CN110040786A - A kind of method of anode material of lithium battery recycling and reusing - Google Patents
A kind of method of anode material of lithium battery recycling and reusing Download PDFInfo
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- CN110040786A CN110040786A CN201910315009.4A CN201910315009A CN110040786A CN 110040786 A CN110040786 A CN 110040786A CN 201910315009 A CN201910315009 A CN 201910315009A CN 110040786 A CN110040786 A CN 110040786A
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
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Abstract
The present invention provides a kind of method of anode material of lithium battery recycling and reusing.The method includes following process: the positive plate of recycling being obtained nickle cobalt lithium manganate powder and silicon source by organic solvent or sodium hydroxide solution or potassium hydroxide solution separated and dissolved, then washed, Ore Leaching, precipitating nickel cobalt manganese hydroxide, washed again, isolated lithium carbonate to nickle cobalt lithium manganate.Method process provided by the invention is simple and convenient to operate, and realizes the complete recycling to positive electrode and plus plate current-collecting body, and the rate of recovery is high.
Description
Technical field
The invention belongs to waste and old lithium dynamical battery recycling fields, and in particular to the recycling of waste and old lithium dynamical battery positive electrode
Method.
Background technique
From the point of view of the lithium battery type used in the existing market, using positive electrode as cobalt acid lithium, nickle cobalt lithium manganate, phosphoric acid
Based on the lithium battery of iron lithium.With the rapid development of new-energy automobile industry, the ternary nickel cobalt manganese hydroxide battery number of generation
Amount is constantly increased sharply, and the recycling of battery material is extremely urgent.
China's new-energy automobile quantity in 2018 is up to 1,000,000, and the metal that correspondence can be recycled from dynamic lithium battery is about
There are 6.4 ten thousand tons.If mishandling, serious environmental pollution on the one hand may cause；On the other hand it may also result in refuse battery
In can secondary use the valuable metals wasting of resources such as nickel, cobalt, manganese, lithium.
Therefore, while greatly developing new energy dynamic lithium battery, waste power lithium battery resource utilization is utilized
Technical research more can not be ignored.It " can not only turn waste into wealth " to the recycling of lithium battery, realize that resource, environment are held
Supervention exhibition can also promote the innovation and development of New Energy Industry chain.
But the method recycled in the prior art to anode material of lithium battery can only be realized several to wherein certain or certain
The recycling of metal cannot all recycle the valuable metal in anode material of lithium battery, and recovery efficiency is low, recycling at
This height.
Summary of the invention
The present invention provides a kind of method of anode material of lithium battery recycling and reusing, to solve the above problem.
To solve the above problems, The technical solution adopted by the invention is as follows:
A kind of method of anode material of lithium battery recycling and reusing, the method includes following process:
Process S1: the positive plate of recycling is added in organic solvent, dissolves the binder in positive plate, isolated nickel
Cobalt manganic acid lithium powder and aluminium foil；Or the positive plate after recycling by break process is added to sodium hydroxide solution or potassium hydroxide
It in solution, is reacted under heating condition, isolated nickle cobalt lithium manganate powder and sodium aluminate solution or aluminic acid potassium solution, by sulphur
Acid is added in the sodium aluminate solution or aluminic acid potassium solution, is adjusted pH value, is reacted under heating condition, crystallization obtains hydrogen
Aluminium oxide.
Process S2: washing nickle cobalt lithium manganate powder described in process S1, filtered, and it is solid to obtain nickle cobalt lithium manganate
Body.
Process S3: nickle cobalt lithium manganate solid and reducing agent described in process S2 are added in sulfuric acid solution, are adjusted
PH value is reacted under heating condition, is handled by acid leaching process, the leachate of isolated nickel and cobalt containing manganese lithium sulfate and leaching
It slags tap.
Process S4: the leachate of nickel and cobalt containing manganese lithium sulfate described in process S3 is mixed with sodium hydroxide solution, is adjusted
PH value is saved, is reacted under heating condition, obtains nickel cobalt manganese hydroxide solids and mother liquor containing lithium.
Process S5: washing nickel cobalt manganese hydroxide solids described in process S4, obtains nickel-cobalt-manganese ternary forerunner
Body product.
Process S6: natrium carbonicum calcinatum is added in mother liquor containing lithium described in process S5 and carries out synthetic reaction, is crystallized
To lithium carbonate product.
