CN108314094A - A kind of preparation method of little particle nickel cobalt aluminum hydroxide - Google Patents
A kind of preparation method of little particle nickel cobalt aluminum hydroxide Download PDFInfo
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- CN108314094A CN108314094A CN201810084041.1A CN201810084041A CN108314094A CN 108314094 A CN108314094 A CN 108314094A CN 201810084041 A CN201810084041 A CN 201810084041A CN 108314094 A CN108314094 A CN 108314094A
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- C01P2004/30—Particle morphology extending in three dimensions
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention discloses a kind of preparation method of little particle nickel cobalt aluminum hydroxide.Prepare nickel cobalt aluminium mixed solution, ammonium bicarbonate soln, monoammonium phosphate solution；Mixed solution, ammonium bicarbonate soln and monoammonium phosphate solution cocurrent are added in the liquid of bottom, after addition, the reaction was continued for dropwise addition hydrogen peroxide and ammonium bicarbonate soln；Pulp after filtering, is then added ammonium hydroxide toward pulp material, and hot pure water washing is added in temperature reaction；It after being dried using tray drier, sieved, remove iron and batch mixing, obtain little particle nickel cobalt aluminum hydroxide.The present invention has obtained that the nickel cobalt aluminum hydroxide that grain size is less than 2.5 microns can be obtained, and sphericity is high, and tap density is high, and is the doping for realizing phosphorus, and simple for process, low energy consumption.
Description
Technical field
The present invention relates to a kind of preparation methods of little particle nickel cobalt aluminum hydroxide, belong to lithium battery new energy materials field.
Background technology
Power battery performance is to determine the restrictive factor of Development of Electric Vehicles, at this stage due to power battery cruising ability
Insufficient, the problems such as charging rate is slow, high expensive, constrains electric vehicle widespread development, this be also allow many consumers hope and
The cost performance of the main reason for step, power lithium battery largely affect the market popularity of electric vehicle.Positive material
Material is the core key material of power lithium battery, and the energy density height and the course continuation mileage of electric vehicle of positive electrode cease manner of breathing
Close, and its cost accounts for about the 1/3 of lithium battery electric core cost, so develop high-energy density, the long-life, high safety, it is low at
This positive electrode is most important to the scale commercialization of power lithium battery, electric vehicle.
Power lithium battery positive electrode technology path mainly has 3 schools both at home and abroad at present：LiFePO4 is sent, LiMn2O4 is sent,
Ternary is sent (nickel cobalt lithium aluminate (NCA) and nickle cobalt lithium manganate (NCM)).Wherein battery charging and discharging of the LiFePO4 as positive electrode
It has extended cycle life, but the disadvantage is that energy density, high temperature performance, charge/discharge rate property have larger gap, and production
Cost is higher, and ferric phosphate lithium cell technology and application have encountered the bottleneck of development；Under lithium manganate battery energy density low and high temperature
Cyclical stability and storage performance it is poor, thus positive electrode of the LiMn2O4 only as international 1st generation power lithium battery；And it is polynary
Material gradually surmounts LiFePO4 and manganese because the double dominant with comprehensive performance and cost is increasingly by industry is of interest and approval
Sour lithium becomes the technology path of mainstream.Especially using 2013 tesla outstanding of Nian Yi armies (Tesla) electric vehicles as representative,
For the TeslaModelS course continuation mileages of release up to 480km, positive electrode used by cylindrical cell is NCA.From battery energy
From the point of view of metric density and electric vehicle course continuation mileage, the ternary system of nickeliferous (Ni) is with the obvious advantage, especially high Ni ternary systems (NCA) material
The battery of making.
The demand of high-energy density power lithium battery has driven the application of the high Ni unitary material of height ratio capacity and lasting promotion,
And selling fast with U.S. Tesla, Panasonic, AESC, Nissan and South Korea LGC, SKI of such as Japan of Li electricity enterprises,
Samsung has focused on material selection above nickelic multicomponent material, by conventional LiNi1/3Co1/3Mn1/3O2(referred to as
NCM111 the multicomponent material LiNi of high nickel content), is gradually turned to0.5Co0.2Mn0.3O2(abbreviation NCM523),
LiNi0.6Co0.2Mn0.2O2(abbreviation NCM622), LiNi0.8Co0.1Mn0.1O2(abbreviation NCM811) and more nickelic Ni contents are
80%~89% NCA materials.
For nickel cobalt lithium aluminate cathode material, in order to improve its compacted density, that is, its energy density, current method are improved
To carry out mixing and doping using the nickel cobalt lithium aluminate of large-sized nickel cobalt lithium aluminate and small particle, its compacted density is improved, generally
It is required that 3 microns of the D50 ＜ of the nickel cobalt lithium aluminate of small particle, then require the grain size of nickel cobalt aluminum hydroxide to be less than 2.5 microns, still
Conventional coprecipitation technology generally cannot get the nickel cobalt aluminum hydroxide that grain size is less than 2.5 microns, obtained small particle nickel hydroxide
Cobalt aluminium sphericity is poor, and tap density is small, and high energy consumption.
Invention content
In view of this, the present invention provides a kind of preparation method of little particle nickel cobalt aluminum hydroxide, it is small grain size can be obtained
In 2.5 microns of nickel cobalt aluminum hydroxide, sphericity is high, and tap density is high, and is the doping for realizing phosphorus, simple for process, energy consumption
It is low.
