CN106395754B - Mono-/multi- metal is co-precipitated the preparation method of hydroxide or carbonated - Google Patents
Mono-/multi- metal is co-precipitated the preparation method of hydroxide or carbonated Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/363—Mixtures of oxides or hydroxides by precipitation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The present invention discloses the preparation method of a kind of mono-/multi- metal co-precipitation hydroxide or carbonated, includes the following steps：1) soluble salt solution for preparing mono-/multi- metal, is added urea, obtains solution I；2) precipitant solution is prepared；3) deionized water and ammonium hydroxide are added into reaction kettle, then pH value=10.5~11.0 are pumped into solution I, precipitant solution and enveloping agent solution using metering pump, carry out coprecipitation reaction；Wherein, solution I enters heated before reaction kettle, makes the resolution ratio 30~100% of urea；4) after the reaction was completed, substance in kettle is separated by solid-liquid separation, collects filter cake, washing removal foreign ion；Drying obtains mono-/multi- metal co-precipitation hydroxide or carbonated.The preparation method realizes the pre- complexing of metal ion in metal salt solution using the characteristic of urea pyrolytic release ammonia, the reaction efficiency of controllable crystallization reaction is improved, to improve the density of product and the spheroidization degree of particle.
Description
Technical field
The present invention relates to battery electrode material preparation fields, are co-precipitated hydroxide more particularly to a kind of mono-/multi- metal
Or the preparation method of carbonated.
Background technique
Metal hydroxides or carbonate compound are very widely used in battery industry, such as nickel-hydrogen battery positive pole material
For ball-shape nickel hydroxide Ni (OH)2, additive is hydroxide cobalt Co (OH)2Or cobalt hydroxide Co (OH)3, lithium ion battery
There are many materials using list or metal co-precipitation hydroxide or carbonate compound as presoma in positive electrode, such as cobalt-lithium oxide
Material using spherical hydroxy cobalt oxide CoOOH or cobalt carbonate CoCO3 as presoma, nickel cobalt binary or nickel cobalt aluminium ternary material with
NixCo1-x(OH)2And Ni1-x-yCoxAly(OH)2The hydroxide being co-precipitated for presoma, nickel-cobalt-manganese ternary material with nickel, cobalt manganese
Ni1-x-yCoxMny(OH)2Or carbonate compound Ni1-x-yCoxMnyCO3For presoma, spinel manganese oxide lithium anode material is with ball
Shape manganese carbonate MnCO3For presoma.Highdensity hydroxide and carbonate compound are also widely used in other industries.
The crystalline perfection and order degree of hydroxide or carbonate compound to the physical property such as tap density of material,
The spheroidization degree of particle has vital influence.Preparation spherical metal hydroxide and carbonate compound technique at present
In, generally use ammonia or ammonium-containing compound as complexing agent, during the reaction with metal salt solution and precipitant solution cocurrent
It is added in reaction kettle.In a kettle, metal ion and ammonia or ammonium ion form metal ammonia and cooperate ion, metal ammonia cooperate from
Son is again in OH-Or CO3 2-Under the action of dissociate, and occur precipitation reaction generate hydroxide or carbonate compound precipitating.Pass through control
The speed that speed control complex ion is formed or dissociated is added in the additional amount of ammonia or ammonium-containing compound processed, to reach control altogether
The purpose of precipitation reaction speed, here it is so-called control crystallization processes.
Me2++6NH3→Me[NH3]6 2+
Me[NH3]6 2++2OH-→Me(OH)2+6NH3
In traditional control crystallization processes, the complexing of ammonia and metal ion is to occur simultaneously with precipitation reaction with dissociation
, cooperate the time of ion shorter for being formed, it is anti-that precipitating can occur for the part metals ion of not yet formation stable complexation ion
It answers, due to precipitation reaction excessive velocities, the lattice order for generating precipitating will be reduced, while also result in tap density and particle
The decline of spheroidization degree.