Method as described above, in process S1, the positive plate of the recycling and the mass ratio of the organic solvent are
1:3, the organic solvent are N-Methyl pyrrolidone, are dissolved at 90 DEG C；
By the quality of the positive plate of break process and the sodium hydroxide solution or potassium hydroxide solution after the recycling
Volume ratio be 1g:5mL, the sodium hydroxide or potassium hydroxide solution concentration are 185g/L, and reaction temperature is 60-90 DEG C.
The sodium aluminate or aluminic acid potassium solution are heated to 50 DEG C, sulphur are added by method as described above in process S1
Acid for adjusting pH=9.
Method as described above, in process S2, the washing step is washed under the conditions of 80 DEG C, in process S5,
The washing step is washed under the conditions of 60 DEG C.
Method as described above, in process S3, the concentration of the sulfuric acid solution is 200-220g/L, and the sulfuric acid is molten
The mass ratio of the quality of sulfuric acid and the nickle cobalt lithium manganate solid is 1.5:1 in liquid, the quality of the nickle cobalt lithium manganate solid with
The mass ratio of the reducing agent is 1:(0.9-1.1).
Method as described above, in process S3, the reducing agent is selected from hydrogen peroxide, sodium thiosulfate, sodium polysulfide,
Reaction temperature is 70 DEG C, pH=4.
Method as described above, in process S4, the concentration of sodium hydroxide solution is 200-250g/L, pH=10-
11, reaction temperature is 70 DEG C.
Method as described above measures the lithium content in mother liquor containing lithium, the quality of lithium and the carbonic acid in process S6
The mass ratio of sodium is 1:9.
Method as described above, the method also includes process S7: Precipitation incomplete in process S6 is contained lithium
Mother liquid evaporation is concentrated to get sulfate crystal or potassium sulfate crystallization, remaining liq return in process S6.
Method as described above carries out in the case that crystallization obtains sodium sulphate product in process S7 at 40 DEG C or more
Crystallization, crystallization obtains anhydrous sodium sulfate product, or is crystallized at 40 DEG C or less, and crystallization obtains Disodium sulfate decahydrate product.
In conclusion by adopting the above-described technical solution, the invention has the following advantages:
Comprehensive reutilization method provided by the invention is directed to nickle cobalt lithium manganate battery, realizes to positive electrode and just
The complete recycling of pole collector can efficiently isolate lithium carbonate, silicon source and nickel cobalt manganese presoma product, and valuable gold
The leaching rate of category is high, and the purpose of scale recycling waste lithium cell positive electrode may be implemented.
Specific embodiment
All features disclosed in this specification can be with any other than mutually exclusive feature and/or step
Mode combines.
In order to it is abundant, completely understand feature of the invention, purpose, effect and advantage, pass through following specific embodiment parties
Formula, the present invention is described in detail.For process of the invention in addition to following methods, remaining is all made of the conventional mark of this field
Quasi- method or apparatus.Following nouns or term by those skilled in the art are normally understood unless otherwise stated, contain
Justice uses.
The present invention provides a kind of methods of anode material of lithium battery recycling and reusing, and the method includes following process:
Process S1: the positive plate of recycling is added in organic solvent, dissolves the binder in positive plate, isolated nickel
Cobalt manganic acid lithium powder and aluminium foil；Or the positive plate after recycling by break process is added to sodium hydroxide solution or potassium hydroxide
It in solution, is reacted under heating condition, isolated nickle cobalt lithium manganate powder and sodium aluminate solution or aluminic acid potassium solution, by sulphur
Acid is added in the sodium aluminate solution or aluminic acid potassium solution, is adjusted pH value, is reacted under heating condition, crystallization obtains hydrogen
Aluminium oxide.
Process S2: washing nickle cobalt lithium manganate powder described in process S1, filtered, and it is solid to obtain nickle cobalt lithium manganate
Body.
Process S3: nickle cobalt lithium manganate solid and reducing agent described in process S2 are added in sulfuric acid solution, are adjusted
PH value is reacted under heating condition, is handled by acid leaching process, the leachate of isolated nickel and cobalt containing manganese lithium sulfate and leaching
It slags tap.
Process S4: the leachate of nickel and cobalt containing manganese lithium sulfate described in process S3 is mixed with sodium hydroxide solution, is adjusted
PH value is saved, is reacted under heating condition, obtains nickel cobalt manganese hydroxide solids and mother liquor containing lithium.
Process S5: washing nickel cobalt manganese hydroxide solids described in process S4, obtains nickel-cobalt-manganese ternary forerunner
Body product.
