CN106611841A - Method for preparing nickel-cobalt-manganese ternary material precursor by using nickel-cobalt slag material - Google Patents
Method for preparing nickel-cobalt-manganese ternary material precursor by using nickel-cobalt slag material Download PDFInfo
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- H—ELECTRICITY
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Abstract
The invention discloses a method for preparing a nickel-cobalt-manganese ternary material precursor by using a nickel-cobalt slag material. The method comprises the following steps: step (1), carrying out acid leaching treatment on the nickel-cobalt slag material with the nickel-cobalt mole ratio of 3/1 to 8/1 at the pH of 1 to 5 and the temperature of 30 to 80 DEG C, and then carrying out solid-liquid separation to obtain an acid leaching slag material with the nickel-cobalt mole ratio of 1: (0.9 to 1.1); step (2), carrying out hydrogen peroxide reduction leaching, chemical subtraction and extraction purification on the acid leaching slag material to obtain a nickel-cobalt solution; and step (3), adding manganese sulfate into the nickel-cobalt solution, and carrying out coprecipitation to obtain the nickel-cobalt-manganese ternary material precursor. In the method, the nickel-cobalt slag material is leached under the synergism of pH and temperature, the acid leaching slag material with the mole ratio of close to 1: 1 is obtained, then the reduction leaching, subtraction, purification and coprecipitation are carried out, and then the nickel-cobalt-manganese ternary material precursor meeting the requirement is obtained in one step.
Description
Technical field
The present invention relates to battery material technical field, and in particular to one kind prepares nickel cobalt using nickel cobalt slag charge and old and useless battery
The method of manganese ternary anode material precursor.
Background technology
Nickel-cobalt-manganternary ternary anode material has that the cost of raw material is relatively low, specific capacity is high, stable cycle performance, security performance compared with
Good the advantages of, the application prospect on lithium-ion-power cell is boundless, is a kind of product for being in close proximity to cobalt acid lithium, its
Cost performance is far above cobalt acid lithium, and the high 10-20% of Capacity Ratio cobalt acid lithium is the novel battery material that may most replace cobalt acid lithium
One of, be referred to as third generation anode material for lithium-ion batteries, its positive electrode domestic demand with 20% annual growth rate gradually
Occupy leading position.Ministry of Industry and Information of China included nickel-cobalt-manganese ternary material in 2012《New material industry " 12 " is planned》Weight
The new high-tech product of point development.At present the country prepares nickel with high-purity cobalt, nickel, manganese and lithium salts as raw material using coprecipitation
The Technology of cobalt-manganese ternary material has been mature on the whole, and in Hunan China fir China fir, the auspicious Xiang in Hunan, Beijing when enterprise's realities such as liter science and technology
Existing large-scale production.As a rule, this traditional resource use patterns are by mineral resources by conventional metallurgical technology
Various components are separated and are obtained pure chemical industry and metallurgical raw material, are then again weighed various components by material preparation technology
Combination nova obtains the material of high added value.Change the utilization of resources of at present low value-added, extensive style at the cost of the environment
Pattern, 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 and challenge, be also the direction of non-ferrous metal future development.Directly prepare metal or inorganic non-metallic from source processing link
Material, so as to the utilization rate for reaching mineral resources is maximum, the target that energy resource consumption is low and environmental pressure is minimum.
Process the process of nickel cobalt waste material both at home and abroad at present, typically all concentrate on Metallurgic Chemical Process this aspect, its
In typical technological process have：First nickel cobalt material is dissolved in nickel and cobalt containing in acid solution in interior non-ferrous metal by acidleach,
Again other metallic elements outside nickel cobalt are removed by metallurgical purification means, obtain the purer solution of nickel-to-cobalt ratio.Finally adopt
With the metallurgical technology means of oxidation-reduction, the high nickel slag charge of comparision contents or cobalt slag are respectively obtained, then be further processed.Pin
Nickel cobalt slag to non-ferrous metals smelting works' output, after also having using ammonia leaching, purification, respectively obtains rich nickel slag, rich cobalt slag.For stone
The nickel cobalt slag charge of oily chemical enterprise.Process the metallurgical technology technology of nickel cobalt garbage both at home and abroad at present, emphasis point is all placed on nickel cobalt
Isolation technics aspect, many experts explore for this, work out many methods and medicament.This pattern is by a series of numerous
Miscellaneous deep impurity-removing process, has been also subject to adjust soda acid, nickel cobalt extract and separate repeatedly.Because nickel cobalt property is similar, nickel cobalt is separated
Sometimes a single workshop is accomplished by, but is prepared production line in ternary material and is but mixed detached nickel cobalt, this is just
Result in cost too high.Obviously, the space that system optimization is carried out in the configured in one piece of technique is very big.