There is researcher to propose a pre- complexing process route, i.e., first ammonium hydroxide is added in salting liquid, is formed stable
It is pumped into reaction kettle again after complex ion and carries out generation precipitation reaction, to improve the order degree of precipitated product lattice.But
The solubility of nickel sulfate ammonia and cobaltous sulfate ammonia that ammonia produces in conjunction with nickel sulfate and cobaltous sulfate is lower, is added after ammonia and precipitating is easily precipitated
Blocking pipeline.Although the solubility of nickel sulfate ammonia and cobaltous sulfate ammonia can be improved in the temperature for increasing solution, but still will cause pipe
The a degree of blocking in road, is unable to satisfy the needs of actual production.Therefore the pre- complexing technique does not push away extensively in actual production
Extensively.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of mono-/multi- metal co-precipitation hydroxide or carbonateds
Preparation method, using urea decomposes under the high temperature conditions discharge ammonia characteristic, realize metal ion in metal salt solution
Pre- complexing, improve the reaction efficiency of controllable crystallization reaction, apply it to the system of spherical hydroxide and carbonate compound
In standby technique, it will be apparent that the order degree and integrality for improving hydroxide and carbonate compound crystal structure, to improve
The density of product and the spheroidization degree of particle.
For this purpose, technical scheme is as follows：
A kind of mono-/multi- metal is co-precipitated the preparation method of hydroxide or carbonated, includes the following steps：
1) soluble salt solution for preparing mono-/multi- metal, is added urea, obtains solution I；
2) precipitant solution is prepared；
3) deionized water and ammonium hydroxide are added into reaction kettle, makes pure water pH value=10.5~11.0 in kettle, then thereto
Be pumped into solution I, precipitant solution and enveloping agent solution using metering pump, stirring, 50 DEG C~90 DEG C, pH value=10.5~12.5
And pH value fluctuation range be less than ± 1.0 under conditions of carry out coprecipitation reaction；Wherein, the solution I enters before reaction kettle through adding
Heat guarantees that wherein the resolution ratio of urea is 30~100% when the solution I enters reaction kettle；
4) after the reaction was completed, substance in reaction kettle is separated by solid-liquid separation, obtains the filter cake of hydroxide or carbonated, it will
The filter cake repeatedly washs removal foreign ion with deionized water；4~10h is dried under the conditions of 100~150 DEG C, is obtained described
Mono-/multi- metal is co-precipitated hydroxide or carbonated.
Further, solution I enters the pipeline before reaction kettle and heats through 70~100 DEG C of sink, or wraps on the outside of pipeline
Heating tape is covered to be heated.
Further, metal described in step 1) be Ni, Co, Mn, Mg, Cu, Al, Fe, Sn and Ti in any one or it is more
Kind.
Further, soluble salt solution described in step 1) is in sulfate, nitrate, chloride, acetate and acetate
Any one or more.
Further, the concentration of soluble salt solution described in step 1) is 0.1~2.5mol/L.
Further, in the solution I, the ratio of the sum of amount of substance of urea and metallic element is 0.5~10:1.
Further, the precipitating reagent is sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydrogen carbonate, carbonic acid ammonia, bicarbonate
Sodium or sodium carbonate.
It is preferred that the precipitant solution be the lithium hydroxide solution that concentration is 0.1~3mol/L or concentration be 0.1~
Perhaps concentration is 0.1~10mol/L sal volatile or concentration to the sodium hydroxide solution or potassium hydroxide solution of 10mol/L
The sodium carbonate liquor that sodium bicarbonate solution or concentration for 0.1~1.3mol/L are 0.1~2.65mol/L.
Further, the complexing agent be one of ammonium hydroxide, ethylenediamine, glutamic acid, EDTA, citric acid, sodium citrate or
It is a variety of.Solute is 0.5~10/1 with the ratio of the amount of the substance of metal ion in enveloping agent solution.
