CN106611841B - A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge - Google Patents
A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge Download PDFInfo
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Abstract
The invention discloses a kind of methods for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge, the following steps are included: step (1): at the nickel cobalt slag charge that nickel cobalt molar ratio is 3/1~8/1 is 1~5,30~80 DEG C in pH acidleach handle, be separated by solid-liquid separation after nickel cobalt molar ratio be 1: 0.9~1.1 acidleach slag charges；Step (2): acidleach slag charge obtains nickel and cobalt solution through hydrogen peroxide reducing leaching, chemical subtraction, extracting and purifying；Step (3): to be incorporated manganese sulfate in nickel and cobalt solution, nickel-cobalt-manganese ternary material precursor is made through being co-precipitated.In the present invention, the nickel cobalt slag charge the pH and at a temperature of collaboration leach under, help to be made molar ratio close to 1: 1 acidleach slag charge, followed by the reducing leaching, removal of impurities, purification and co-precipitation, and then satisfactory nickel-cobalt-manganese ternary material precursor is made in a step.
Description
Technical field
The present invention relates to battery material technical fields, and in particular to a kind of to prepare nickel cobalt using nickel cobalt slag charge and old and useless battery
The method of manganese ternary anode material precursor.
Background technique
Nickel-cobalt-manganternary ternary anode material have the cost of raw material is lower, specific capacity is high, stable cycle performance, security performance compared with
The advantages that good, the application prospect on lithium-ion-power cell is boundless, is a kind of product for being in close proximity to cobalt acid lithium,
Cost performance is much higher than cobalt acid lithium, and capacity is 10-20% higher than cobalt acid lithium, is the novel battery material that may most replace cobalt acid lithium
One of, referred to as third generation anode material for lithium-ion batteries, positive electrode domestic demand with 20% annual growth rate gradually
Occupy leading position.Nickel-cobalt-manganese ternary material was included in " planning of new material industry " 12th Five-Year Plan " " weight in 2012 by Ministry of Industry and Information, China
The new high-tech product of point development.The country prepares nickel using coprecipitation using high-purity cobalt, nickel, manganese and lithium salts as raw material at present
The technology of cobalt-manganese ternary material has been mature on the whole, and real when rising the enterprises such as science and technology in Hunan China fir China fir, the auspicious Xiang in Hunan, Beijing
Existing large-scale production.Usually, this traditional resource use patterns be will be in mineral resources by conventional metallurgical technology
Various components are separated and obtain pure chemical industry and metallurgical raw material, are then weighed various components again by material preparation technology
The material of Combination nova acquisition high added value.Change low value-added at present, extensive style at the cost of the environment the utilization of resources
Mode realizes the cleaning high-value-use of nonferrous metal resource, is that nonferrous metal property chain makes a breakthrough the machine that sexual development faced
Meet the direction with challenge and non-ferrous metal future development.Metal or inorganic non-metallic are directly prepared from source processing link
Material, to reach utilization rate maximum, low energy consumption and the smallest target of environmental pressure of mineral resources.
The process for handling nickel cobalt waste material both at home and abroad at present, generally all concentrates on Metallurgic Chemical Process this aspect,
In typical process flow have: nickel cobalt material is dissolved in the non-ferrous metal including nickel and cobalt containing in acid solution by acidleach first,
Other metallic elements except nickel cobalt are removed by metallurgical purification means again, obtain the purer solution of nickel cobalt.Finally adopt
With the metallurgical technology means of oxidationreduction, comparision contents high nickel slag charge or cobalt slag are respectively obtained, then is further processed.Needle
To the nickel cobalt slag of non-ferrous metals smelting works' output, after also having using ammonia leaching, purifying, rich nickel slag, rich cobalt slag are respectively obtained.For stone
The nickel cobalt slag charge of oily chemical company.The metallurgical technology technology of processing nickel cobalt waste, emphasis point are all placed on nickel cobalt both at home and abroad at present
Isolation technics in terms of, many experts explore thus, develop many methods and medicament.This mode is by a series of numerous
Miscellaneous deep impurity-removing process has been also subject to adjust soda acid, nickel cobalt extraction and separation repeatedly.Since nickel cobalt property is similar, nickel cobalt is separated
Sometimes an individual workshop is just needed, however prepares production line in ternary material and but mixes isolated nickel cobalt, this is just
It is too high to result in cost.Obviously, the space that system optimization is carried out in the configured in one piece of technique is very big.