The grade of valuable metal is far above ore resource in nickel cobalt slag charge and old and useless battery, be the cobalt of high-quality, manganese, nickel, zinc,
Copper, lithium resource, the economic worth of recycling is very high.Process that such as can not be appropriate, also band future while the wasting of resources
Benefit is serious to obtain heavy metal pollution problem.Effectively reclaim and comprehensively utilize with regard to secondary resource, bring certain economic worth
Simultaneously environment is also improved, meet national industrial policies, be conducive to resource regeneration and environmental friendliness development.
The Chinese patent literature of Publication No. CN103384002A discloses one kind and prepares electronics ternary material using nickel cobalt slag
The method of material precursor, by the castaway slag or garbage to all kinds of nickel and cobalt containings pretreatment is carried out, and will be pretreated each useless
Slag mixing compounding is obtained nickel cobalt element ratio；And then again nickel and cobalt solution is obtained through Ore Leaching technique, by metallurgical technology technology,
Directly generate the nickel cobalt oxide presoma being suitable for for ternary electronic material.The technical scheme is by being that various nickel cobalt slag charges are entered
What row was processed, the single waste material of nickel cobalt cannot be accomplished, their first proportioning nickel cobalt ratios before leaching, by the proportioning of different material,
The species of impurity is which adds, follow-up remove impurity brings inconvenience.And various materials balance nickel cobalt is wanted to leaching condition
Ask relatively also higher.
The content of the invention
To solve the defects such as prior art high cost, complex process, the invention provides a kind of prepared using nickel cobalt slag charge
The method of nickel-cobalt-manganternary ternary anode material presoma；Simplified flowsheet is intended to, process costs are reduced.
A kind of method that utilization nickel cobalt slag charge prepares nickel-cobalt-manganese ternary material precursor, comprises the following steps：
Step (1)：Nickel cobalt mol ratio is 3/1～8/1 nickel cobalt slag charge acidleach process in the case where pH is for 1～5,30～80 DEG C,
Jing solid-liquid separation obtains nickel cobalt mol ratio for 1: 0.9～1.1 acidleach slag charges with after；
Step (2)：Acidleach slag charge Jing hydrogen peroxide reducing leachings, chemical subtraction, extracting and purifying obtain nickel and cobalt solution；
Step (3)：To have allocated manganese sulfate in nickel and cobalt solution into, Jing co-precipitation is obtained nickel-cobalt-manganese ternary material precursor.
In the present invention, described nickel cobalt slag charge described pH and at a temperature of collaboration leach under, contribute to being obtained mole
Acidleach slag charge than close 1: 1, is co-precipitated followed by described reducing leaching, remove impurity, purification and manganese source, and then a step
Satisfactory nickel-cobalt-manganese ternary material precursor is obtained.The process that the inventive method passes through the step (1), can a step by institute
The nickel cobalt mol ratio of the nickel cobalt slag charge stated is adjusted to close 1: 1, simple to operate, and individually pre- without the need for carrying out to all kinds of nickel cobalt slag charges
Process, handling process is greatly simplified, preparation cost reduction is obvious, and does not need special installation, be applicable to industrial-scale life
Produce.
In the present invention, it is preferred to use nickel and cobalt containing waste residue produced in smelter production process is used as preferred feedstock (example
Such as the nickel cobalt slag produced in wet smelting process), further preferably, the nickel cobalt mol ratio of the nickel cobalt slag charge for being adopted is for 5～8:
1。
The inventors discovered that, under described acid leaching process, can be by the nickel cobalt ratio of the acidleach slag charge of described nickel cobalt slag charge
Regulate and control to described scope；The drawbacks of avoiding the need for the independent pretreatment by nickel cobalt waste residue of all categories and manually compound.