Pre- complexing control crystallization processes provided by the invention are compared with Traditional control crystallization processes, gained hydroxide and carbon
The particle sphericity of acid compound is more preferable, and tap density is improved, and to form the metal ion such as Mn of spheric granules for being difficult to2 +、Al3+Etc. there is higher spheroidization effect.In addition, effectively being solved compared with the pre- complexing technique that ammonium hydroxide is added into salting liquid
The problem of pipeline blockage of having determined, is conducive to the large-scale promotion that this process industry metaplasia produces.
Detailed description of the invention
Fig. 1 is the flow chart of preparation method provided by the invention.
Specific embodiment
A kind of specific embodiment of the invention is added to a certain amount of urea in metal salt solution to be reacted, instead
At once salting liquid is pumped into reaction kettle with metering pump, the one section of pipeline that will be close to reaction kettle is immersed in water bath.Water bath
In be equipped with heating element, the water in slot is heated to 70 DEG C~100 DEG C by heating element.According to the flow velocity of pump, pass through adjusting
The length of pipe for immersing water-bath slot part can get suitable solution heating time, to guarantee that the urea decomposition that has ample time is released
It puts ammonium ion and forms complex ion with metal ion, following reaction occurs：
CO(NH2)2+H2O→2NH3+CO2↑
Me2++4NH3→[Me(NH3)4]2+
Wherein Me is one of Ni, Co, Mn, Mg, Cu, Al, Fe, Sn, Ti etc. or a variety of.
Precipitating reagent, complexing agent and salting liquid are pumped into reaction kettle simultaneously, are continuously stirred at a certain temperature, are completed altogether
Precipitation reaction obtains high-density spherical hydroxide or carbonate compound presoma.
Technical solution of the present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
Urea is added in the ratio of 3g/L into the nickel sulfate solution that concentration is 0.1mol/L, at this time urea and gold in solution
Belong to Ni2+Amount of substance ratio be 0.5:1.Precipitating reagent is sodium hydroxide, and concentration 6mol/L, complexing agent is ammonium hydroxide, and concentration is
20wt%.Deionized water is added into reaction kettle in advance to bottom blade is not crossed, be then added ammonium hydroxide adjust pH value to 10.5~
11.0, reactor temperature is then risen to 60~70 DEG C.Using internal diameter for 10mm silicone rubber tube as transfer pipeline, nickel sulfate is molten
Liquid is pumped into reaction kettle with the speed of 5ml/min, and adjusting the length of pipe entered in water bath is 6.5cm, and nickel sulfate solution exists
Residence time in water bath is 1min.Ammonium hydroxide is pumped into reaction kettle that (ammonium hydroxide is divided into two simultaneously with the speed of 2.8ml/min
Point, sub-fraction is added is previously implanted in the pure water of reaction kettle before the reaction, as bottom liquid, for adjusting pH value and as initial
Complexing agent；Need constantly to supplement complexing agent during the reaction, therefore most of ammonium hydroxide passes through pump pump during the reaction
Enter reaction kettle), NH at this time4 +/Ni2+(molar ratio) is about 3, pH in the flow control reaction kettle by adjusting sodium hydroxide solution
In 11.2~11.4 ranges, reaction stops being pumped into each material solution after carrying out 30 hours value, keeps temperature to continue stirring 4 small
When, obtained slurry is 8~10 hours dry at a temperature of 120 DEG C by being separated by solid-liquid separation, washing, and obtains 1 spherical Ni of sample
(OH)2Material.
Embodiment 2
Into the nickel sulfate manganese solution that concentration is 1mol/L by the ratio addition urea of every liter of 6g, Ni/Mn=1 in solution,
Urea amount of substance and W metal in solution at this time2+With Mn2+Total material amount ratio be 2:1.Precipitating reagent is sodium hydroxide, concentration
For 4mol/L, complexing agent is ammonium hydroxide, concentration 20wt%.In advance into reaction kettle be added deionized water to do not cross bottom blade,
Then ammonium hydroxide is added and adjusts pH value to 10.5~11.0, reactor temperature is then risen to 60~70 DEG C.It is 10mm with internal diameter
Silicone rubber tube be transfer pipeline, salting liquid is pumped into reaction kettle with the speed of 50ml/min, adjusts the pipe entered in water bath
Road length is 200cm, and residence time of the salting liquid in water bath is 3.1min.Ammonium hydroxide is with the speed of 9.2ml/min and salt, heavy
Shallow lake agent solution is pumped into reaction kettle simultaneously, at this time NH4 +/(Ni2++Mn2+) (molar ratio) be about 2, pass through and adjusts sodium hydroxide solution
Flow control reaction kettle in pH value in 11.2~11.4 ranges, when reaction, is passed through nitrogen protection.After reaction carries out 30 hours
Stopping is pumped into each material solution, continues stirring 4 hours, and obtained slurry is done at a temperature of 120 DEG C by being separated by solid-liquid separation, washing
Dry 8~10 hours, obtain 2 spherical Ni of sample0.5Mn0.5(OH)2Material.