Process S6: natrium carbonicum calcinatum is added in mother liquor containing lithium described in process S5 and carries out synthetic reaction, is crystallized
To lithium carbonate product.
Process S1. separates silicon source
Positive electrode in battery is coated on collector by organic binder, in order to keep battery in use
Stability, the combination of the two is very closely, both can not to make to be kept completely separate at all only by mechanical means.The present invention
In, binder is dissolved using organic solvent, reaches and efficiently separates anode material nickel cobalt manganic acid lithium and current collector aluminum foil
Purpose.Preferably, in process S1, the mass ratio of the positive plate of the recycling and the organic solvent is 1:3, described organic molten
Agent is N-Methyl pyrrolidone, is dissolved at 90 DEG C, therefore can isolate current collector aluminum foil to the greatest extent, separation effect
Fruit is good.
Alternatively, dissolving anode waste using sodium hydroxide solution or potassium hydroxide solution in the present invention, make current collector aluminum foil
Enter solution in the form of sodium metaaluminate or potassium metaaluminate, is returned in the form of aluminium hydroxide with after sulfuric acid progress neutralization reaction
It receives.Preferably, the quality of the positive plate after the recycling by break process and the sodium hydroxide solution or potassium hydroxide are molten
The volume ratio of liquid is 1g:5mL, and the sodium hydroxide solution or potassium hydroxide solution concentration are 185g/L, reaction temperature 60-
90 DEG C, preferably 90 DEG C, under the conditions of the concentration and the reaction temperature, the rate that lye dissolves aluminium is higher, can make big portion
Aluminium is divided to separate with anode material nickel cobalt manganic acid lithium, while nickle cobalt lithium manganate does not almost dissolve, recycling obtains nickel cobalt mangaic acid after filtering
Lithium powder avoids loss valuable metal.Preferably, in process S1, sodium aluminate solution or aluminic acid potassium solution are heated to 50 DEG C,
Sulfuric acid is added and adjusts pH=9, obtained aluminum hydroxide solid purity is high.
Process S2. washing impurity-removing
Washing impurity-removing is carried out to the nickle cobalt lithium manganate powder that is collected into, is typically chosen and is washed with deionized water, when washing
It can stop when washing to neutrality.Specifically, take the nickle cobalt lithium manganate powder being collected into be slowly added under certain temperature go from
It is stirring while adding in sub- water, it is stirred continuously the dissolution that can accelerate soluble component, washing a period of time is filtered, and surveys filter
The pH value of liquid is repeatedly washed repeatedly, is filtered, until filtrate is in neutrality, thus removed if filtrate made alkaline
The nickle cobalt lithium manganate solid of the soluble components such as sodium, aluminium.Preferably, in process S2, the washing step is under the conditions of 80 DEG C
Washing can accelerate the rate of dissolution of soluble component at this temperature, improve detersive efficiency, and effectively removing sodium/potassium, aluminium etc. are solvable
Property ingredient, obtain the higher nickel cobalt manganese LiMn2O4 solid of degree of purity, be conducive to carry out next step acidic leaching process.
Process S3. sulfuric acid leaching
The present invention carries out special Ore Leaching technique using sulfuric acid-reducing agent system, so that the nickel cobalt manganese in nickle cobalt lithium manganate
Lithium is entered in solution in the form of sulfate, and the binder etc. in electrode stays in leached mud.Preferably, in process S3, institute
The concentration for stating sulfuric acid solution is 200-220g/L, the matter of the quality of sulfuric acid and the nickle cobalt lithium manganate solid in the sulfuric acid solution
Amount is than being 1.5:1, and the quality of the nickle cobalt lithium manganate and the mass ratio of the reducing agent are 1:(0.9-1.1), and reaction temperature is
70 DEG C, pH=4, with this condition, the leaching rate of nickel cobalt manganese lithium are higher, up to 98% or more.As the reducing agent, specifically
It is enumerated as hydrogen peroxide, sodium thiosulfate, sodium polysulfide, the reducing agent reproducibility is strong, can make nickle cobalt lithium manganate effectively and quickly
Be decomposed into metal ion, so as to improve the leaching rate of valuable metal.
Process S4. precipitates nickel cobalt manganese hydroxide
The nickel cobalt manganese ion obtained after acidic leaching is reacted with sodium hydroxide solution, and it is solid to be settled out nickel cobalt manganese hydroxide
Body, and separate and obtain mother liquor containing lithium.Preferably, in process S4, the concentration of sodium hydroxide solution is 200-250g/L, pH
=10-11, reaction temperature are 70 DEG C, and with this condition, the nickel cobalt manganese hydroxide solids settling rate is very fast.