The present invention solves above-mentioned technical problem by following technological means：
A kind of preparation method of little particle nickel cobalt aluminum hydroxide, is following steps：
(1) match liquid, nickel cobalt aluminium mixed solution in nickel cobalt aluminium salt mixed dissolution to pure water, will be obtained, acid ＆ alkali liquid is added and adjusts
The pH of mixed solution is 1.0-1.2, then carries out removing iron by fluid deferrization device, and accurate mistake is carried out using accurate filter
Filter, it is 30-35 DEG C to be then placed in constant temperature to temperature in thermostat；Pure water dissolving is added in ammonium hydrogen carbonate, then passes through fluid
Iron remover carries out removing iron, and secondary filter is carried out using accurate filter, and it is 30- to be then placed in constant temperature to temperature in thermostat
35℃；Pure water dissolving is added in monoammonium phosphate, then carries out removing iron by fluid deferrization device, be carried out using accurate filter
Secondary filter, it is 30-35 DEG C to be then placed in constant temperature to temperature in thermostat；
(2) it reacts, mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution cocurrent that step (1) is obtained are added
On earth in liquid, stablize the flow of the flow and monoammonium phosphate solution of mixed solution, the flow for adjusting ammonium bicarbonate soln maintains
The pH of reaction process is 6-6.5, and the time for adding material is 60-90min, and it is 35-40 DEG C that charging process, which maintains temperature, is stirred simultaneously
It is 250-350r/min to mix speed, after adding material, is 50-60 DEG C and maintains this temperature with temperature is warming up to, dioxygen is added dropwise
Water and ammonium bicarbonate soln, maintenance pH are 6-6.5, the reaction was continued after addition 10-30min, are then separated by solid-liquid separation, and obtain the
Hot pure water washing is added in one filter residue and the first filtrate, the first filter residue, washs to the conductivity of washings≤100 μ S/cm；
(3) pulp in polyolefins hyper-dispersant solution is added in precipitation conversion, the first filter residue after step (2) is washed,
The mass ratio of first filter residue and polyolefins hyper-dispersant solution is 1:5-10, it is 40-50 DEG C and perseverance that temperature is warming up to after pulp
Then ammonium hydroxide is added toward pulp material in temperature, it is 7.5-8.0 to maintain the pH of dropwise addition process, and after addition, it is 75- to be warming up to temperature
It 85 DEG C, after being stirred to react 30-40min, is separated by solid-liquid separation, obtains the second filter residue and the second filtrate, heat is added in the second filter residue
The conductivity of pure water washings is≤20 μ S/cm；
(4) it after the second filter residue after washing step (3) is dried using tray drier, sieved, remove iron and batch mixing,
Obtain little particle nickel cobalt aluminum hydroxide.
Step (1) the nickel cobalt aluminium purity salt is LITHIUM BATTERY, the total mole number of finally obtained nickel cobalt aluminium mixed solution
For 1.5-2mol/L, a concentration of 0.5-0.6mol/L of ammonium hydrogen carbonate, a concentration of 1-1.2mol/L of monoammonium phosphate, accurate mistake
Filter uses ceramic element, and the aperture of ceramic element is 20-100nm.
A concentration of 0.1-0.12mol/L of monoammonium phosphate in step (2) the midsole liquid, while it is molten that ammonium hydrogen carbonate is added
Liquid so that the pH of bottom liquid is 6-6.5, and the volume of bottom liquid is mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution being added
The 1/15-1/12 of total volume, the flow and monoammonium phosphate solution average rate of mixed solution are added in the liquid of bottom, maintain mixed solution
Nickel cobalt aluminium total mole number and monoammonium phosphate solution in the molar ratio of monoammonium phosphate be 3:2.1-2.15, the hydrogen peroxide of addition
Mass fraction be 25-30%, the hydrogen peroxide molal quantity of addition be to feed to finish the total mole number of nickel cobalt ion in Mother liquor
2-2.5 again.
The temperature for the hot pure water that the first residue washing uses in the step (2) is 70-75 DEG C, by the first filtrate and washing
The washings of first filter residue mix, and it is 2-3 that acid solution, which is then added, and adjusts the pH of solution, and TBP is then added and is extracted, by phosphorus
Acid extraction comes out, and ammonia scrubbing is added and recycles to obtain ammonium phosphate, raffinate crystallizes to obtain ammonium salt by concentration and evaporation.
A concentration of 0.01-0.02% of polyolefins hyper-dispersant solution in the step (3), mixing speed is when pulp
300-350r/min, slurry time 30-50min, ammonia concn 5-6mol/L, the total time for dripping ammonium hydroxide are 30-
45min。
The step (3) mixes the washings of the second filter residue of the second filtrate and washing, and it is 7.5- that ammonium hydroxide, which is added, and adjusts pH
8, after secondary filter, condensing crystallizing obtains monoammonium phosphate, returns and obtains monoammonium phosphate solution with liquid.
It is dried to moisture in the step (4) and is less than 0.5%, screening is sieved using 225 mesh, except iron uses electromagnetism
The magnetic induction intensity of iron remover, electric magnetic iron remover is 15000-25000 Gausses.