The present inventor's research finds, is the nickel-to-cobalt ratio for realizing acid-soaked waste residue obtained in a step control, needs strict control step
Suddenly the pH and temperature of the acid leaching process process of (1).
In the present invention, acidleach process is preferably using the aqueous solution of inorganic acid, more 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 in nickel cobalt slag charge, wherein solid-to-liquid ratio is preferably 1g: 5
～10mL.Described solid-to-liquid ratio is nickel cobalt slag charge weight and sulfuric acid solution volume ratio；That is to say, every gram of nickel cobalt slag charge adds 5～
10mL sulfuric acid solutions.
Preferably, in step (1), the pH for controlling acidleach process is 2～4；More preferably 2.5.
Under the preferred pH, preferably, in step (1), acidleach treatment temperature is 40～60 DEG C.
Acidleach under the conditions of described is processed, and then passes through solid-liquid separation process, solid portion washing, dry, crushing
Described acidleach slag charge (the acidleach slag charge of nickel cobalt mol ratio close 1) is obtained afterwards；Liquid portion mainly contains nickel, cobalt, ferrum, copper, aluminum
Deng；Described high nickel solution can the technique recovery such as Jing chemical subtractions, extracting and purifying, electrolysis prepare nickel material.
In the present invention, under the Parameter Conditions of described step (1), acidleach process time is 1～3h.
In the present invention, reducing leaching is carried out to acidleach slag charge obtained in step (1)；In the present invention, it is preferred to use hydrogen peroxide
As reducing agent；Sulphuric acid is used as leachate.
Preferably, in step (2), the concentration of hydrogen peroxide is 20～30wt%, dosage for theoretical amount 1.4～
2.5 again.
Preferably, in step (2), the molar concentration of the sulphuric acid that reducing leaching process is adopted is for 1.0～2.5mol/L.
The volume and acidleach slag charge weight ratio of the hydrogen peroxide is 2～5ml/g.Every gram of acidleach slag charge adds the double of 2～5ml
Oxygen water.
The reaction for carrying out reducing leaching using hydrogen peroxide is, for example,：
2NiOOH+4H++H2O2→2Ni2++4H2O+O2
2CoOOH+4H++H2O2→2Co2++4H2O+O2
Described hydrogen peroxide adds mole and can be calculated according to above-mentioned reaction equation.
Preferably, reducing leaching temperature is 30～100 DEG C；More preferably 50～90 DEG C.
Preferably, in step (2), during reducing leaching, the solid envelope-bulk to weight ratio of liquid is 5～10mL: 1g.That is to say,
Every gram of acidleach slag charge adds the sulphuric acid and hydrogen peroxide of 5～10mL.
Under described reducing leaching process conditions, preferably, the reducing leaching time is 2～4h.
In the present invention, nickel, cobalt, ferrum, zinc, calcium, magnesium plasma are included in reducing leaching liquid, the step (2) is preferably adopted
Ferrum, fluoride process removing calcium and magnesium are removed with yellow modumite method, then deep impurity-removing is carried out with p204 extractants+sulfonated kerosene.
Present invention preferably employs pH gradient impurity-removing method to reducing leaching liquid carrying out remove impurity process.
Preferably, in step (2), being to the chemical subtraction step of reducing leaching liquid：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 stirs and maintains the pH1.0～2.0h at 80～95 DEG C；Subsequently it is cooled to room temperature, adjustment pH to be 3.5～4.0 and throw
Plus ammonium fluoride 1.0～2.0h of stirring reaction, filter to obtain nickel cobalt remove impurity liquid.
In the present invention, extracting and purifying process is carried out to the nickel cobalt remove impurity liquid after step (2) chemical subtraction, obtain nickel cobalt scavenging solution
(nickel and cobalt solution).
Preferably, in step (2), during extracting and purifying, adopt extractant for P204- semi-annular jade pendant kerosene, P204 with
The percentage by volume of sulfonated kerosene be respectively 10～30% and 90～70%, P204 saponification rate be 20～80%.
Preferably, step (2) extraction is using 5～10 grades of extractions, every grade of extraction time is 3～5 minutes.