Process S5. washing impurity-removing
Washing impurity-removing process further is carried out to the nickel cobalt manganese hydroxide solids that process S4 is settled out, removal wherein remains
Lithium ion, sodium ion/potassium ion, sulfate ion, hydroxide ion and other trace soluble impurity, obtain nickel cobalt manganese
Ternary precursor product may be directly applied to the preparation of anode material of lithium battery.Preferably, in process S5, the washing
Step is washed under the conditions of 60 DEG C, so that removal of impurities is thoroughly, obtained nickel-cobalt-manganese ternary presoma product purity is higher.
Process S6. separates lithium carbonate
In process S6, reacted using sodium carbonate with the mother liquor containing lithium that process S4 is separated to isolate lithium carbonate.Tool
Body, the lithium content in mother liquor containing lithium is measured, lithium mother liquor will be contained and reacted according to a certain percentage with the sodium carbonate, carbon is obtained
Sour lithium.It preferably, is 1:9 charging according to the mass ratio of the quality of lithium and the sodium carbonate, so that the lithium in mother liquor containing lithium separates
Thoroughly, lithium source waste is not will cause, and isolated lithium carbonate product purity is higher, up to 99% or more.
Process S7. separates sylvite/sodium salt
Method provided by the invention further includes process S7: the mother liquid evaporation containing lithium of Precipitation incomplete in process S6 is dense
Contracting obtains sulfate crystal or potassium sulfate crystallization, remaining liq are returned in process S6 and reused.
It reacts corresponding to process S6 with sodium carbonate with mother liquor containing lithium to separate lithium carbonate, it is preferred that in process S7, evaporation
When being concentrated to get sulfate crystal, when the evaporation-concentration step is crystallized at 40 DEG C or more, crystallization obtains anhydrous sodium sulfate
Product, or when being crystallized at 40 DEG C or less, crystallization obtains Disodium sulfate decahydrate product.
The positive plate of recycling is passed through organic solvent or hydrogen-oxygen using the principle of co-precipitation complicated between each raw material by the present invention
Change sodium solution or potassium hydroxide solution separated and dissolved obtains nickle cobalt lithium manganate and silicon source.Pass through washing, sulfuric acid leaching, coprecipitated nickel hydroxide again
Cobalt manganese hydroxide, is washed again, and sodium carbonate is added to prepare the processes such as lithium carbonate, so that nickel cobalt manganese is separated with lithium source, is reached to lithium
The purpose that the synthetical recovery of cell positive material and plus plate current-collecting body recycles.
Further illustrate that the present invention, the present invention are not merely only limited in embodiment below by the mode of embodiment
Within the scope of specific.The experimental method of specific implementation condition is not specified in the following example, according to conventional criteria experiment flow
Condition and method operation.Raw material, the reagent being related in the following example be the conventional raw material for meeting relevant regulations in the market,
Reagent is examined, detection method is country, standard test detection method as defined in industry.
Embodiment 1
(1) it weighs after 200g is recycled by broken positive plate, 1000mL is slowly added into the ratio of 1:5 (g:mL) and is contained
Amount is in the sodium hydroxide solution of 185g/L, and when addition should be added while stirring, to guarantee adequately to be dissolved in hydroxide
It in sodium solution, and keeps reaction temperature at 90 DEG C, persistently stirs 3h, dissolve the metallic aluminium in positive plate.It is produced when reaction
Raw a certain amount of bubble, and generated with a small amount of hydrogen.After the reaction was completed, by filter device, nickle cobalt lithium manganate powder is obtained
And sodium aluminate solution.
(2) measure (1) in generate sodium aluminate solution 100mL, be heated to 50 DEG C while stirring, be slowly added to 98% it is dense
Sulfuric acid adjusts pH=9, reacts 2.5h, obtains aluminum hydroxide solid.
(3) the undissolved nickle cobalt lithium manganate powder 200g generated in (1) is added to the distilled water that 500mL temperature is 80 DEG C
In, it is stirring while adding, 1.5h is reacted, continues to repeat to be washed to filtrate after filtering as neutral (pH=7), the sodium that is removed, aluminium etc.
The nickle cobalt lithium manganate of soluble component.
(4) sulfuric acid solution for preparing 200g/L, the nickel that (3) are added and obtain according to 2/3 times of sulfuric acid quality in sulfuric acid solution
Cobalt manganic acid lithium is slowly added to 0.9 times of dioxygen water reducing agent of nickle cobalt lithium manganate quality, keeps temperature 70 C to adjust pH=4, instead
2h is answered, the leaching rate of nickel cobalt manganese lithium reaches 98% or more.Leachate, leached mud is obtained by filtration.
(5) sodium hydroxide solution of leachate and 200g/L are added in reaction kettle simultaneously while stirring, speed is added dropwise in control
Degree makes its pH value of solution be maintained at 10-11, and color stops liquid feeding when being light blue, is warming up to 70 DEG C, and after reacting 4h, solution becomes
Nickel-cobalt-manganese ternary presoma and mother liquor containing lithium is obtained by filtration in khaki.
(6) nickel-cobalt-manganese ternary presoma obtained in (5) is added in the distilled water of 500mL, is heated to 60 DEG C, stirring
1h removes lithium ion, sodium ion, sulfate ion, hydroxide ion and other trace soluble impurity therein, obtains three
First presoma product.
(7) it takes the 25mL of mother liquor containing lithium in reaction kettle, measures its lithium content, be heated to 60 DEG C, it is slow by 9 times of lithium total amount
Natrium carbonicum calcinatum is added, stirring 2h obtains the mother liquor containing lithium of lithium carbonate precipitating and incomplete Precipitation, filters to obtain lithium carbonate production
Product, purity are 99% or more.
(8) device of mother liquid evaporation containing lithium of incomplete Precipitation is concentrated by evaporation, the liquid being evaporated repeats (7) carbonic acid
Lithium settling step.The solid of concentration is sulfate crystal, and the above are anhydrous sodium sulfates at 40 DEG C for thickening temperature, and 40 DEG C the following are ten
Hydrated sulfuric acid sodium.
Embodiment 2
(1) it weighs after 200g is recycled by broken positive plate, 1000mL is slowly added into the ratio of 1:5 (g:mL) and is contained
Amount is in the sodium hydroxide solution of 185g/L, and when addition should be added while stirring, to guarantee adequately to be dissolved in hydroxide
It in sodium solution, and keeps reaction temperature at 60 DEG C, persistently stirs 3h, dissolve the metallic aluminium in positive plate.It is produced when reaction
Raw a certain amount of bubble, and generated with a small amount of hydrogen.After the reaction was completed, by filter device, nickle cobalt lithium manganate powder is obtained
And sodium aluminate solution.
(2) measure (1) in generate sodium aluminate solution 100mL, be heated to 50 DEG C while stirring, be slowly added to 98% it is dense
Sulfuric acid adjusts pH=9, reacts 2.5h, obtains aluminum hydroxide solid.
(3) the nickle cobalt lithium manganate powder 200g in (1) is added in the distilled water that 500mL temperature is 80 DEG C, side edged
1.5h is reacted in stirring, continues to repeat to be washed to filtrate after filtering as neutrality, the nickel cobalt of the soluble components such as the sodium that is removed, aluminium
LiMn2O4.
(4) sulfuric acid solution for preparing 210g/L, the nickel that (3) are added and obtain according to 2/3 times of sulfuric acid quality in sulfuric acid solution
1.0 times of sodium thiosulfate solid reductant of nickle cobalt lithium manganate quality is added portionwise in cobalt manganic acid lithium, and temperature 70 C is kept to adjust
PH=4, reacts 2h, and the leaching rate of nickel cobalt manganese lithium reaches 98% or more.Centrifugation obtains leachate, leached mud.
(5) sodium hydroxide solution of leachate and 250g/L are added into reaction kettle simultaneously while stirring, control is added dropwise
Speed makes its pH value of solution be maintained at 10-11, and color stops liquid feeding when being light blue, is warming up to 70 DEG C, and after reacting 4h, solution becomes
For khaki, nickel-cobalt-manganese ternary presoma and mother liquor containing lithium is obtained by filtration.
(6) nickel-cobalt-manganese ternary presoma obtained in (5) is added in the distilled water of 500mL, is heated to 60 DEG C, stirring
1h removes lithium ion, sodium ion, sulfate ion, hydroxide ion and other trace soluble impurity therein, obtains three
First presoma product.
(7) it takes the 25mL of mother liquor containing lithium in reaction kettle, measures its lithium content, be heated to 60 DEG C, it is slow by 9 times of lithium gross mass
Slow that sodium carbonate is added, stirring 2h obtains the mother liquor containing lithium of lithium carbonate precipitating and incomplete Precipitation, and centrifugation obtains lithium carbonate production
Product, 99% or more purity.