Then the present invention adds ammonium hydroxide, calcium phosphate precipitation is turned by the way that the calcium phosphate precipitation of nickel cobalt aluminium is first prepared
It is melted into hydroxide precipitation, to obtain nickel cobalt aluminum hydroxide, when preparing nickel cobalt aluminum precipitation, by controlling reaction condition, is obtained
To small particle, nickel cobalt aluminium that nickel cobalt aluminium is evenly distributed calcium phosphate precipitation, the index of obtained calcium phosphate precipitation is as follows：
| Index | D10 | D50 | D90 | BET | Tap density |
| Numerical value | 0.5-0.7μm | 1.5-1.8μm | 2.3-2.5μm | 8-12m2/g | 1.2-1.5g/mL |
Then plus ammonium hydroxide carries out precipitation conversion, is converted into hydroxide precipitation, using processing, finally obtained little particle
Nickel cobalt aluminum hydroxide index is as follows：
| Index | Ni+Co+Al | P | D10 | D50 | D90 |
| Numerical value | 60-61.5% | 2000-2500ppm | 0.4-0.6μm | 1.2-1.5μm | 2.0-2.3μm |
| D100 | Cd | Mg | Na | Mn | Ca |
| 5 μm of ＜ | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm |
| K | Zn | Cu | Ti | Pb | Si |
| ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm |
| Tap density | Sulfate radical | Chlorion | BET | pH | Pattern |
| 1.4-1.6g/mL | ＜ 20ppm | ＜ 20ppm | 5-8m2/g | 6-8 | It is spherical |
The nickel cobalt aluminum hydroxide that this technique obtains is green powder, and good fluidity, pattern is spherical shape.
In order to improve the rate of recovery of cobalt nickel, when using calcium phosphate precipitation, hydrogen peroxide is added and is aoxidized, will can not sink
The nickel cobalt ion in shallow lake further precipitates, and improves the rate of recovery of nickel cobalt.
The mother liquor of final precipitation conversion, condensing crystallizing obtain monoammonium phosphate and return to use, further reduce costs.
The beneficial effects of the invention are as follows：The nickel cobalt aluminum hydroxide that grain size is less than 2.5 microns can be obtained, sphericity is high, shakes
Real density is high, and is the doping for realizing phosphorus, and simple for process, low energy consumption.
Specific implementation mode
Below with reference to specific embodiment, the present invention is described in detail, a kind of little particle nickel hydroxide of the present embodiment
The preparation method of cobalt aluminium is following steps：
(1) match liquid, nickel cobalt aluminium mixed solution in nickel cobalt aluminium salt mixed dissolution to pure water, will be obtained, acid ＆ alkali liquid is added and adjusts
The pH of mixed solution is 1.0-1.2, then carries out removing iron by fluid deferrization device, and accurate mistake is carried out using accurate filter
Filter, it is 30-35 DEG C to be then placed in constant temperature to temperature in thermostat；Pure water dissolving is added in ammonium hydrogen carbonate, then passes through fluid
Iron remover carries out removing iron, and secondary filter is carried out using accurate filter, and it is 30- to be then placed in constant temperature to temperature in thermostat
35℃；Pure water dissolving is added in monoammonium phosphate, then carries out removing iron by fluid deferrization device, be carried out using accurate filter
Secondary filter, it is 30-35 DEG C to be then placed in constant temperature to temperature in thermostat；
(2) it reacts, mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution cocurrent that step (1) is obtained are added
On earth in liquid, stablize the flow of the flow and monoammonium phosphate solution of mixed solution, the flow for adjusting ammonium bicarbonate soln maintains
The pH of reaction process is 6-6.5, and the time for adding material is 60-90min, and it is 35-40 DEG C that charging process, which maintains temperature, is stirred simultaneously
It is 250-350r/min to mix speed, after adding material, is 50-60 DEG C and maintains this temperature with temperature is warming up to, dioxygen is added dropwise
Water and ammonium bicarbonate soln, maintenance pH are 6-6.5, the reaction was continued after addition 10-30min, are then separated by solid-liquid separation, and obtain the
Hot pure water washing is added in one filter residue and the first filtrate, the first filter residue, washs to the conductivity of washings≤100 μ S/cm；
(3) pulp in polyolefins hyper-dispersant solution is added in precipitation conversion, the first filter residue after step (2) is washed,
The mass ratio of first filter residue and polyolefins hyper-dispersant solution is 1:5-10, it is 40-50 DEG C and perseverance that temperature is warming up to after pulp
Then ammonium hydroxide is added toward pulp material in temperature, it is 7.5-8.0 to maintain the pH of dropwise addition process, and after addition, it is 75- to be warming up to temperature
It 85 DEG C, after being stirred to react 30-40min, is separated by solid-liquid separation, obtains the second filter residue and the second filtrate, heat is added in the second filter residue
The conductivity of pure water washings is≤20 μ S/cm；
(4) it after the second filter residue after washing step (3) is dried using tray drier, sieved, remove iron and batch mixing,
Obtain little particle nickel cobalt aluminum hydroxide.
Step (1) the nickel cobalt aluminium purity salt is LITHIUM BATTERY, the total mole number of finally obtained nickel cobalt aluminium mixed solution
For 1.5-2mol/L, a concentration of 0.5-0.6mol/L of ammonium hydrogen carbonate, a concentration of 1-1.2mol/L of monoammonium phosphate, accurate mistake
Filter uses ceramic element, and the aperture of ceramic element is 20-100nm.