In the present invention, preferred extraction mode 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 obtained to step (2), nickel cobalt is made
Mol ratio between manganese is 1: 1: 1.Co-precipitation process is carried out after mixing, described presoma is obtained.
Described manganese source is the high purity manganese sulfate by outside purchase.
Nickel cobalt manganese solution is co-precipitated with NaOH, ammonia, gained solid passes through washing, is dried to obtain after reaction terminates
Nickel-cobalt-manganternary ternary anode material presoma.
Preferably, in step (3), in coprecipitation process, the hybrid ionic concentration of nickel cobalt manganese is in mixed solution
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
Spend for 30～60 DEG C；PH is kept to be 11 in course of reaction.
In step (3), ammonia content is controlled in 1～3g/L in reaction system.
In step (3), after coprecipitation reaction terminates, solid-liquid separation is carried out to reactant liquor, gained solid is through washing, being dried
Obtain nickel-cobalt-manganternary ternary anode material presoma.
In the present invention, by the parameter for regulating and controlling acidleach process, so as to realize the regulation and control of nickel cobalt ratio, and then nickel cobalt is realized
Recycling of forming a team, process is simple, low cost.
Description of the drawings
Fig. 1 is process chart of the present invention.
Specific implementation method
Following examples are intended to illustrate rather than limitation of the invention further.
Embodiment 1
The raw material nickel cobalt slag charge that the present embodiment is adopted takes 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 dissolving 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 sulphuric acid of 0.5mol/L, and the pH of control system is 2.5～3.0；And 40～
Stirring reaction 2h at 50 DEG C.Solution after acid-leaching reaction filtered, is washed, being dried, grinding obtains nickel cobalt acidleach slag charge and rich nickel
Solution (can return to electrolytic nickel system or prepare nickelic ternary precursor) through chemical subtraction and extractant deep impurity-removing；
The nickel-to-cobalt ratio of described nickel cobalt acidleach slag charge is 1: 1.
Step (2)：
Step (2-a)：Reducing leaching：
Sulphuric acid (sulphuric acid volume and the nickel cobalt acid that concentration is 1.5mol/L is added to nickel cobalt acidleach slag charge obtained in step (1)
Phase analysis material weight is than 10mL/g) and hydrogen peroxide (30wt%；The volume of hydrogen peroxide is 2.0ml/ with nickel cobalt acidleach slag charge weight ratio
g)；Controlling reaction temperature is 50 DEG C, response time 2.5h；Nickel cobalt reducing leaching solution, wherein leading ion be nickel, cobalt, ferrum,
Aluminum, calcium, magnesium, copper plasma.
Step (2-b)：Reducing leaching solution chemistry remove impurity：
Measure nickel cobalt reducing leaching solution, in solution add mass fraction be 10% NaOH solution adjust pH (1.0～
1.5), 1.0h is stirred, is subsequently adding saturated sodium carbonate and adjusts pH value to 2.5～3.0, in 90～95 DEG C of temperature, led in the reaction
Crossing addition alkali keeps pH stably to react 150min, cold filtration.PH value of solution is adjusted to 4, the ammonium fluoride of 1.5 times of amounts is added, normal
Two hours of lower reaction under the conditions of temperature；Obtain nickel cobalt remove impurity liquid.
Step (2-c)：Extracting and purifying：
Adopt 30 volumes % p204 (saponification rate is 30%) and 70 volume % sulfonated kerosenes mixed liquor as extractant；
Nickel cobalt remove impurity liquid is extracted by 1: 1 extractant of volume ratio, extraction series is 5 grades to 8 grades；Extraction mode extracts for adverse current
Take, be enriched with to obtain extracting and purifying liquid.
Step (3)：Manganese sulfate is allocated into in extracting and purifying liquid, it is (few without being introduced from outside into for 1: 1: 1 to make nickel cobalt manganese mol ratio
The nickel cobalt manganese of amount)；The total ion concentration of nickel cobalt manganese is 2mol/L, is subsequently added ammonia and sodium hydroxide (1.5mol/L) arrives coprecipitated
Coprecipitation reaction is carried out in the reactor of shallow lake, reaction system pH is controlled 11 in course of reaction, ammonia content control in reaction system exists
2g/L, at 50 DEG C, mixing speed 500r/min is passed through argon and protects, argon flow amount 0.6ml/min for temperature of reaction system control,
5 hours of reaction.After coprecipitation reaction terminates, the slurry to obtaining continues to stir, and Chen Hua 2h, then spend under the conditions of 50 DEG C
Ion water washing, washs to filtrate pH=8.0, and 100 DEG C of drying 10h, 200 mesh sieves point obtain the extremely low ternary of impure content
Positive electrode material precursor.