In nickel cobalt slag charge and old and useless battery the grade of valuable metal be much higher than ore resource, be good cobalt, manganese, nickel, zinc,
The economic value of copper, lithium resource, recycling is very high.Processing that such as cannot be appropriate, also band future while the wasting of resources
Benefit is serious to obtain heavy metal pollution problem.It effectively recycles and comprehensively utilizes about secondary resource, bring certain economic value
Environment is also improved simultaneously, meets national industrial policies, is conducive to resource regeneration and environmental-friendly development.
The Chinese patent literature of Publication No. CN103384002A, which discloses, a kind of prepares electronics ternary material using nickel cobalt slag
The method of material precursor is pre-processed by castaway slag to all kinds of nickel and cobalt containings or waste, and will be pretreated each useless
Slag mixing, which compounds, is made nickel cobalt element ratio；And then using Ore Leaching technique nickel and cobalt solution is obtained, by metallurgical technology technology,
Directly generate the nickel cobalt oxide presoma being applicable in for ternary electronic material.The technical solution by a variety of nickel cobalt slag charges into
Row processing, the single waste material of nickel cobalt can not accomplish that they first match nickel cobalt ratio before leaching, by the proportion of different material,
Which adds the type of impurity, subsequent removal of impurities brings inconvenience.And various materials balance nickel cobalt wants leaching condition
Ask relatively also higher.
Summary of the invention
The defects of to solve the prior art at high cost, complex process, is prepared the present invention provides a kind of using nickel cobalt slag charge
The method of nickel-cobalt-manganternary ternary anode material presoma；It is intended to simplify technique, reduces process costs.
A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge, comprising the following steps:
Step (1): acidleach is handled at the nickel cobalt slag charge that nickel cobalt molar ratio is 3/1~8/1 is 1~5,30~80 DEG C in pH,
Be separated by solid-liquid separation after nickel cobalt molar ratio be 1: 0.9~1.1 acidleach slag charges；
Step (2): acidleach slag charge obtains nickel and cobalt solution through hydrogen peroxide reducing leaching, chemical subtraction, extracting and purifying；
Step (3): to be incorporated manganese sulfate in nickel and cobalt solution, nickel-cobalt-manganese ternary material precursor is made through being co-precipitated.
In the present invention, the nickel cobalt slag charge the pH and at a temperature of collaboration leach under, help to be made mole
It than the acidleach slag charge close to 1: 1, is co-precipitated followed by the reducing leaching, removal of impurities, purification and manganese source, and then a step
Satisfactory nickel-cobalt-manganese ternary material precursor is made.The method of the present invention by the processing of the step (1), can a step by institute
The nickel cobalt molar ratio for the nickel cobalt slag charge stated is adjusted to close to 1: 1, easy to operate and individually pre- without carrying out to all kinds of nickel cobalt slag charges
Processing, treatment process greatly simplify, and preparation cost reduction is obvious, and does not need special installation, and it is raw to be applicable to industrial-scale
It produces.
In the present invention, it is preferred to use generated nickel and cobalt containing waste residue is as preferred raw material (example in smelter production process
Such as the nickel cobalt slag generated in wet smelting process), further preferably, the nickel cobalt molar ratio of used nickel cobalt slag charge is 5~8:
1。
The inventors discovered that under the acid leaching process, it can be by the nickel cobalt ratio of the acidleach slag charge of the nickel cobalt slag charge
In regulation to the range；The drawbacks of avoiding the need for the independent pretreatment and artificial compounding by nickel cobalt waste residue of all categories.
The present inventor the study found that for realize a step control made from acid-soaked waste residue nickel-to-cobalt ratio, need strict control to walk
Suddenly the pH and temperature of the acid leaching process process of (1).
In the present invention, acidleach process preferably uses the aqueous solution of inorganic acid, further preferably sulfuric acid solution.Described
Sulfuric acid solution concentration is preferably 0.1~0.5mol/L.
Preferably, adding the sulfuric acid solution of the molar concentration into nickel cobalt slag charge, wherein solid-to-liquid ratio is preferably 1g: 5
~10mL.The solid-to-liquid ratio is nickel cobalt slag charge weight and sulfuric acid solution volume ratio；It that is to say, every gram of nickel cobalt slag charge adds 5~
10mL sulfuric acid solution.
Preferably, the pH of control acidleach process is 2~4 in step (1)；Further preferably 2.5.
At the preferred pH, preferably, acidleach treatment temperature is 40~60 DEG C in step (1).
It is handled by the acidleach under the conditions of described, then passes through solid-liquid separation treatment, solid portion washing, dry, crushing
Afterwards the acidleach slag charge (nickel cobalt molar ratio close to 1 acidleach slag charge)；Liquid portion mainly contains nickel, cobalt, iron, copper, aluminium
Deng；The high nickel solution can prepare nickel material through the techniques recycling such as chemical subtraction, extracting and purifying, electrolysis.
In the present invention, under the Parameter Conditions of the step (1), acidleach handles the time as 1~3h.
In the present invention, reducing leaching is carried out to acidleach slag charge made from step (1)；In the present invention, it is preferred to use hydrogen peroxide
As reducing agent；Sulfuric acid is as leachate.
Preferably, in step (2), the concentration of hydrogen peroxide is 20~30wt%, dosage be theoretical amount 1.4~
2.5 again.
Preferably, the molar concentration for the sulfuric acid that reducing leaching process uses is 1.0~2.5mol/L in step (2).
The volume and acidleach slag charge weight ratio of the hydrogen peroxide are 2~5ml/g.Every gram of acidleach slag charge adds the double of 2~5ml
Oxygen water.
The reaction of reducing leaching is carried out for example using hydrogen peroxide are as follows:
2NiOOH+4H++H2O2→2Ni2++4H2O+O2
2CoOOH+4H++H2O2→2Co2++4H2O+O2
The hydrogen peroxide adds mole and can be calculated according to above-mentioned reaction equation.
Preferably, reducing leaching temperature is 30~100 DEG C；Further preferably 50~90 DEG C.
Preferably, during reducing leaching, it is 5~10mL: 1g that liquid, which consolidates envelope-bulk to weight ratio, in step (2).It that is to say,
Every gram of acidleach slag charge adds the sulfuric acid and hydrogen peroxide of 5~10mL.
Under the reducing leaching process conditions, preferably, the reducing leaching time is 2~4h.
It include nickel, cobalt, iron, zinc, calcium, magnesium plasma in reducing leaching liquid in the present invention, the step (2) is preferably adopted
Iron, fluoride process removing calcium and magnesium are removed with yellow modumite method, then carries out deep impurity-removing with p204 extractant+sulfonated kerosene.
Present invention preferably employs pH gradient impurity-removing methods to carry out removal of impurities processing to reducing leaching liquid.
Preferably, in step (2), to the chemical subtraction step of reducing leaching liquid are as follows: adjusted with alkali metal hydroxide
The pH of reducing leaching liquid is 1.0~1.5, stirs 1.0~2.0h；Then it is 2.0~3.0 and is risen with alkali carbonate adjustment pH
Temperature is to stirring at 80~95 DEG C and maintain the pH1.0~2.0h；Subsequently being cooled to room temperature, adjusting pH is 3.5~4.0 and to throw
Add ammonium fluoride to be stirred to react 1.0~2.0h, filters to obtain nickel cobalt removal of impurities liquid.