A concentration of 0.1-0.12mol/L of monoammonium phosphate in step (2) the midsole liquid, while it is molten that ammonium hydrogen carbonate is added
Liquid so that the pH of bottom liquid is 6-6.5, and the volume of bottom liquid is mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution being added
The 1/15-1/12 of total volume, the flow and monoammonium phosphate solution average rate of mixed solution are added in the liquid of bottom, maintain mixed solution
Nickel cobalt aluminium total mole number and monoammonium phosphate solution in the molar ratio of monoammonium phosphate be 3:2.1-2.15, the hydrogen peroxide of addition
Mass fraction be 25-30%, the hydrogen peroxide molal quantity of addition be to feed to finish the total mole number of nickel cobalt ion in Mother liquor
2-2.5 again.
The temperature for the hot pure water that the first residue washing uses in the step (2) is 70-75 DEG C, by the first filtrate and washing
The washings of first filter residue mix, and it is 2-3 that acid solution, which is then added, and adjusts the pH of solution, and TBP is then added and is extracted, by phosphorus
Acid extraction comes out, and ammonia scrubbing is added and recycles to obtain ammonium phosphate, raffinate crystallizes to obtain ammonium salt by concentration and evaporation.
A concentration of 0.01-0.02% of polyolefins hyper-dispersant solution in the step (3), mixing speed is when pulp
300-350r/min, slurry time 30-50min, ammonia concn 5-6mol/L, the total time for dripping ammonium hydroxide are 30-
45min。
The step (3) mixes the washings of the second filter residue of the second filtrate and washing, and it is 7.5- that ammonium hydroxide, which is added, and adjusts pH
8, after secondary filter, condensing crystallizing obtains monoammonium phosphate, returns and obtains monoammonium phosphate solution with liquid.
It is dried to moisture in the step (4) and is less than 0.5%, screening is sieved using 225 mesh, except iron uses electromagnetism
The magnetic induction intensity of iron remover, electric magnetic iron remover is 15000-25000 Gausses.
Finally obtained little particle nickel cobalt aluminum hydroxide index is as follows：
| Index | Ni+Co+Al | P | D10 | D50 | D90 |
| Numerical value | 60-61.5% | 2000-2500ppm | 0.4-0.6μm | 1.2-1.5μm | 2.0-2.3μm |
| D100 | Cd | Mg | Na | Mn | Ca |
| 5 μm of ＜ | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm |
| K | Zn | Cu | Ti | Pb | Si |
| ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm | ＜ 10ppm |
| Tap density | Sulfate radical | Chlorion | BET | pH | Pattern |
| 1.4-1.6g/mL | ＜ 20ppm | ＜ 20ppm | 5-8m2/g | 6-8 | It is spherical |
Embodiment 1
A kind of preparation method of little particle nickel cobalt aluminum hydroxide, is following steps：
(1) match liquid, nickel cobalt aluminium mixed solution in nickel cobalt aluminium salt mixed dissolution to pure water, will be obtained, acid ＆ alkali liquid is added and adjusts
The pH of mixed solution is 1.15, then carries out removing iron by fluid deferrization device, carries out secondary filter using accurate filter, so
After to be put into thermostat constant temperature to temperature be 31.5 DEG C；Pure water dissolving is added in ammonium hydrogen carbonate, then passes through fluid deferrization device
It carries out removing iron, secondary filter is carried out using accurate filter, it is 31.5 DEG C to be then placed in constant temperature to temperature in thermostat；It will
Pure water dissolving is added in monoammonium phosphate, then carries out removing iron by fluid deferrization device, and accurate mistake is carried out using accurate filter
Filter, it is 31.5 DEG C to be then placed in constant temperature to temperature in thermostat；
(2) it reacts, mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution cocurrent that step (1) is obtained are added
On earth in liquid, stablize the flow of the flow and monoammonium phosphate solution of mixed solution, the flow for adjusting ammonium bicarbonate soln maintains
The pH of reaction process is 6.35, and the time for adding material is 80min, and it is 36 DEG C that charging process, which maintains temperature, while mixing speed
For 315r/min, after adding material, it is 53 DEG C and maintains this temperature with temperature is warming up to, hydrogen peroxide is added dropwise and ammonium hydrogen carbonate is molten
Liquid, it is 6.35, the reaction was continued after addition 20min to maintain pH, is then separated by solid-liquid separation, obtains the first filter residue and the first filtrate,
Hot pure water washing is added in first filter residue, washs to the conductivity of washings≤100 μ S/cm；
(3) pulp in polyolefins hyper-dispersant solution is added in precipitation conversion, the first filter residue after step (2) is washed,
The mass ratio of first filter residue and polyolefins hyper-dispersant solution is 1:8, it is 45 DEG C of simultaneously constant temperature that temperature is warming up to after pulp, then
Ammonium hydroxide is added toward pulp material, it is 7.8 to maintain the pH of dropwise addition process, and after addition, it is 79 DEG C to be warming up to temperature, is stirred to react
It after 35min, is separated by solid-liquid separation, obtains the second filter residue and the second filtrate, hot pure water, which is added, in the second filter residue washs washings
Conductivity is≤20 μ S/cm；
(4) it after the second filter residue after washing step (3) is dried using tray drier, sieved, remove iron and batch mixing,
Obtain little particle nickel cobalt aluminum hydroxide.