Embodiment 3
Urea, Ni/Co/ in solution is added in the ratio of every liter of 360g into the sulfuric acid nickel cobalt manganese solution that concentration is 2mol/L
Mn=1, at this time urea amount of substance and metal (Ni in solution2++Co2++Mn2+) total material amount ratio be 2:1.Precipitating reagent is hydrogen
Sodium oxide molybdena, concentration 10mol/L, complexing agent are ammonium hydroxide, concentration 20wt%.Deionized water is added into reaction kettle in advance to not having
Bottom blade is crossed, ammonium hydroxide is then added and adjusts pH value to 10.5~11.0, reactor temperature is then risen to 50~60 DEG C.With
The silicone rubber tube that internal diameter is 10mm is transfer pipeline, and salting liquid is pumped into reaction kettle with the speed of 100ml/min, adjusts and enters water
Length of pipe in bath is 1275cm, and residence time of the salting liquid in water bath is 10min.Ammonium hydroxide is with the speed of 23ml/min
Degree is pumped into reaction kettle simultaneously with salt, precipitant solution, at this time NH4 +/(Ni2++Co2++Mn2+) (molar ratio) be about 2.5, pass through
Adjusting pH value in the flow control reaction kettle of sodium hydroxide solution, in 11.2~11.4 ranges, when reaction, is passed through nitrogen protection.
Reaction progress stopped being pumped into each material solution after 30 hours, continued stirring 4 hours, and obtained slurry, which passes through, to be separated by solid-liquid separation, washs,
It is 8~10 hours dry at a temperature of 120 DEG C, obtain 3 spherical Ni of sample1/3Co1/3Mn1/3(OH)2Material.
Urea, solution is added in the ratio of every liter of 450g into the sulfuric acid nickel and cobalt solution that concentration is 2.5mol/L in embodiment 4
Middle Ni/Co=8/2, at this time urea amount of substance and metal (Ni in solution2++Co2+) total material amount ratio be 10:1.Precipitating reagent
For sodium hydroxide, concentration 6mol/L, complexing agent is ammonium hydroxide, concentration 20wt%.Deionized water is added into reaction kettle in advance
To bottom blade is not crossed, ammonium hydroxide is then added and adjusts pH value to 10.5~11.0, reactor temperature is then risen to 50~60
℃.Using internal diameter for 10mm silicone rubber tube as transfer pipeline, salting liquid is pumped into reaction kettle with the speed of 80ml/min, adjust into
Entering the length of pipe in water bath is 10250cm, and residence time of the salting liquid in water bath is 10min.Ammonium hydroxide is with 9.2ml/
The speed and salt, precipitant solution of min is pumped into reaction kettle simultaneously, at this time NH4+/(Ni2++Co2+) (molar ratio) be about 0.5, lead to
Overregulating pH value in the flow control reaction kettle of sodium hydroxide solution, in 11.2~11.4 ranges, reaction stops after carrying out 30 hours
It is only pumped into each material solution, continues stirring 4 hours, obtained slurry is by being separated by solid-liquid separation, washing, dry 8 at a temperature of 120 DEG C
~10 hours, obtain 4 spherical Ni of sample0.8Co0.2(OH)2Material.