In the present invention, extracting and purifying processing is carried out to the nickel cobalt removal of impurities liquid after step (2) chemical subtraction, obtains nickel cobalt scavenging solution
(nickel and cobalt solution).
Preferably, in step (2), during extracting and purifying, used extractant is P204- semi-annular jade pendant kerosene, P204 with
The percentage by volume of sulfonated kerosene is respectively 10~30% and 90~70%, and the saponification rate of P204 is 20~80%.
Preferably, step (2) extraction, using 5~10 grades of extractions, every grade of extraction time is 3~5 minutes.
In the present invention, the preferred mode that extracts is counter-current extraction.
In the present invention, with manganese source solution and a certain amount of high-purity cobalt in the nickel cobalt scavenging solution that obtains to step (2), make nickel cobalt
Molar ratio between manganese is 1: 1: 1.Co-precipitation processing is carried out after mixing, and the presoma is made.
The manganese source is the high purity manganese sulfate by outside purchase.
Nickel cobalt manganese solution and NaOH, ammonium hydroxide are co-precipitated, obtained solid is by washing, being dried to obtain after reaction
Nickel-cobalt-manganternary ternary anode material presoma.
Preferably, in coprecipitation process, the hybrid ionic concentration of nickel cobalt manganese is in mixed solution in step (3)
0.5~2.5mol/L；The concentration of the NaOH solution is 1.0~3.0mol/L, and ammonia concn is 0.5~2mol/L；Reaction temperature
Degree is 30~60 DEG C；It is 11 that pH is kept in reaction process.
In step (3), ammonia content control is in 1~3g/L in reaction system.
In step (3), after coprecipitation reaction, reaction solution is separated by solid-liquid separation, obtained solid is by washing, drying
Obtain nickel-cobalt-manganternary ternary anode material presoma.
In the present invention, by regulating and controlling the parameter of acidleach process, to realize the regulation of nickel cobalt ratio, and then nickel cobalt is realized
Recycling of forming a team, simple process and low cost.
Detailed description of the invention
Fig. 1 is process flow diagram of the present invention.
Specific implementation method
Following embodiment is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1
Raw material nickel cobalt slag charge used by the present embodiment is derived from the smelting slag (nickel cobalt of Xinjiang coloured smelting factory institute output
Nickel-to-cobalt ratio in slag charge is from 40: 7), by being commercially available manganese sulfate.
Step (1): the nickel sulfate hexahydrate crystal dissolved in slag charge dissolution slag charge is first washed with deionized, is then with liquid-solid ratio
8mL/g (on the basis of nickel cobalt slag charge weight) adds the sulfuric acid of 0.5mol/L, and the pH of control system is 2.5~3.0；And 40~
2h is stirred to react at 50 DEG C.Solution after acid-leaching reaction is filtered, washed, is dried, grinds and obtains nickel cobalt acidleach slag charge and rich nickel
Solution (back to electrolytic nickel system or can prepare nickelic ternary precursor by chemical subtraction and extractant deep impurity-removing)；
The nickel-to-cobalt ratio of the nickel cobalt acidleach slag charge is 1: 1.
Step (2):
Step (2-a): reducing leaching:
Sulfuric acid (sulfuric acid volume and the nickel cobalt acid that concentration is 1.5mol/L are added to nickel cobalt acidleach slag charge made from step (1)
Phase analysis material weight ratio 10mL/g) and hydrogen peroxide (30wt%；The volume and nickel cobalt acidleach slag charge weight ratio of hydrogen peroxide are 2.0ml/
g)；Controlling reaction temperature is 50 DEG C, reaction time 2.5h；Nickel cobalt reducing leaching solution, wherein leading ion be nickel, cobalt, iron,
Aluminium, calcium, magnesium, copper plasma.