(8) mother liquid evaporation containing lithium of incomplete Precipitation is concentrated, the liquid being evaporated repeats (7) lithium carbonate precipitating
Step.The solid of concentration is sulfate crystal, and thickening temperature is at 40 DEG C the above are anhydrous sodium sulfate, and 40 DEG C the following are ten hydration sulphur
Sour sodium.
Embodiment 3
(1) it weighs after the recycling of 200g by broken positive plate, 1000mL is slowly added into the ratio of 1:5 (g:mL)
Content is in the potassium hydroxide solution of 185g/L, and when addition should be added while stirring, to guarantee adequately to be dissolved in hydrogen-oxygen
Change in potassium solution, and keep reaction temperature at 90 DEG C, persistently stirs 3h, dissolve the metallic aluminium in positive plate.When reaction
A certain amount of bubble is generated, and is generated with a small amount of hydrogen.After the reaction was completed, by filter device, nickle cobalt lithium manganate powder is obtained
End and aluminic acid potassium solution.
(2) measure (1) in generate aluminic acid potassium solution 100mL, be heated to 50 DEG C while stirring, be slowly added to 98% it is dense
Sulfuric acid adjusts the pH=9 of filtrate, reacts 2.5h, obtains aluminum hydroxide solid.
(3) (1) nickle cobalt lithium manganate powder 200g is added in the distilled water that 500mL temperature is 80 DEG C, it is stirring while adding,
1.5h is reacted, continues to repeat to be washed to filtrate after filtering as neutrality, the nickel cobalt mangaic acid of the soluble components such as the potassium that is removed, aluminium
Lithium.
(4) sulfuric acid solution for preparing 210g/L, the nickel that (3) are added and obtain according to 2/3 times of sulfuric acid quality in sulfuric acid solution
1.0 times of sodium thiosulfate solid reductant of nickle cobalt lithium manganate quality is added portionwise in cobalt manganic acid lithium, and temperature 70 C is kept to adjust
PH=4, reacts 2h, and the leaching rate of nickel cobalt manganese lithium reaches 98% or more.Centrifugation obtains leachate, leached mud.
(5) sodium hydroxide solution of leachate or leached mud and 230g/L is added into reaction kettle simultaneously while stirring,
Rate of addition is controlled, its pH value of solution is made to be maintained at 10-11, color stops liquid feeding when being light blue, is warming up to 70 DEG C, reacts 4h
Afterwards, solution becomes khaki, and nickel-cobalt-manganese ternary presoma and mother liquor containing lithium is obtained by filtration.
(6) nickel-cobalt-manganese ternary presoma obtained in (5) is added in the distilled water of 500mL, is heated to 60 DEG C, stirring
1h removes lithium ion, potassium ion, sulfate ion, hydroxide ion and other trace soluble impurity therein, obtains three
First presoma product.
(7) it takes the 25mL of mother liquor containing lithium in reaction kettle, measures its lithium content, be heated to 60 DEG C, it is slow by 9 times of lithium gross mass
Slow that sodium carbonate is added, stirring 2h obtains the mother liquor containing lithium of lithium carbonate precipitating and incomplete Precipitation, is centrifuged to obtain lithium carbonate product,
99% or more purity.
(8) mother liquid evaporation containing lithium of incomplete Precipitation is concentrated, the liquid being evaporated repeats (7) lithium carbonate precipitating
Step.The solid of condensing crystallizing is potassium sulfate.
Embodiment 4
(1) positive plate for weighing 200g recycling at random, it is organic molten to be slowly added into N-Methyl pyrrolidone with the ratio of 1:3
In agent, 2h is reacted at a temperature of 90 DEG C and dissolves binder PVDF, through the isolated nickle cobalt lithium manganate powder of filter device and aluminium foil.
(2) it takes the undissolved nickle cobalt lithium manganate powder 200g generated in (1) to be slowly added into 500mL temperature and is 80 DEG C
It is stirring while adding in ionized water, after reacting 1.5h, stop washing when surveying the pH to neutral (pH=7) of solution.Conversely, mistake again
Filtered solid is carried out the secondary pH value of solution that is washed to neutrality by filter, stops washing, the sodium that is removed, aluminium etc. it is soluble at
The nickle cobalt lithium manganate divided.
