supporting AuPd alloy mesoporous nanosphere and preparation method and application thereof | |
| CN105271443B (en) | Method for preparing flaky nano CoO or Co3O4 through assistant microwave heating | |
| CN106006551B (en) | Application of the Ni B catalyst of terpolymer nanosphere load in catalysis sodium borohydride and hydrolytic hydrogen production reaction | |
| CN1265921C (en) | Wet manufacturing method for high vibrancy solid ultra micro sphere metal nickel powder | |
| CN104815685A (en) | Magnetic multistage nuclear @ shell structure nano-palladium catalyst and preparation method thereof | |
| CN101722314B (en) | Method for preparing Cu2O-Cu composite microsphere by adopting bean flour as template | |
| KR102331722B1 (en) | Reactor, methods for preparing precursors of cathode active materials for lithium ion secondary batteries by using the same, precursors prepared by the same, cathode active materials | |
| CN101380679A (en) | Method for preparing monodisperse superfine globular nickel powder using precursor complexes | |
| CN1448216A (en) | Prep. of high-load bi-and multi-component precious metallic catalyst | |
| KR101314990B1 (en) | Manufacturing method of conductive copper powder | |
| CN1513767A (en) | Preparation method of superfine manganese dioxide | |
| CN102211201B (en) | Method for preparing Pt, Pd and Pt-M (M is Cu, Ag and Pd) alloy nanoparticles | |
| CN106334802A (en) | Metal powder of spongy microstructure, preparation method thereof, and conductive material | |
| CN1046683C (en) | Liquid phase superfine zinc oxide preparing process through stepped nucleating growth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100210 Termination date: 20160524 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |