CN109437336A - A method of ternary lithium ion battery presoma is prepared from crude cobalt hydroxide - Google Patents

A method of ternary lithium ion battery presoma is prepared from crude cobalt hydroxide Download PDF

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CN109437336A
CN109437336A CN201811415578.8A CN201811415578A CN109437336A CN 109437336 A CN109437336 A CN 109437336A CN 201811415578 A CN201811415578 A CN 201811415578A CN 109437336 A CN109437336 A CN 109437336A
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added
filtrate
solution
ternary
cobalt
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CN109437336B (en
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刘芳洋
蒋良兴
贾明
潘逸宁
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/40Nickelates
    • C01G53/42Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention provides a kind of method from crude cobalt hydroxide preparation ternary lithium ion battery presoma, in this method, passes sequentially through excellent molten removal of impurities, Na2SO3Reducing leaching cobalt hydroxide, sodium jarosite tentatively except iron, neutralize heavy aluminium, the preliminary decopperized lead of vulcanization, be fluorinated most impurity element in addition to heavy calcium and magnesium, the separation of cobalt sodium and acid is molten, these steps of P204 extracting copper zinc remove cobalt nickel manganese, pass through the content and ternary material LiNi of the cobalt that purification obtainsxMnyCozO2In x, y value determine the additive amount of nickel sulfate and manganese sulfate, and added into cobalt-carrying solution, wherein x+y+z=1;Volatile carbonate is finally added into solution, cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.The present invention not only prepares the diversification of feedstock of presoma by the direct synthesis of ternary presoma of one-step method, but also by optimal impurity removal process, controls cost.