Embodiment 5
Urea, Ni/ in solution is added in the ratio of every liter of 90g into the sulfuric acid nickel cobalt aluminum solutions that concentration is 1.5mol/L
Co/Al=80/15/5, at this time urea amount of substance and metal (Ni in solution2++Co2+) total material amount ratio be 5:1, then to salt
EDTA is added in the ratio of 5.6g/L in solution.In advance into reaction kettle be added deionized water to do not cross bottom blade, then plus
Enter ammonium hydroxide and adjust pH value to 10.5~11.0, reactor temperature is then risen to 50~60 DEG C.It is the silicon rubber of 10mm with internal diameter
Sebific duct is transfer pipeline, and salting liquid is pumped into reaction kettle with the speed of 50ml/min, adjusts the length of pipe entered in water bath
For 640cm, residence time of the salting liquid in water bath is 10min.By the flow control reaction for adjusting sodium hydroxide solution
In 11.2~11.4 ranges, reaction stops being pumped into each material solution after carrying out 30 hours pH value in kettle, continues stirring 4 hours,
Obtained slurry is 8~10 hours dry at a temperature of 150 DEG C by being separated by solid-liquid separation, washing, and it is spherical to obtain sample 5
Ni0.8Co0.15Al0.05(OH)2Material.
Embodiment 6
Urea dissolution is added in the ratio of every liter of 450g into the cobalt sulfate solution that concentration is 2.5mol/L, at this time in solution
Urea amount of substance and Co2+Total material amount ratio be 3:1, then EDTA is added in the ratio of 9.4g/L into salting liquid.In advance to
Deionized water is added in reaction kettle to bottom blade is not crossed, then addition ammonium hydroxide adjusting pH value, then will be anti-to 10.5~11.0
Temperature in the kettle is answered to rise to 40~50 DEG C.Using internal diameter for 10mm silicone rubber tube as transfer pipeline, salting liquid is with the speed of 50ml/min
Degree is pumped into reaction kettle, and adjusting the length of pipe entered in water bath is 640cm, and residence time of the salting liquid in water bath be
10min, water temperature is 90 DEG C in sink.Using 2.0mol/L sodium carbonate liquor as precipitating reagent, by the flow velocity for adjusting sodium carbonate liquor
Controlling pH value in reaction kettle, in 7.5~8.5 ranges, reaction stops being pumped into each material solution after carrying out 30 hours, continues stirring 4
Hour, obtained slurry is 8~10 hours dry at a temperature of 100 DEG C by being separated by solid-liquid separation, washing, and it is spherical to obtain sample 6
CoCO3Material.
Embodiment 7
Urea dissolution is added in the ratio of every liter of 450g into the cobalt sulfate solution that concentration is 2.5mol/L, at this time in solution
Urea amount of substance and Co2+Total material amount ratio be 3:1.In advance into reaction kettle be added deionized water to do not cross bottom blade,
Then ammonium hydroxide is added and adjusts pH value to 10.5~11.0, reactor temperature is then risen to 40~50 DEG C.It is 10mm with internal diameter
Silicone rubber tube be transfer pipeline, salting liquid is pumped into reaction kettle with the speed of 50ml/min, adjusts the pipe entered in water bath
Road length is 640cm, and residence time of the salting liquid in water bath is 10min, and water temperature is higher than 90 DEG C in sink.With 2.65mol/
L sodium carbonate liquor is precipitating reagent, through pH value in the flow control reaction kettle of adjusting sodium carbonate liquor in 7.5~8.5 ranges,
Reaction progress stopped being pumped into each material solution after 30 hours, continued stirring 4 hours, and obtained slurry, which passes through, to be separated by solid-liquid separation, washs,
It is 8~10 hours dry at a temperature of 100 DEG C, obtain 7 spherical shape CoCO of sample3Material.