(3) sulfuric acid solution for preparing 220g/L, the nickel that (2) are added and obtain according to 2/3 times of sulfuric acid quality in sulfuric acid solution
Cobalt manganic acid lithium, stirring and dissolving, then 0.9 times of dioxygen water reducing agent of nickle cobalt lithium manganate quality is measured, it is slowly dropped in solution.
PH=4 is adjusted under conditions of 70 DEG C reacts 2h.Leachate, the leached mud of isolated nickel and cobalt containing manganese lithium.
(4) leachate of 100mL nickel and cobalt containing manganese lithium is measured, the sodium hydroxide solution that 5mL concentration is 200g/L is slow simultaneously
Reaction vessel is added and stirs, adjusts pH=10-11, solution colour stops liquid feeding when being light blue, is heated to 70 DEG C, reaction
4h, it is reaction end that solution colour, which becomes khaki, and nickel cobalt manganese hydroxide solids and mother liquor containing lithium is obtained by filtration.
(5) 200g nickel cobalt manganese hydroxide solids are weighed to be slowly added into the deionized water of 500mL, 60 DEG C is heated to and stirs
1h is mixed, lithium ion, sodium ion, sulfate ion, hydroxide ion and other trace soluble impurity therein is removed, obtains
Ternary precursor product.
(6) it takes the 25mL of mother liquor containing lithium in reaction kettle, measures its lithium content, be heated to 60 DEG C, it is slow by 9 times of lithium gross mass
Slow that natrium carbonicum calcinatum is added, stirring 2h obtains the mother liquor containing lithium of lithium carbonate precipitating and incomplete Precipitation, is centrifuged to obtain lithium carbonate
Product, 99% or more purity.
(7) by the mother liquor containing lithium of incomplete Precipitation by serpentine condenser be concentrated by evaporation, crystallization temperature 40 DEG C with
On crystallize out anhydrous sodium sulfate, 40 DEG C the following are Disodium sulfate decahydrates.The liquid being evaporated repeats (6) step.
Detailed content of the present invention discloses in the above-described embodiments, but it will be understood by those skilled in the art that these realities
It applies example and is only used as description the content of present invention, but should not be understood as limitation range of the invention.It is all to be described with the embodiment of the present invention
Equivalent reaction, variation, displacement etc. should all be set as covering in scope of the presently claimed invention.Protection scope of the present invention is answered
It is subject to the range defined in claims.
Claims (10)
1. a kind of method of anode material of lithium battery recycling and reusing, which is characterized in that the method includes following process:
Process S1: the positive plate of recycling is added in organic solvent, dissolves the binder in positive plate, isolated nickel cobalt manganese
Sour lithium powder and aluminium foil；Or the positive plate after recycling by break process is added to sodium hydroxide solution or potassium hydroxide solution
In, reacted under heating condition, isolated nickle cobalt lithium manganate powder and sodium aluminate solution or aluminic acid potassium solution, by sulfuric acid plus
Enter into the sodium aluminate solution or aluminic acid potassium solution, adjusts pH value, reacted under heating condition, crystallization obtains hydroxide
Aluminium.
Process S2: nickle cobalt lithium manganate powder described in process S1 is washed, is filtered, nickle cobalt lithium manganate solid is obtained.
Process S3: nickle cobalt lithium manganate solid and reducing agent described in process S2 are added in sulfuric acid solution, adjust pH value,
It is reacted under heating condition, is handled by acid leaching process, the leachate and leached mud of isolated nickel and cobalt containing manganese lithium sulfate.
Process S4: the leachate of nickel and cobalt containing manganese lithium sulfate described in process S3 is mixed with sodium hydroxide solution, adjusts pH
It is worth, is reacted under heating condition, obtain nickel cobalt manganese hydroxide solids and mother liquor containing lithium.
Process S5: washing nickel cobalt manganese hydroxide solids described in process S4, obtains the production of nickel-cobalt-manganese ternary presoma
Product.
Process S6: natrium carbonicum calcinatum being added in mother liquor containing lithium described in process S5 and carries out synthetic reaction, and crystallization obtains carbon
Sour lithium product.
2. the method as described in claim 1, which is characterized in that in process S1, the positive plate of the recycling with it is described organic
The mass ratio of solvent is 1:3, and the organic solvent is N-Methyl pyrrolidone, is dissolved at 90 DEG C；
By the body of the quality of the positive plate of break process and the sodium hydroxide solution or potassium hydroxide solution after the recycling
Product ratio is 1g:5mL, and the sodium hydroxide or potassium hydroxide solution concentration are 185g/L, and reaction temperature is 60-90 DEG C.