Description

A method of ternary lithium ion battery presoma is prepared from crude cobalt hydroxide
Technical field
The present invention relates to field of lithium ion battery, more particularly to one kind to prepare ternary lithium ion battery from crude cobalt hydroxide The method of presoma.
Background technique
Lithium ion battery is the new generation of green high-energy battery of performance brilliance, it has also become the emphasis of hi-tech development it One.Lithium ion battery has the following characteristics that high voltage, high capacity, low consumption, memory-less effect, nuisanceless, small in size, internal resistance It is small, self discharge is few, cycle-index is more.Because of its These characteristics, lithium ion battery has application to mobile phone, laptop, takes the photograph Camera, digital camera etc. be numerous civilian and military field.The main composition material of lithium ion battery includes electrolyte, isolation material Material, positive and negative pole material etc..Positive electrode occupies larger proportion (mass ratio of positive and negative pole material is 3:1~4:1), because of positive material The performance of material directly affects the performance of lithium ion battery, and cost also directly determines battery cost height.Currently, lithium-ion electric The positive electrode active materials in pond mainly have cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiMn2O4 (LiMn2O4) and ferrous acid lithium (LiFePO4), ternary material LiNixCoyMnzO2(x+y+z=1) etc., with the development of power lithium battery pool technology, lithium ion power Cell positive material gradually develops towards the direction of high voltage, high security, low cost, high-energy density.Ternary material is with it Lower price, high multiplying power discharging property, good cycle performance have obtained the common concern of people.Especially when voltage model It encloses when improving from 3.0-4.2V to 3.0-4.3V, the electric discharge gram volume performance of ternary material can be from original 160-170mAh/g Left and right is promoted to 171-182mAh/g, is that power battery preferably selects.Currently, ternary material precursor, is with nickel salt, cobalt Salt, manganese salt are that raw material carries out production acquisition, and raw material is single, and cost controlled range is small.
Summary of the invention
The present invention is directed at least solve one of above-mentioned technical problem.
The purpose of the present invention is to provide a kind of methods from the direct synthesis of ternary presoma of ore raw materials one-step method.
To achieve the goals above, proposed by the present invention a kind of from crude cobalt hydroxide preparation ternary lithium ion battery forerunner The impurity of the method for body, the crude cobalt hydroxide includes silicon, iron, copper, zinc, calcium, magnesium, lead and aluminium, and the method includes following Step:
A, excellent molten removal of impurities
It is stirred under conditions of liquid-solid ratio 4-10:1,50-70 DEG C of temperature with hot water and washes crude cobalt hydroxide, so that zinc, copper, magnesium Partial removal;
B, reducing leaching
H is added into the substance after step A washing2SO4And Na2SO3, pH is adjusted to 1.5-2.0, so that cobalt hydroxide quilt Reduction of dissolved, silica are transformed into silicic acid;
C, sodium jarosite tentatively removes iron
The substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 80-99 DEG C, and crystalline substance is added Kind and sodium sulphate, pH are still controlled in 1.5-2.0;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, NaOH is added into filtrate and adjusts pH to 5.0- 6.0;
E, vulcanize preliminary copper removal, lead
NaOH is continuously added after to the heavy aluminium of step D in liquid and adjusts pH > 7.5, Na is added2S, solution temperature are 50-70 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, NaF, reaction temperature 50- are added into filtrate 70℃;
G, the separation of cobalt sodium is molten with acid
Na is added in the filtrate obtained to step F2CO3Until pH is adjusted to 9.0 or more, sediment is obtained;By sediment Washing is to after neutrality, with sulfuric acid dissolution, and solution ph is controlled in 3.0-4.0;
H, P204 extracting copper, zinc
P204 after synergic reagent and NaOH saponification are added in the solution obtained to step G, is extracted, at room temperature wherein assisting The volume ratio for extracting agent is 3%-6%, and the volume ratio of P204 is 15%-25%, and the volume ratio of organic phase and water phase is 0.8-1.2: 1, extraction stoste pH is still controlled in 3.0-4.0;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true Determine the additive amount of nickel sulfate and manganese sulfate, and added into raffinate, wherein x+y+z=1;
J, cocurrent synthesizes
Volatile carbonate is added in the solution obtained to step I, cobalt, nickel, manganese are precipitated as carbonate;Carbonate mistake Washing obtains required ternary lithium ion battery presoma to neutrality after filter.
Preferably, the liquid-solid ratio in the step A is 6:1, and temperature is 60-65 DEG C.
Preferably, in the step B, Na2SO3Actual amount be 1.5-2 times of theoretical amount.
Preferably, in the step C, filtrate is heated to 95 DEG C.
Preferably, in the step D, Na2The actual amount of S is 2-5 times of theoretical amount.
Preferably, in the step E, reaction temperature is 65-70 DEG C.
Preferably, the reaction temperature in the step F is 60 DEG C, and the actual amount of NaF is the 1.5-2.0 of theoretical amount Times.
Preferably, in the step H, synergic reagent volume ratio is that 4%, P204 volume ratio is 20%, organic phase and water phase Volume ratio is 1:1.
Basic ideas and technical principle of the invention are as follows:
The soluble impurity carried secretly in crude cobalt hydroxide, can stir to wash in process and removed in hot water.Stir wash can make its zinc, Copper, nickel, magnesium, sodium partial removal.To wash the cobalt that process is lost in wash water be about 0.5% stirring.
Then by material reduction of dissolved, insoluble impurities, reaction equation are as follows: 2Co (OH) are removed3+Na2SO3+2H2SO4= 2CoSO4+Na2SO4+5H20.To obtain the red, transparent solution without black particle as criterion, the end of reduction of dissolved reaction is determined Point.The step needs to carry out in acid condition, therefore in next removal step, it then follows the principle of pH from low to high is kept away Exempt from that pH value need to be adjusted on a large scale repeatedly, to save supplementary product consumption.The process can also effectively remove silicon impurities, and silicon impurities are generally with two Oxidation Silicon forms are present in raw material.Silica vitriolization can generate the silicic acid insoluble in sulfuric acid and water, can pass through Filter is removed, but because its content is less, therefore silicic acid filtration step is merged with the filtration step of reduction of dissolved.
Then it carries out tentatively removing iron, if iron precipitate colloid directly can be made using the method for increasing pH value, absorption is a large amount of Containing cobalt, nickel, manganese solution, lead to production loss, and colloid is difficult to filter, therefore take yellow modumite method except iron.Sodium jarosite It is the double salt of the sulfate of two or more metals.General formula is Na2O3·3Fe2O3·6H2O or Me+Fe(SO4)2(OH)6Or Me2+Fe6 (SO4)4(OH)12, belong to complicated basic salt precipitating, the characteristics of there is well-crystallized, be easy filtering.It is lost in iron removal step Cobalt in scum is about 1%.
Aluminium is removed except adding sodium hydroxide after iron and continuing to increase pH value.Vulcanized sodium copper removal, lead step can be in neutral items It is carried out under part, and is not suitable for carrying out in acid condition, therefore by decopperized lead procedure after except aluminium.Vulcanized sodium decopperized lead Principle be: PbS, CuS solubility product are respectively less than CoS, and after vulcanized sodium is added, copper removal rate is up to 99% or more, and liquid cupric is small after copper removal In 0.04g/L.There are about 5% or so Co2+It avales simultaneously.Vulcanized slag contains Co 20~30%, can further recycle Co.
Sodium fluoride removing calcium and magnesium also needs to carry out in neutral conditions.Battery grade cobalt sulfate, it is more demanding to magnesium, calcium content.It is logical Crossing addition NaF is precipitating reagent, Ca2+、Mg2+Equal elements are precipitated with fluoride, and reach purification separation.Its reaction equation is as follows:
Mg2++2F-=MgF2
Ca2++2F-=CaF2