Step (2-b): the removal of impurities of reducing leaching solution chemistry:
Measure nickel cobalt reducing leaching solution, be added in solution the NaOH solution that mass fraction is 10% adjust pH (1.0~
1.5) 1.0h, is stirred, saturated sodium carbonate is then added and adjusts pH value to 2.5~3.0, at 90~95 DEG C of temperature, leads in the reaction
Crossing addition alkali keeps pH to stablize reaction 150min, cold filtration.PH value of solution is adjusted to 4, the ammonium fluoride of 1.5 times of amounts is added, normal
It is lower under the conditions of temperature to react two hours；Obtain nickel cobalt removal of impurities liquid.
Step (2-c): extracting and purifying:
The mixed liquor of the p204 (saponification rate 30%) and 70 volume % sulfonated kerosenes that use 30 volume % are as extractant；
The extractant for being 1: 1 with volume ratio extracts nickel cobalt removal of impurities liquid, and extraction series is 5 grades to 8 grades；Extraction mode is that adverse current extracts
It takes, is enriched with to obtain extracting and purifying liquid.
Step (3): being incorporated manganese sulfate into extracting and purifying liquid, keeps nickel cobalt manganese molar ratio 1: 1: 1 (few without being introduced from outside into
The nickel cobalt manganese of amount)；The total ion concentration of nickel cobalt manganese is 2mol/L, and ammonium hydroxide and sodium hydroxide (1.5mol/L) is then added to coprecipitated
Coprecipitation reaction is carried out in the reaction kettle of shallow lake, reaction system pH control ammonia content control in 11, reaction system exists in reaction process
2g/L, temperature of reaction system are controlled at 50 DEG C, mixing speed 500r/min, are passed through argon gas and are protected, argon flow 0.6ml/min,
React 5 hours.After to coprecipitation reaction, obtained slurry is continued to stir, Chen Hua 2h, then spends under the conditions of 50 DEG C
Ion water washing, washing to filtrate pH=8.0,100 DEG C of drying 10h, 200 meshes point obtain the extremely low ternary of impure content
Positive electrode material precursor.
Embodiment 2
It is compared with embodiment 1, difference is only that, in step (1), after adding the sulfuric acid solution, the pH of control system is
1.0；And 2h is stirred to react at 50 DEG C.The nickel-to-cobalt ratio of the nickel cobalt acidleach slag charge is 0.87: 1.In addition, step (3): Xiang Cui
Supplying manganese source solution in scavenging solution is taken, being introduced from outside into a small amount of nickel cobalt manganese makes nickel cobalt manganese molar ratio 1: 1: 1, is then co-precipitated
Ternary anode material precursor is made.But during first step Weak-acid leaching, containing the cobalt ions of 1.5g/L in nickel solution, lead
Cause that a part of solution for returning to electrolytic nickel system except some troubles of miscellaneous band.
Embodiment 3
It is compared with embodiment 1, difference is only that, in step (1), after adding the sulfuric acid solution, the pH of control system is
3.5；And 2h is stirred to react at 50 DEG C.The nickel-to-cobalt ratio of the nickel cobalt acidleach slag charge is 1.03: 1.In addition, step (3): Xiang Cui
Supplying manganese source solution in scavenging solution is taken, being introduced from outside into a small amount of nickel cobalt manganese makes nickel cobalt manganese molar ratio 1: 1: 1, is then co-precipitated
Ternary anode material precursor is made.
Embodiment 4
It is compared with embodiment 1, difference is only that, in step (1), after adding the sulfuric acid solution, the pH of control system is
4.0；And 2h is stirred to react at 50 DEG C.The nickel-to-cobalt ratio of the nickel cobalt acidleach slag charge is 1.05: 1.In addition, step (3): Xiang Cui
Supplying manganese source solution in scavenging solution is taken, being introduced from outside into a small amount of nickel cobalt manganese makes nickel cobalt manganese molar ratio 1: 1: 1, is then co-precipitated
Ternary anode material precursor is made.
Embodiment 5
It is compared with embodiment 1, difference is only that, in step (2-a), sulfuric acid (sulfuric acid volume and the nickel cobalt acid of 1.0mol/L
Phase analysis material weight ratio 10mL/g) and hydrogen peroxide (30wt%；The volume and nickel cobalt acidleach slag charge weight ratio of hydrogen peroxide are 2.0ml/
g)；Controlling reaction temperature is 50 DEG C, reaction time 2.5h；Total leaching rate of nickel cobalt is respectively 91.3%, 83.4%.
Comparative example 1
It is compared with embodiment 1, difference is only that, in step (1), after adding the sulfuric acid solution, the pH of control system is
0.5；And 2h is stirred to react at 50 DEG C.The nickel-to-cobalt ratio of the nickel cobalt acidleach slag charge is 0.47: 1.Since nickel cobalt ratio is higher,
It needs to buy a large amount of cobalt, higher cost when needing to configure ternary precursor.
Claims (4)
1. a kind of method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge, which comprises the following steps:
Step (1): acidleach is handled at the nickel cobalt slag charge that nickel cobalt molar ratio is 3/1~8/1 is 2~4,40~60 DEG C in pH, acidleach
Using the sulfuric acid solution of 0.1~0.5mol/L, every gram of nickel cobalt slag charge adds 5~10mL sulfuric acid solution, acidleach handle the time be 1~
3h, be separated by solid-liquid separation after nickel cobalt molar ratio be 1: 0.9~1.1 acidleach slag charges；
Step (2): acidleach slag charge obtains nickel and cobalt solution, hydrogen peroxide through hydrogen peroxide and sulfate reduction leaching, chemical subtraction, extracting and purifying
Concentration be 20~30wt%, dosage is 1.4~2.5 times of theoretical amount, and the molar concentration of sulfuric acid is 1.0~2.5mol/
L, reducing leaching temperature are 50~90 DEG C, and every gram of acidleach slag charge adds the sulfuric acid and hydrogen peroxide of 5~10mL, and the reducing leaching time is
2~4h；
Step (3): to be incorporated manganese sulfate in nickel and cobalt solution, making the molar ratio 1: 1: 1 between nickel cobalt manganese, is made through being co-precipitated
Nickel-cobalt-manganese ternary material precursor.
2. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as described in claim 1, which is characterized in that
In step (2), during extracting and purifying, used extractant is P204- sulfonated kerosene, the volume basis of P204 and sulfonated kerosene
Number is respectively 10~30% and 90~70%, and the saponification rate of P204 is 20~80%.
3. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as described in claim 1, which is characterized in that
Step (2) extraction is 3~5 minutes using 5~10 grades of extractions, every grade of extraction time.
4. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as described in claim 1, which is characterized in that
In step (3), in coprecipitation process, nickel cobalt manganese solution and NaOH, ammonium hydroxide are co-precipitated, nickel cobalt manganese in mixed solution
Hybrid ionic concentration be 0.5~2.5mol/L；The concentration of the NaOH solution is 1.0~3.0mol/L, ammonia concn 0.5
~2mol/L；Reaction temperature is 30~60 DEG C.
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| CN107117661B (en) * | 2017-05-26 | 2019-01-25 | 金川集团股份有限公司 | The method for preparing ternary hydroxide using nickel cobalt manganese in the waste and old lithium ion battery of liquid phase method recycling |
| CN107369830B (en) * | 2017-06-06 | 2020-03-03 | 中国恩菲工程技术有限公司 | Method for preparing anode ternary precursor powder |
| CN108306071A (en) * | 2018-01-16 | 2018-07-20 | 深圳市比克电池有限公司 | A kind of waste lithium ion cell anode material recovery technique |
| CN112310498A (en) * | 2019-07-30 | 2021-02-02 | 山东涵宇锐特新能源有限公司 | Method for preparing nickel-cobalt-manganese ternary material precursor by using waste ternary battery |
| CN111366489B (en) * | 2020-03-26 | 2022-05-20 | 湖南长远锂科股份有限公司 | Semi-quantitative detection method for lithium content in primary mixed material sample of ternary cathode material |
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