Comparative example 1
The nickel sulfate manganese solution of 1mol/L is pumped into reaction kettle with the speed of 50ml/min.Precipitating reagent is sodium hydroxide, dense
Degree is 4mol/L, and complexing agent is ammonium hydroxide, and deionized water is added to no mistake bottom paddle in concentration 20wt% into reaction kettle in advance
Then leaf is added ammonium hydroxide and adjusts pH value to 10.5~11.0, reactor temperature is then risen to 60~70 DEG C.With 9.2ml/
The speed and salt, precipitant solution of min is pumped into reaction kettle simultaneously, by the flow control reaction kettle for adjusting sodium hydroxide solution
For interior pH value in 11.2~11.4 ranges, when reaction, is passed through nitrogen protection.It is molten to be pumped into each raw material for stopping after reaction carries out 30 hours
Liquid continues stirring 4 hours, and obtained slurry is 8~10 hours dry at a temperature of 120 DEG C by being separated by solid-liquid separation, washing, and obtains
Comparative sample 1Ni0.5Mn0.5(OH)2Material.
Comparative example 2
Ni/Co/Mn=1 in the sulfuric acid nickel cobalt manganese solution of 2mol/L, precipitating reagent are sodium hydroxide, concentration 10mol/L, network
Mixture is ammonium hydroxide, concentration 20wt%.Deionized water is added into reaction kettle in advance to bottom blade is not crossed, ammonium hydroxide is then added
PH value is adjusted to 10.5~11.0, reactor temperature is then risen to 50~60 DEG C.Salting liquid is pumped with the speed of 100ml/min
Enter in reaction kettle, ammonium hydroxide is pumped into reaction kettle simultaneously with the speed of 23ml/min and salt, sodium hydroxide solution, at this time NH4 +/Me
(molar ratio) is about 2.5, through pH value in the flow control reaction kettle of adjusting sodium hydroxide solution in 11.2~11.4 ranges,
Nitrogen protection is passed through when reaction.Reaction stops being pumped into each material solution after carrying out 30 hours, continues stirring 4 hours, obtained slurry
Material is 8~10 hours dry at a temperature of 120 DEG C by being separated by solid-liquid separation, washing, and obtains 2 spherical Ni of comparative sample1/3Co1/3Mn1/3
(OH)2Material.
Comparative example 3
Ni/Co/Al=80/15/5 in the sulfuric acid nickel cobalt aluminum solutions of 1.5mol/L is added in salting liquid by 5.6g/L
EDTA.Deionized water is added into reaction kettle in advance to bottom blade is not crossed, be then added ammonium hydroxide adjust pH value to 10.5~
11.0, reactor temperature is then risen to 50~60 DEG C.Salting liquid is pumped into reaction kettle with the speed of 50ml/min.With hydrogen-oxygen
Change sodium is precipitating reagent, and pH value is in 11.2~11.4 ranges in the flow control reaction kettle by adjusting sodium hydroxide solution, instead
Stopping being pumped into each material solution after should carrying out 30 hours, continues stirring 4 hours, obtained slurry, which passes through, to be separated by solid-liquid separation, washs,
It is 8~10 hours dry at a temperature of 150 DEG C, obtain 5 spherical Ni of sample0.8Co0.15Al0.05(OH)2Material.
Comparative example 4
Deionized water is added into reaction kettle in advance to bottom blade is not crossed, be then added ammonium hydroxide adjust pH value to 10.5~
11.0, reactor temperature is then risen to 40~50 DEG C.The cobalt sulfate solution of 2.5mol/L is pumped into instead with 50ml/min speed
Kettle is answered, while 20% ammonium hydroxide is pumped into the speed of 23ml/min, using 2.65mol/L sodium carbonate liquor as precipitating reagent, passes through adjusting
In 7.5~8.5 ranges, reaction stops being pumped into each original after carrying out 30 hours pH value in the flow control reaction kettle of sodium carbonate liquor
To expect solution, continues stirring 4 hours, obtained slurry is 8~10 hours dry at a temperature of 100 DEG C by being separated by solid-liquid separation, washing,
Obtain 7 spherical shape CoCO of sample3Material.
The performance of product is obtained in testing example and comparative example, as shown in the table.