Embodiment 2
Compare with embodiment 1, differ only in, in step (1), after adding the sulfuric acid solution, the pH of control system is
1.0；And at 50 DEG C stirring reaction 2h.The nickel-to-cobalt ratio of described nickel cobalt acidleach slag charge is 0.87: 1.In addition, step (3)：Xiang Cui
Take and allocate in scavenging solution manganese source solution, it is 1: 1: 1 to be introduced from outside into a small amount of nickel cobalt manganese and make nickel cobalt manganese mol ratio, subsequently co-precipitation
Prepared ternary anode material precursor.But during first step Weak-acid leaching, the cobalt ion containing 1.5g/L, leads in nickel solution
Cause returns that a part of solution remove impurity band of electrolytic nickel system, and some are bothered.
Embodiment 3
Compare with embodiment 1, differ only in, in step (1), after adding the sulfuric acid solution, the pH of control system is
3.5；And at 50 DEG C stirring reaction 2h.The nickel-to-cobalt ratio of described nickel cobalt acidleach slag charge is 1.03: 1.In addition, step (3)：Xiang Cui
Take and allocate in scavenging solution manganese source solution, it is 1: 1: 1 to be introduced from outside into a small amount of nickel cobalt manganese and make nickel cobalt manganese mol ratio, subsequently co-precipitation
Prepared ternary anode material precursor.
Embodiment 4
Compare with embodiment 1, differ only in, in step (1), after adding the sulfuric acid solution, the pH of control system is
4.0；And at 50 DEG C stirring reaction 2h.The nickel-to-cobalt ratio of described nickel cobalt acidleach slag charge is 1.05: 1.In addition, step (3)：Xiang Cui
Take and allocate in scavenging solution manganese source solution, it is 1: 1: 1 to be introduced from outside into a small amount of nickel cobalt manganese and make nickel cobalt manganese mol ratio, subsequently co-precipitation
Prepared ternary anode material precursor.
Embodiment 5
Compare with embodiment 1, differ only in, in step (2-a), sulphuric acid (sulphuric acid volume and the nickel cobalt acid of 1.0mol/L
Phase analysis material weight is than 10mL/g) and hydrogen peroxide (30wt%；The volume of hydrogen peroxide is 2.0ml/ with nickel cobalt acidleach slag charge weight ratio
g)；Controlling reaction temperature is 50 DEG C, response time 2.5h；Total leaching rate of nickel cobalt is respectively 91.3%, 83.4%.
Comparative example 1
Compare with embodiment 1, differ only in, in step (1), after adding the sulfuric acid solution, the pH of control system is
0.5；And at 50 DEG C stirring reaction 2h.The nickel-to-cobalt ratio of described nickel cobalt acidleach slag charge is 0.47: 1.Due to nickel cobalt ratio it is higher,
Need to need to buy substantial amounts of cobalt when configuring ternary precursor, it is relatively costly.
Claims (10)
1. a kind of method that utilization nickel cobalt slag charge prepares nickel-cobalt-manganese ternary material precursor, it is characterised in that comprise the following steps：
Step (1)：Nickel cobalt mol ratio is 3/1～8/1 nickel cobalt slag charge acidleach process in the case where pH is for 1～5,30～80 DEG C, subsequently
Jing solid-liquid separation obtains nickel cobalt mol ratio for 1: 0.9～1.1 acidleach slag charges；
Step (2)：Acidleach slag charge Jing hydrogen peroxide reducing leachings, chemical subtraction, extracting and purifying obtain nickel and cobalt solution；
Step (3)：To allocate manganese sulfate in nickel and cobalt solution into, Jing co-precipitation is obtained nickel-cobalt-manganese ternary material precursor.
2. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 1, it is characterised in that
In step (1), the pH for controlling acidleach process is 2～4.
3. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 2, it is characterised in that
In step (1), acidleach treatment temperature is 40～60 DEG C.
4. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 3, it is characterised in that
Acidleach process time is 1～3h.
5. the method that the utilization nickel cobalt slag charge as described in any one of Claims 1 to 4 prepares nickel-cobalt-manganese ternary material precursor, its
It is characterised by, in step (2), the concentration of hydrogen peroxide is 20～30wt%, and dosage is 1.4～2.5 times of theoretical amount.
6. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 5, it is characterised in that
Reducing leaching temperature is 30～100 DEG C.
7. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 6, it is characterised in that
The reducing leaching time is 2～4h.
8. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 1, it is characterised in that
In step (2), during extracting and purifying, extractant is adopted for P204- sulfonated kerosenes, the volume basis of P204 and sulfonated kerosene
The saponification rate of number respectively 10～30% and 90～70%, P204 is 20～80%.
9. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 1, it is characterised in that
Using 5～10 grades of extractions, every grade of extraction time is 3～5 minutes for step (2) extraction.
10. the method for preparing nickel-cobalt-manganese ternary material precursor using nickel cobalt slag charge as claimed in claim 1, its feature exists
In in step (3), in coprecipitation process, the hybrid ionic concentration of nickel cobalt manganese is 0.5～2.5mol/L in mixed solution；
The concentration of the NaOH solution is 1.0～3.0mol/L, and ammonia concn is 0.5～2mol/L；Reaction temperature is 30～60 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117661A (en) * | 2017-05-26 | 2017-09-01 | 金川集团股份有限公司 | The method that nickel cobalt manganese prepares ternary hydroxide in the waste and old lithium ion battery reclaimed using liquid phase method |
| CN107369830A (en) * | 2017-06-06 | 2017-11-21 | 中国恩菲工程技术有限公司 | The method for preparing positive pole 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 |
| CN111366489A (en) * | 2020-03-26 | 2020-07-03 | 湖南长远锂科股份有限公司 | Semi-quantitative detection method for lithium content in primary mixed sample of ternary cathode material |
| 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 |
| CN112678880A (en) * | 2020-12-23 | 2021-04-20 | 贵州大龙汇成新材料有限公司 | Method for recycling manganese slag |
| CN112725628A (en) * | 2020-12-23 | 2021-04-30 | 贵州大龙汇成新材料有限公司 | Method for recovering valuable elements from manganese sulfide slag |
| CN112813260A (en) * | 2020-12-28 | 2021-05-18 | 广东佳纳能源科技有限公司 | Reduction leaching method |
| CN113060712A (en) * | 2021-03-15 | 2021-07-02 | 中南大学 | Method for preparing iron phosphate and nickel cobalt manganese hydroxide battery precursor material from metal nickel cobalt iron powder |
| CN113862474A (en) * | 2021-08-18 | 2021-12-31 | 池州西恩新材料科技有限公司 | Continuous acid leaching system and method adopting aeration to control reaction temperature |
| CN115216629A (en) * | 2022-06-28 | 2022-10-21 | 湖南中伟新能源科技有限公司 | Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1777304A1 (en) * | 2004-05-27 | 2007-04-25 | Pacific Metals Co., Ltd. | Method of recovering nickel or cobalt |
| CN101323908A (en) * | 2008-07-31 | 2008-12-17 | 广西冶金研究院 | Method for reclaiming cobalt from manganese cobalt slag |
| CN101450815A (en) * | 2008-10-07 | 2009-06-10 | 佛山市邦普镍钴技术有限公司 | Method for preparing nickel and cobalt doped lithium manganate by using waste and old lithium ionic cell as raw material |
| CN102492858A (en) * | 2011-12-22 | 2012-06-13 | 河南省冶金研究所有限责任公司 | Method for separating enriched nickel and cobalt from battery waste leaching solution |
| CN102534235A (en) * | 2012-02-13 | 2012-07-04 | 株洲冶炼集团股份有限公司 | Method for recovering valued metals from cobalt-nickel residue obtained through antimony trioxide purification in zinc hydrometallurgy |