Step (1) the nickel cobalt aluminium purity salt is LITHIUM BATTERY, the total mole number of finally obtained nickel cobalt aluminium mixed solution
For 1.8mol/L, a concentration of 0.54mol/L of ammonium hydrogen carbonate, a concentration of 1.12mol/L of monoammonium phosphate, accurate filter is adopted
Aperture with ceramic element, ceramic element is 80nm.
A concentration of 0.11mol/L of monoammonium phosphate in step (2) the midsole liquid, while ammonium bicarbonate soln is added makes
The pH for obtaining bottom liquid is 6.35, and the volume of bottom liquid is that the mixed solution being added, ammonium bicarbonate soln and monoammonium phosphate solution are overall
Long-pending 1/14, the flow and monoammonium phosphate solution average rate of mixed solution are added in the liquid of bottom, maintain the nickel cobalt aluminium of mixed solution
The molar ratio of total mole number and monoammonium phosphate in monoammonium phosphate solution is 3:2.12, the mass fraction of the hydrogen peroxide of addition is
28%, the hydrogen peroxide molal quantity of addition is 2.15 times that charging finishes the total mole number of nickel cobalt ion in Mother liquor.
The temperature for the hot pure water that the first residue washing uses in the step (2) is 72.5 DEG C, by the first filtrate and washing
The washings of first filter residue mix, and it is 2.3 that acid solution, which is then added, and adjusts the pH of solution, and TBP is then added and is extracted, by phosphorus
Acid extraction comes out, and ammonia scrubbing is added and recycles to obtain ammonium phosphate, raffinate crystallizes to obtain ammonium salt by concentration and evaporation.
A concentration of the 0.013% of polyolefins hyper-dispersant solution in the step (3), mixing speed is when pulp
320r/min, slurry time 35min, ammonia concn 5.3mol/L, the total time for dripping ammonium hydroxide are 41min.
The step (3) mixes the washings of the second filter residue of the second filtrate and washing, and it is 7.8 that ammonium hydroxide, which is added, and adjusts pH,
After secondary filter, condensing crystallizing obtains monoammonium phosphate, returns and obtains monoammonium phosphate solution with liquid.
It is dried to moisture in the step (4) and is less than 0.5%, screening is sieved using 225 mesh, except iron uses electromagnetism
The magnetic induction intensity of iron remover, electric magnetic iron remover is 20000 Gausses.
Finally obtained little particle nickel cobalt aluminum hydroxide index is as follows：
| Index | Ni+Co+Al | P | D10 | D50 | D90 |
| Numerical value | 60.5% | 2230ppm | 0.45μm | 1.37μm | 2.18μm |
| D100 | Cd | Mg | Na | Mn | Ca |
| 4.87μm | 6ppm | 7ppm | 8ppm | 5.1ppm | 8.1ppm |
| K | Zn | Cu | Ti | Pb | Si |
| 1.2ppm | 2.8ppm | 0.25ppm | 5.6ppm | 2.8ppm | 8.7ppm |
| Tap density | Sulfate radical | Chlorion | BET | pH | Pattern |
| 1.52g/mL | 18.4ppm | 5.9ppm | 5.8m2/g | 6.8 | It is spherical |
Embodiment 2
A kind of preparation method of little particle nickel cobalt aluminum hydroxide, is following steps：
(1) match liquid, nickel cobalt aluminium mixed solution in nickel cobalt aluminium salt mixed dissolution to pure water, will be obtained, acid ＆ alkali liquid is added and adjusts
The pH of mixed solution is 1.08, then carries out removing iron by fluid deferrization device, carries out secondary filter using accurate filter, so
After to be put into thermostat constant temperature to temperature be 33.8 DEG C；Pure water dissolving is added in ammonium hydrogen carbonate, then passes through fluid deferrization device
It carries out removing iron, secondary filter is carried out using accurate filter, it is 33.8 DEG C to be then placed in constant temperature to temperature in thermostat；It will
Pure water dissolving is added in monoammonium phosphate, then carries out removing iron by fluid deferrization device, and accurate mistake is carried out using accurate filter
Filter, it is 33.8 DEG C to be then placed in constant temperature to temperature in thermostat；
(2) it reacts, mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution cocurrent that step (1) is obtained are added
On earth in liquid, stablize the flow of the flow and monoammonium phosphate solution of mixed solution, the flow for adjusting ammonium bicarbonate soln maintains
The pH of reaction process is 6.15, and the time for adding material is 70min, and it is 38.5 DEG C that charging process, which maintains temperature, while stirring speed
Degree is 275r/min, after adding material, is 52 DEG C and maintains this temperature with temperature is warming up to, hydrogen peroxide and ammonium hydrogen carbonate is added dropwise
Solution, it is 6.15, the reaction was continued after addition 20min to maintain pH, is then separated by solid-liquid separation, and obtains the first filter residue and the first filter
Hot pure water washing is added in liquid, the first filter residue, washs to the conductivity of washings≤100 μ S/cm；
(3) pulp in polyolefins hyper-dispersant solution is added in precipitation conversion, the first filter residue after step (2) is washed,
The mass ratio of first filter residue and polyolefins hyper-dispersant solution is 1:9, it is 43 DEG C of simultaneously constant temperature that temperature is warming up to after pulp, then
Ammonium hydroxide is added toward pulp material, it is 7.9 to maintain the pH of dropwise addition process, and after addition, it is 79 DEG C to be warming up to temperature, is stirred to react
It after 33min, is separated by solid-liquid separation, obtains the second filter residue and the second filtrate, hot pure water, which is added, in the second filter residue washs washings
Conductivity is≤20 μ S/cm；
(4) it after the second filter residue after washing step (3) is dried using tray drier, sieved, remove iron and batch mixing,
Obtain little particle nickel cobalt aluminum hydroxide.