In above several steps, all introduce a large amount of sodium ion impurity, therefore sodium ion need to be removed, sodium carbonate be added, with cobalt, Nickel, manganese produce carbonate deposition, and sodium ion stops in the solution, to achieve the purpose that remove sodium ion.
The present invention has the advantages that compared with the technology of existing preparation ternary lithium ion battery presoma
(1) directly using ore is raw material, and optimal impurity removal process is provided according to the impurity component of ore raw materials, is obtained The material of ternary lithium ion battery presoma.The diversification of feedstock of presoma is not only prepared, but also optimal removal of impurities can be passed through Technique reduces supplementary product consumption, controls cost, effectively reduces the generation of exhaust gas, waste water, waste residue.
(2) present invention passes through the direct synthesis of ternary presoma of one-step method.Without using other chemicals by cobalt, nickel, manganese Separation;Dry without by nickel sulfate, cobaltous sulfate, manganese sulfate evaporation as solid, then to pass through cocurrent synthesis step molten by three kinds of salt Solve cocurrent.
Detailed description of the invention
Fig. 1 is the process flow chart for the method that the present invention prepares ternary lithium ion battery presoma from crude cobalt hydroxide.
Specific embodiment
Illustrate embodiments of the present invention below by embodiment, following embodiment be intended to illustrate invention rather than The scope of the present invention is further limited.
Following embodiment is implemented using process flow chart shown in Fig. 1.
Embodiment 1
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4With 612.93gNa2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, protect reaction starting, terminal pH adjusting always It holds 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, is added 25gNa2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 2
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 4000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 3
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 10000g sufficiently to stir and is washed, is filtered, removing part makes Obtain the impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4With 612.93gNa2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, protect reaction starting, terminal pH adjusting always It holds 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, is added 25gNa2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 4
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 50 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 5
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 70 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 6
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.8, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 7
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 2.0, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 8
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4With 612.93gNa2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, protect reaction starting, terminal pH adjusting always It holds 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 80 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 9
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.8;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 10
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 2.0;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, is added 25gNa2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 11
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.5;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 12
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 6.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, is added 25gNa2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 13
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 50 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 14
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 70 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 15
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.5;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 16
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 4.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2204mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 17
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 87mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2233mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 3%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 18
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 174mL synergic reagent and 580mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2146mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 19
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 435mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2349mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 15%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 20
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 116mL synergic reagent and 725mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2059mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 25%, organic phase and water phase Volume ratio 1:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 21
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 92.8mL synergic reagent and 464mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 1763.2mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water Phase volume ratio 0.8:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.
Embodiment 22
Using the crude cobalt hydroxide of 1000g as raw material, wherein 382.10g containing cobalt, magnesium 124.67g, manganese 42.70g, copper 16.08g, iron 11.87g, silicon 10.95g, aluminium 10.57g, calcium 6.01g, zinc 3.47g, nickel 2.48g, lead 1.02g.
A, excellent molten removal of impurities
The crude cobalt hydroxide raw material of 1000g is added in 60 DEG C of hot water of 6000g sufficiently to stir and is washed, is filtered, part is removed and makes The impurity such as zinc, copper, magnesium;
B, reducing leaching
The H for being slowly added to that 3250g volume fraction is 19.6% is added into the substance after step A washing2SO4And 612.93g Na2SO3, as reaction carries out, H constantly is added to reaction solution2SO4, remain at reaction starting, terminal pH adjusting 1.5, so that cobalt hydroxide is reduced dissolution, silica is transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 95 DEG C, and be added crystal seed and Sodium sulphate, PH are still controlled 1.5;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, the NaOH of volume fraction 8% is added into filtrate Solution adjusts pH to 5.0;
E, vulcanize preliminary copper removal, lead
The NaOH solution for continuously adding mass fraction 8% after to the heavy aluminium of step D in liquid adjusts pH > 7.5, and 25g is added Na2S, solution temperature are 65 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, 266g NaF, reaction temperature are added into filtrate It is 60 DEG C;
G, the separation of cobalt sodium is molten with acid
The Na of mass fraction 15% is added in the filtrate obtained to step F2CO3Solution is adjusted to 9.0 or more up to pH, Obtain sediment;Sediment is washed to neutrality, the H for being 19.6% with volume fraction2SO42900g dissolution, and by pH value of solution Value control is 3.0;
H, P204 extracting copper, zinc
P204 after 139.2mL synergic reagent and 696mL NaOH saponification are added in the solution obtained to step G, sulfonated kerosene 2644.8mL is extracted at room temperature, and the volume ratio that wherein volume ratio of synergic reagent is 4%, P204 is 20%, organic phase and water Phase volume ratio 1.2:1;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value come it is true The additive amount for determining nickel sulfate and manganese sulfate then needs addition nickel sulfate 12055.43g if 811 materials, i.e. x:y:z=8:1:1, Manganese sulfate 749.13g then needs addition nickel sulfate 4513.86g, manganese sulfate if 622 materials, i.e. x:y:z=6:2:2 749.13g;If 523 materials, i.e. x:y:z=5:2:3, then addition nickel sulfate 2502.78g, manganese sulfate 460.30g are needed, if 111 materials, i.e. x:y:z=1:1:1 then need addition nickel sulfate 1497.23g, manganese sulfate 749.13g.
J, cocurrent synthesizes
(NH is added in the solution obtained to step I4)2CO3If ternary material is 811 in step I, (NH is added4)2CO3 (NH is added if ternary material is 622 in step I in 6616.73g4)2CO33308.36g, if ternary material is in step I 523, then (NH is added4)2CO3(NH is added if ternary material is 111 in step I in 2205.58g4)2CO31985.02g with Cobalt, nickel, manganese are precipitated as carbonate;Washing obtains required ternary lithium ion battery presoma to neutrality after carbonate filtering.