Claims (9)
1. the preparation method of a kind of mono-/multi- metal co-precipitation hydroxide or carbonated, it is characterised in that include the following steps：
1) soluble salt solution for preparing mono-/multi- metal, is added urea, obtains solution I；
2) precipitant solution is prepared；
3) deionized water and ammonium hydroxide are added into reaction kettle, makes pure water pH value=10.5~11.0 in kettle, then utilizes thereto
Metering pump is pumped into solution I, precipitant solution and enveloping agent solution, in stirring, 50 DEG C~90 DEG C, pH value=10.5~12.5 and pH
Value fluctuation range carries out coprecipitation reaction under conditions of being less than ± 1.0；Wherein, the solution I enters heated, guarantor before reaction kettle
Demonstrate,prove when the solution I enters reaction kettle that wherein the resolution ratio of urea is 30~100%；
Solution I enters the pipeline before reaction kettle and heats through 70~100 DEG C of sink, or coats heating tape on the outside of pipeline and carry out
Heating；
4) after the reaction was completed, substance in reaction kettle is separated by solid-liquid separation, obtains the filter cake of hydroxide or carbonated, it will be described
Filter cake repeatedly washs removal foreign ion with deionized water；4~10h is dried under the conditions of 100~150 DEG C, obtains the mono-/multi-
Metal is co-precipitated hydroxide or carbonated.
2. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
Metal described in step 1) is any one or more in Ni, Co, Mn, Mg, Cu, Al, Fe, Sn and Ti.
3. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
Soluble salt solution described in step 1) is any one or more in sulfate, nitrate, chloride and acetate.
4. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
The concentration of soluble salt solution described in step 1) is 0.1~2.5mol/L.
5. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
In the solution I, the ratio of the sum of amount of substance of urea and metallic element is 0.5~10:1.
6. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
The precipitating reagent is sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, sodium bicarbonate or sodium carbonate.
7. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
The precipitant solution is the lithium hydroxide solution that concentration is 0.1~3mol/L or concentration is the hydrogen-oxygen of 0.1~10mol/L
Change sodium solution or potassium hydroxide solution perhaps concentration be 0.1~10mol/L sal volatile or concentration be 0.1~
The sodium bicarbonate solution or concentration of 1.3mol/L is the sodium carbonate liquor of 0.1~2.65mol/L.
8. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
The complexing agent is one of ammonium hydroxide, ethylenediamine, glutamic acid, EDTA, citric acid, sodium citrate or a variety of.
9. the preparation method of mono-/multi- metal co-precipitation hydroxide as described in claim 1 or carbonated, it is characterised in that：
Solute is 0.5~10/1 with the ratio of the amount of the substance of metal ion in enveloping agent solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611008517.0A CN106395754B (en) | 2016-11-16 | 2016-11-16 | Mono-/multi- metal is co-precipitated the preparation method of hydroxide or carbonated |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611008517.0A CN106395754B (en) | 2016-11-16 | 2016-11-16 | Mono-/multi- metal is co-precipitated the preparation method of hydroxide or carbonated |
Publications (2)
| Publication Number | Publication Date |
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| CN101570348A (en) * | 2008-09-11 | 2009-11-04 | 浙江华友钴业股份有限公司 | Preparation method for compact crystallographic form cobalt hydrate |
| CN105152231A (en) * | 2015-09-20 | 2015-12-16 | 成都育芽科技有限公司 | Method for preparing lithium battery anode material cobaltous hydroxide |
| CN105304897A (en) * | 2014-11-29 | 2016-02-03 | 董亚伦 | Preparation method for large particle cobalt hydroxide battery material |
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| CN101570348A (en) * | 2008-09-11 | 2009-11-04 | 浙江华友钴业股份有限公司 | Preparation method for compact crystallographic form cobalt hydrate |
| CN105304897A (en) * | 2014-11-29 | 2016-02-03 | 董亚伦 | Preparation method for large particle cobalt hydroxide battery material |
| CN105152231A (en) * | 2015-09-20 | 2015-12-16 | 成都育芽科技有限公司 | Method for preparing lithium battery anode material cobaltous hydroxide |
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