Step (1) the nickel cobalt aluminium purity salt is LITHIUM BATTERY, the total mole number of finally obtained nickel cobalt aluminium mixed solution
For 1.8mol/L, a concentration of 0.55mol/L of ammonium hydrogen carbonate, a concentration of 1.15mol/L of monoammonium phosphate, accurate filter is adopted
Aperture with ceramic element, ceramic element is 40nm.
A concentration of 0.112mol/L of monoammonium phosphate in step (2) the midsole liquid, while ammonium bicarbonate soln is added
So that the pH of bottom liquid is 6.15, the volume of bottom liquid be that the mixed solution, ammonium bicarbonate soln and monoammonium phosphate solution of addition are total
The 1/13 of volume, the flow and monoammonium phosphate solution average rate of mixed solution are added in the liquid of bottom, maintain the nickel cobalt of mixed solution
The molar ratio of aluminium total mole number and monoammonium phosphate in monoammonium phosphate solution is 3:2.12, the mass fraction of the hydrogen peroxide of addition
It is 27%, the hydrogen peroxide molal quantity of addition is 2.35 times that charging finishes the total mole number of nickel cobalt ion in Mother liquor.
The temperature for the hot pure water that the first residue washing uses in the step (2) is 73.5 DEG C, by the first filtrate and washing
The washings of first filter residue mix, and it is 2.15 that acid solution, which is then added, and adjusts the pH of solution, and TBP is then added and is extracted, will
Phosphoric acid extraction comes out, and ammonia scrubbing is added and recycles to obtain ammonium phosphate, raffinate crystallizes to obtain ammonium salt by concentration and evaporation.
A concentration of the 0.013% of polyolefins hyper-dispersant solution in the step (3), mixing speed is when pulp
315r/min, slurry time 45min, ammonia concn 5.5mol/L, the total time for dripping ammonium hydroxide are 41min.
The step (3) mixes the washings of the second filter residue of the second filtrate and washing, and it is 7.85 that ammonium hydroxide, which is added, and adjusts pH,
After secondary filter, condensing crystallizing obtains monoammonium phosphate, returns and obtains monoammonium phosphate solution with liquid.
It is dried to moisture in the step (4) and is less than 0.5%, screening is sieved using 225 mesh, except iron uses electromagnetism
The magnetic induction intensity of iron remover, electric magnetic iron remover is 20000 Gausses.
Finally obtained little particle nickel cobalt aluminum hydroxide index is as follows：
| Index | Ni+Co+Al | P | D10 | D50 | D90 |
| Numerical value | 60.8% | 2150ppm | 0.47μm | 1.39μm | 2.17μm |
| D100 | Cd | Mg | Na | Mn | Ca |
| 4.68μm | 3.2ppm | 5.7ppm | 2.9ppm | 5.9ppm | 6.8ppm |
| K | Zn | Cu | Ti | Pb | Si |
| 5.9ppm | 7.1ppm | 6.7ppm | 3.8ppm | 1.8ppm | 4.9ppm |
| Tap density | Sulfate radical | Chlorion | BET | pH | Pattern |
| 1.51g/mL | 13ppm | 10.9ppm | 6.8m2/g | 7.2 | It is spherical |
Embodiment 3
A kind of preparation method of little particle nickel cobalt aluminum hydroxide, is following steps：
(1) match liquid, nickel cobalt aluminium mixed solution in nickel cobalt aluminium salt mixed dissolution to pure water, will be obtained, acid ＆ alkali liquid is added and adjusts
The pH of mixed solution is 1.13, then carries out removing iron by fluid deferrization device, carries out secondary filter using accurate filter, so
After to be put into thermostat constant temperature to temperature be 33.8 DEG C；Pure water dissolving is added in ammonium hydrogen carbonate, then passes through fluid deferrization device
It carries out removing iron, secondary filter is carried out using accurate filter, it is 33.8 DEG C to be then placed in constant temperature to temperature in thermostat；It will
Pure water dissolving is added in monoammonium phosphate, then carries out removing iron by fluid deferrization device, and accurate mistake is carried out using accurate filter
Filter, it is 33.8 DEG C to be then placed in constant temperature to temperature in thermostat；
(2) it reacts, mixed solution, ammonium bicarbonate soln and the monoammonium phosphate solution cocurrent that step (1) is obtained are added
On earth in liquid, stablize the flow of the flow and monoammonium phosphate solution of mixed solution, the flow for adjusting ammonium bicarbonate soln maintains
The pH of reaction process is 6.25, and the time for adding material is 80min, and it is 38 DEG C that charging process, which maintains temperature, while mixing speed
For 335r/min, after adding material, it is 55 DEG C and maintains this temperature with temperature is warming up to, hydrogen peroxide is added dropwise and ammonium hydrogen carbonate is molten
Liquid, it is 6.25, the reaction was continued after addition 25min to maintain pH, is then separated by solid-liquid separation, obtains the first filter residue and the first filtrate,
Hot pure water washing is added in first filter residue, washs to the conductivity of washings≤100 μ S/cm；
(3) pulp in polyolefins hyper-dispersant solution is added in precipitation conversion, the first filter residue after step (2) is washed,
The mass ratio of first filter residue and polyolefins hyper-dispersant solution is 1:9, it is 43 DEG C of simultaneously constant temperature that temperature is warming up to after pulp, then
Ammonium hydroxide is added toward pulp material, it is 7.9 to maintain the pH of dropwise addition process, and after addition, it is 79 DEG C to be warming up to temperature, is stirred to react
It after 35min, is separated by solid-liquid separation, obtains the second filter residue and the second filtrate, hot pure water, which is added, in the second filter residue washs washings
Conductivity is≤20 μ S/cm；
(4) it after the second filter residue after washing step (3) is dried using tray drier, sieved, remove iron and batch mixing,
Obtain little particle nickel cobalt aluminum hydroxide.