3. the method as described in claim 1, which is characterized in that in process S1, the sodium aluminate or aluminic acid potassium solution are added
Heat is added sulfuric acid and adjusts pH=9 to 50 DEG C.
4. the method as described in claim 1, which is characterized in that in process S2, the washing step is that 80 DEG C of conditions are lauched
It washes, in process S5, the washing step is washed under the conditions of 60 DEG C.
5. the method as described in claim 1, which is characterized in that in process S3, the concentration of the sulfuric acid solution is 200-
220g/L, the mass ratio of the quality of sulfuric acid and the nickle cobalt lithium manganate solid is 1.5:1, the nickel cobalt manganese in the sulfuric acid solution
The quality of sour lithium solid and the mass ratio of the reducing agent are 1:(0.9-1.1).
6. the method as described in claim 1, which is characterized in that in process S3, the reducing agent is selected from hydrogen peroxide, thio sulphur
Sour sodium, sodium polysulfide, reaction temperature are 70 DEG C, pH=4.
7. the method as described in claim 1, which is characterized in that in process S4, the concentration of sodium hydroxide solution is 200-
250g/L, pH=10-11, reaction temperature are 70 DEG C.
8. the method as described in claim 1, which is characterized in that in process S6, the lithium content in mother liquor containing lithium is measured, lithium
The mass ratio of quality and the sodium carbonate is 1:9.
9. the method according to claim 1, which is characterized in that the method also includes process S7: by process S6
In incomplete Precipitation mother liquid evaporation containing lithium be concentrated to get sulfate crystal or potassium sulfate crystallization, remaining liq return to work
In sequence S6.
10. method as claimed in claim 9, which is characterized in that in process S7, crystallize the case where obtaining sodium sulphate product
Under, it is crystallized at 40 DEG C or more, crystallization obtains anhydrous sodium sulfate product, or is crystallized at 40 DEG C or less, and crystallization obtains ten
Hydrated sulfuric acid sodium product.
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| CN110767954A (en) * | 2019-09-16 | 2020-02-07 | 天齐锂业（江苏）有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
| CN111039312A (en) * | 2019-12-26 | 2020-04-21 | 甘肃睿思科新材料有限公司 | Treatment method of nickel cobalt lithium manganate positive electrode material |
| CN111206153A (en) * | 2020-02-20 | 2020-05-29 | 贵州红星电子材料有限公司 | Method for recovering positive electrode material of nickel-cobalt-manganese acid lithium battery |
| CN113981226A (en) * | 2021-09-29 | 2022-01-28 | 贵州中伟资源循环产业发展有限公司 | Method for pretreating ternary positive plate to be recycled |
| CN114573006A (en) * | 2022-03-24 | 2022-06-03 | 甘肃睿思科新材料有限公司 | Method for purifying by-product lithium-containing crude sodium sulfate in lithium extraction process of recycling nickel cobalt lithium manganate cathode material and recycling lithium |
| CN114583309A (en) * | 2022-03-08 | 2022-06-03 | 骆驼集团资源循环襄阳有限公司 | Method for preparing precursor by recycling waste ternary lithium ion battery |
| WO2022183243A1 (en) * | 2021-03-02 | 2022-09-09 | The University Of Queensland | Precipitation of metals |
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| CN110767954A (en) * | 2019-09-16 | 2020-02-07 | 天齐锂业（江苏）有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
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| WO2022183243A1 (en) * | 2021-03-02 | 2022-09-09 | The University Of Queensland | Precipitation of metals |
| CN113981226A (en) * | 2021-09-29 | 2022-01-28 | 贵州中伟资源循环产业发展有限公司 | Method for pretreating ternary positive plate to be recycled |
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| CN114583309A (en) * | 2022-03-08 | 2022-06-03 | 骆驼集团资源循环襄阳有限公司 | Method for preparing precursor by recycling waste ternary lithium ion battery |
| CN114573006A (en) * | 2022-03-24 | 2022-06-03 | 甘肃睿思科新材料有限公司 | Method for purifying by-product lithium-containing crude sodium sulfate in lithium extraction process of recycling nickel cobalt lithium manganate cathode material and recycling lithium |
| CN114573006B (en) * | 2022-03-24 | 2023-06-30 | 甘肃睿思科新材料有限公司 | Method for purifying and recovering lithium by-product lithium-containing crude sodium sulfate in lithium extraction process of nickel cobalt lithium manganate anode material recovery |
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