Claims (8)

1. a kind of method from crude cobalt hydroxide preparation ternary lithium ion battery presoma, which is characterized in that the crude hydrogen The impurity of cobalt oxide includes silicon, iron, copper, zinc, calcium, magnesium, lead and aluminium, be the described method comprises the following steps:
A, excellent molten removal of impurities
It is stirred under conditions of liquid-solid ratio 4-10:1,50-70 DEG C of temperature with hot water and washes crude cobalt hydroxide, so that zinc, copper, magnesium part Removing;
B, reducing leaching
H is added into the substance after step A washing2SO4And Na2SO3, pH is adjusted to 1.5-2.0 so that cobalt hydroxide be reduced it is molten Solution, silica are transformed into silicic acid;
C, sodium jarosite tentatively removes iron
Substance that step B is obtained is subjected to filters pressing and obtains filter residue and filtrate, filtrate is heated to 80-99 DEG C, and be added crystal seed and Sodium sulphate, pH are still controlled in 1.5-2.0;
D, heavy aluminium is neutralized
The substance that step C is obtained is subjected to filters pressing and obtains filter residue and filtrate, NaOH is added into filtrate and adjusts pH to 5.0-6.0;
E, vulcanize preliminary copper removal, lead
NaOH is continuously added after to the heavy aluminium of step D in liquid and adjusts pH > 7.5, Na is added2S, solution temperature are 50-70 DEG C;
F, heavy calcium, magnesium are fluorinated
The substance that step E is obtained is subjected to filters pressing and obtains filter residue and filtrate, NaF, reaction temperature 50-70 are added into filtrate ℃;
G, the separation of cobalt sodium is molten with acid
Na is added in the filtrate obtained to step F2CO3Until pH is adjusted to 9.0 or more, sediment is obtained;Sediment is washed To neutrality, control with sulfuric acid dissolution, and by solution ph in 3.0-4.0;
H, P204 extracting copper, zinc
P204 after synergic reagent and NaOH saponification are added in the solution obtained to step G, is extracted, wherein synergic reagent at room temperature Volume ratio be 3%-6%, the volume ratio of P204 is 15%-25%, and the volume ratio of organic phase and water phase is 0.8-1.2:1, extraction Stoste pH is taken still to control in 3.0-4.0;
I, nickel sulfate and manganese sulfate are added according to the ratio
The content of cobalt and ternary material LiNi in the raffinate obtained according to step HxMnyCozO2In x, y value determine sulfuric acid The additive amount of nickel and manganese sulfate, and being added into raffinate, wherein x+y+z=1;
J, cocurrent synthesizes
Volatile carbonate is added in the solution obtained to step I, cobalt, nickel, manganese are precipitated as carbonate;After carbonate filtering Washing obtains required ternary lithium ion battery presoma to neutrality.
2. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In the liquid-solid ratio in the step A is 6:1, and temperature is 60-65 DEG C.
3. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In, in the step B, Na2SO3Actual amount be 1.5-2 times of theoretical amount.
4. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In in the step C, filtrate is heated to 95 DEG C.
5. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In, in the step D, Na2The actual amount of S is 2-5 times of theoretical amount.
6. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In in the step E, reaction temperature is 65-70 DEG C.
7. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In the reaction temperature in the step F is 60 DEG C, and the actual amount of NaF is 1.5-2.0 times of theoretical amount.
8. as described in claim 1 from the method for crude cobalt hydroxide preparation ternary lithium ion battery presoma, feature exists In in the step H, the volume ratio that the volume ratio of synergic reagent is 4%, P204 is 20%, and the volume ratio of organic phase and water phase is 1:1。
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Citations (1)

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CN102101701A (en) * 2010-12-31 2011-06-22 湖南邦普循环科技有限公司 Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite

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Publication number Priority date Publication date Assignee Title
CN102101701A (en) * 2010-12-31 2011-06-22 湖南邦普循环科技有限公司 Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite

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