Step (1) the nickel cobalt aluminium purity salt is LITHIUM BATTERY, the total mole number of finally obtained nickel cobalt aluminium mixed solution
For 1.85mol/L, a concentration of 0.54mol/L of ammonium hydrogen carbonate, a concentration of 1.12mol/L of monoammonium phosphate, accurate filter
Using ceramic element, the aperture of ceramic element is 40nm.
A concentration of 0.11mol/L of monoammonium phosphate in step (2) the midsole liquid, while ammonium bicarbonate soln is added makes
The pH for obtaining bottom liquid is 6.25, and the volume of bottom liquid is that the mixed solution being added, ammonium bicarbonate soln and monoammonium phosphate solution are overall
Long-pending 1/12, the flow and monoammonium phosphate solution average rate of mixed solution are added in the liquid of bottom, maintain the nickel cobalt aluminium of mixed solution
The molar ratio of total mole number and monoammonium phosphate in monoammonium phosphate solution is 3:2.13, the mass fraction of the hydrogen peroxide of addition is
29%, the hydrogen peroxide molal quantity of addition is 2.35 times that charging finishes the total mole number of nickel cobalt ion in Mother liquor.
The temperature for the hot pure water that the first residue washing uses in the step (2) is 72 DEG C, by the first filtrate and washing the
The washings of one filter residue mix, and it is 2.5 that acid solution, which is then added, and adjusts the pH of solution, and TBP is then added and is extracted, by phosphoric acid
It extracts, ammonia scrubbing is added and recycles to obtain ammonium phosphate, raffinate crystallizes to obtain ammonium salt by concentration and evaporation.
A concentration of the 0.015% of polyolefins hyper-dispersant solution in the step (3), mixing speed is when pulp
325r/min, slurry time 40min, ammonia concn 5.3mol/L, the total time for dripping ammonium hydroxide are 42min.
The step (3) mixes the washings of the second filter residue of the second filtrate and washing, and it is 7.75 that ammonium hydroxide, which is added, and adjusts pH,
After secondary filter, condensing crystallizing obtains monoammonium phosphate, returns and obtains monoammonium phosphate solution with liquid.
It is dried to moisture in the step (4) and is less than 0.5%, screening is sieved using 225 mesh, except iron uses electromagnetism
The magnetic induction intensity of iron remover, electric magnetic iron remover is 18000 Gausses.
Finally obtained little particle nickel cobalt aluminum hydroxide index is as follows：
| Index | Ni+Co+Al | P | D10 | D50 | D90 |
| Numerical value | 60.9% | 2080ppm | 0.51μm | 1.38μm | 2.09μm |
| D100 | Cd | Mg | Na | Mn | Ca |
| 4.18μm | 3.8ppm | 2.7ppm | 6.9ppm | 5.9ppm | 2.9ppm |
| K | Zn | Cu | Ti | Pb | Si |
| 2.9ppm | 2.9ppm | 0.9ppm | 4.8ppm | 2.9ppm | 5.9ppm |
| Tap density | Sulfate radical | Chlorion | BET | pH | Pattern |
| 1.57g/mL | 12.9ppm | 10.8ppm | 6.8m2/g | 6.95 | It is spherical |
The product mix lithium carbonate that embodiment 1,2,3 obtains is sintered, the positive electrode of obtained nickel cobalt lithium aluminate
Index it is as follows
The nickle cobalt lithium manganate that the nickel cobalt lithium aluminate of this small particle is 15-20 μm with grain size is doped, is uniformly mixed：
It can obtain, the nickel cobalt lithium aluminate of the small particle of the small particle nickel cobalt aluminum hydroxide preparation of this patent is with grain size
15-20 μm of nickle cobalt lithium manganate is doped, and can significantly improve the compacted density of positive electrode.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (7)
1. a kind of preparation method of little particle nickel cobalt aluminum hydroxide, which is characterized in that be following steps：
(1) match liquid, nickel cobalt aluminium mixed solution in nickel cobalt aluminium salt mixed dissolution to pure water, will be obtained, acid ＆ alkali liquid is added and adjusts mixing
The pH of solution is 1.0-1.2, then carries out removing iron by fluid deferrization device, carries out secondary filter using accurate filter, so
After to be put into thermostat constant temperature to temperature be 30-35 DEG C；Pure water dissolving is added in ammonium hydrogen carbonate, then passes through fluid deferrization device
It carries out removing iron, secondary filter is carried out using accurate filter, it is 30-35 DEG C to be then placed in constant temperature to temperature in thermostat；
Pure water dissolving is added in monoammonium phosphate, then carries out removing iron by fluid deferrization device, be carried out using accurate filter accurate
Filtering, it is 30-35 DEG C to be then placed in constant temperature to temperature in thermostat；
(2) it reacts, mixed solution, ammonium bicarbonate soln and monoammonium phosphate solution cocurrent that step (1) obtains is added to bottom
In liquid, stablize the flow of the flow and monoammonium phosphate solution of mixed solution, the flow for adjusting ammonium bicarbonate soln maintains reaction