| CN103384002A (en) * | 2012-05-04 | 2013-11-06 | 湖南科飞特高新技术有限公司 | Method for preparing electronic ternary material precursor from Ni-Co residues |
| CN103773961A (en) * | 2014-01-23 | 2014-05-07 | 广西有色金属集团汇元锰业有限公司 | Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue |
| CN104674006A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院过程工程研究所 | Clean production method for separating manganese and magnesium from laterite-nickel ore normal-temperature acid leaching liquid employing alkaline oxidation |
| CN105789724A (en) * | 2014-12-24 | 2016-07-20 | 中国电子工程设计院 | Treatment method for waste lithium-ion battery |
-
2016
- 2016-12-19 CN CN201611180242.9A patent/CN106611841B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1777304A1 (en) * | 2004-05-27 | 2007-04-25 | Pacific Metals Co., Ltd. | Method of recovering nickel or cobalt |
| CN101323908A (en) * | 2008-07-31 | 2008-12-17 | 广西冶金研究院 | Method for reclaiming cobalt from manganese cobalt slag |
| CN101450815A (en) * | 2008-10-07 | 2009-06-10 | 佛山市邦普镍钴技术有限公司 | Method for preparing nickel and cobalt doped lithium manganate by using waste and old lithium ionic cell as raw material |
| CN102492858A (en) * | 2011-12-22 | 2012-06-13 | 河南省冶金研究所有限责任公司 | Method for separating enriched nickel and cobalt from battery waste leaching solution |
| CN102534235A (en) * | 2012-02-13 | 2012-07-04 | 株洲冶炼集团股份有限公司 | Method for recovering valued metals from cobalt-nickel residue obtained through antimony trioxide purification in zinc hydrometallurgy |
| CN103384002A (en) * | 2012-05-04 | 2013-11-06 | 湖南科飞特高新技术有限公司 | Method for preparing electronic ternary material precursor from Ni-Co residues |
| CN103773961A (en) * | 2014-01-23 | 2014-05-07 | 广西有色金属集团汇元锰业有限公司 | Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue |
| CN105789724A (en) * | 2014-12-24 | 2016-07-20 | 中国电子工程设计院 | Treatment method for waste lithium-ion battery |
| CN104674006A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院过程工程研究所 | Clean production method for separating manganese and magnesium from laterite-nickel ore normal-temperature acid leaching liquid employing alkaline oxidation |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107117661A (en) * | 2017-05-26 | 2017-09-01 | 金川集团股份有限公司 | The method that nickel cobalt manganese prepares ternary hydroxide in the waste and old lithium ion battery reclaimed using liquid phase method |
| CN107369830A (en) * | 2017-06-06 | 2017-11-21 | 中国恩菲工程技术有限公司 | The method for preparing positive pole ternary precursor powder |
| WO2018223931A1 (en) * | 2017-06-06 | 2018-12-13 | 中国恩菲工程技术有限公司 | Method for preparing positive electrode ternary precursor powder |
| 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 |
| CN111366489A (en) * | 2020-03-26 | 2020-07-03 | 湖南长远锂科股份有限公司 | Semi-quantitative detection method for lithium content in primary mixed sample of ternary cathode material |
| CN112678880A (en) * | 2020-12-23 | 2021-04-20 | 贵州大龙汇成新材料有限公司 | Method for recycling manganese slag |
| CN112725628A (en) * | 2020-12-23 | 2021-04-30 | 贵州大龙汇成新材料有限公司 | Method for recovering valuable elements from manganese sulfide slag |
| CN112813260A (en) * | 2020-12-28 | 2021-05-18 | 广东佳纳能源科技有限公司 | Reduction leaching method |
| CN113060712A (en) * | 2021-03-15 | 2021-07-02 | 中南大学 | Method for preparing iron phosphate and nickel cobalt manganese hydroxide battery precursor material from metal nickel cobalt iron powder |
| CN113862474A (en) * | 2021-08-18 | 2021-12-31 | 池州西恩新材料科技有限公司 | Continuous acid leaching system and method adopting aeration to control reaction temperature |
| CN115216629A (en) * | 2022-06-28 | 2022-10-21 | 湖南中伟新能源科技有限公司 | Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste |
| CN115216629B (en) * | 2022-06-28 | 2023-08-04 | 湖南中伟新能源科技有限公司 | Method for comprehensively recovering metal elements in tungsten-doped ternary precursor waste |
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