The pH of process is 6-6.5, and the time for adding material is 60-90min, and it is 35-40 DEG C that charging process, which maintains temperature, while stirring speed
Degree is 250-350r/min, after adding material, is 50-60 DEG C and maintains this temperature with temperature is warming up to, be added dropwise hydrogen peroxide and
Ammonium bicarbonate soln, maintenance pH are 6-6.5, the reaction was continued after addition 10-30min, are then separated by solid-liquid separation, obtain the first filter
Hot pure water washing is added in slag and the first filtrate, the first filter residue, washs to the conductivity of washings≤100 μ S/cm；
(3) precipitation converts, pulp in the first filter residue addition polyolefins hyper-dispersant solution after step (2) is washed, and first
The mass ratio of filter residue and polyolefins hyper-dispersant solution is 1:5-10, it is 40-50 DEG C of simultaneously constant temperature that temperature is warming up to after pulp, so
Ammonium hydroxide is added toward pulp material afterwards, it is 7.5-8.0 to maintain the pH of dropwise addition process, and after addition, it is 75-85 DEG C to be warming up to temperature,
It after being stirred to react 30-40min, is separated by solid-liquid separation, obtains the second filter residue and the second filtrate, the second filter residue addition hot pure water is washed
The conductivity for washing washings is≤20 μ S/cm；
(4) it after the second filter residue after washing step (3) is dried using tray drier, sieved, remove iron and batch mixing, obtained
Little particle nickel cobalt aluminum hydroxide.
2. a kind of preparation method of little particle nickel cobalt aluminum hydroxide according to claim 1, it is characterised in that：The step
(1) nickel cobalt aluminium purity salt is LITHIUM BATTERY, and the total mole number of finally obtained nickel cobalt aluminium mixed solution is 1.5-2mol/L, carbonic acid
A concentration of 0.5-0.6mol/L of hydrogen ammonium, a concentration of 1-1.2mol/L of monoammonium phosphate, accurate filter use ceramic element,
The aperture of ceramic element is 20-100nm.
3. a kind of preparation method of little particle nickel cobalt aluminum hydroxide according to claim 1, it is characterised in that：The step
(2) in midsole liquid monoammonium phosphate a concentration of 0.1-0.12mol/L, while ammonium bicarbonate soln is added and so that the pH of bottom liquid is
The volume of 6-6.5, bottom liquid are the mixed solution being added, the 1/15-1/ of ammonium bicarbonate soln and monoammonium phosphate overall solution volume
12, the flow and monoammonium phosphate solution average rate of mixed solution are added in the liquid of bottom, maintain the nickel cobalt aluminium total moles of mixed solution
The molar ratio of number and monoammonium phosphate in monoammonium phosphate solution is 3:The mass fraction of 2.1-2.15, the hydrogen peroxide of addition is
25-30%, the hydrogen peroxide molal quantity of addition are 2-2.5 times that charging finishes the total mole number of nickel cobalt ion in Mother liquor.
4. a kind of preparation method of little particle nickel cobalt aluminum hydroxide according to claim 1, it is characterised in that：The step
(2) temperature for the hot pure water that the first residue washing uses in is 70-75 DEG C, by the washings of the first filtrate and the first filter residue of washing
Mixing, it is 2-3 that acid solution, which is then added, and adjusts the pH of solution, and TBP is then added and is extracted, phosphoric acid extraction is come out, is added
Ammonia scrubbing recycles to obtain ammonium phosphate, and raffinate crystallizes to obtain ammonium salt by concentration and evaporation.
5. a kind of preparation method of little particle nickel cobalt aluminum hydroxide according to claim 1, it is characterised in that：The step
(3) a concentration of 0.01-0.02% of polyolefins hyper-dispersant solution in, mixing speed is 300-350r/min, slurry when pulp
The change time is 30-50min, ammonia concn 5-6mol/L, and the total time for dripping ammonium hydroxide is 30-45min.
6. a kind of preparation method of little particle nickel cobalt aluminum hydroxide according to claim 1, it is characterised in that：The step
(3) washings of the second filter residue of the second filtrate and washing are mixed, it is 7.5-8 that ammonium hydroxide, which is added, and adjusts pH, after secondary filter,
Condensing crystallizing obtains monoammonium phosphate, returns and obtains monoammonium phosphate solution with liquid.
7. a kind of preparation method of little particle nickel cobalt aluminum hydroxide according to claim 1, it is characterised in that：The step
(4) it is dried to moisture in and is less than 0.5%, screening is sieved using 225 mesh, except iron uses electric magnetic iron remover, electromagnetism to remove iron
The magnetic induction intensity of device is 15000-25000 Gausses.
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