CN108384955A - A method of from selectively carrying lithium in waste material containing lithium battery - Google Patents
A method of from selectively carrying lithium in waste material containing lithium battery Download PDFInfo
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- CN108384955A CN108384955A CN201810231801.7A CN201810231801A CN108384955A CN 108384955 A CN108384955 A CN 108384955A CN 201810231801 A CN201810231801 A CN 201810231801A CN 108384955 A CN108384955 A CN 108384955A
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- lithium
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- containing lithium
- sinker
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The present invention provides a kind of methods selectively carrying lithium from waste material containing lithium battery.It the described method comprises the following steps：(1) pretreated waste material containing lithium battery is mixed with oxide water solution, Leach reaction is carried out to obtained raw material slurry, obtains leaching slurry after reaction；(2) regulating step (1) pH to 7 13 for leaching slurry, is separated by solid-liquid separation obtained reaction slurry, obtains solid slag and scavenging solution containing lithium；(3) carbonate is added into scavenging solution containing lithium described in step (2), carry out sinker reaction, it is separated by solid-liquid separation after reaction and obtains lithium carbonate product and sinker tail washings, the sinker tail washings is after being adjusted to acidity in the Leach reaction system of return to step (1).Method provided by the invention has broad applicability, and flow is short, easy to operate, and reaction condition is mild, and reaction raw materials are of low cost, whole flow process three-waste free discharge, realizes the highly selective recycling of lithium resource in waste material containing lithium battery.
Description
Technical field
The present invention relates to the recovery technology fields of lithium resource in lithium ion battery waste material, and in particular to one kind is from containing lithium battery
The method that lithium is selectively carried in waste material.
Background technology
Lithium ion battery because with energy height, light weight, have extended cycle life, the advantages such as memory-less effect are widely used in moving
The fields such as the 3C such as mobile phone, laptop, digital camera digital products and electric vehicle, energy storage.Only 2011, China's lithium ion
The output of battery is as high as 2,900,000,000.It is adjoint therewith, the generations of a large amount of waste and old lithium ion batteries to China or even
Global electron wastes processing and environmental protection propose stern challenge.Have in one side waste and old lithium ion battery
The harmful constituents such as the inflammable electrolyte of poison, heavy metal if serious water body and soil pollution can be caused by dealing with improperly, or even cause fire
Calamity explosion safety accident etc.；Contain the metals such as a large amount of lithium, cobalt, nickel, manganese, copper, aluminium money in another aspect waste and old lithium ion battery
Source not only has considerable economic value, but also can largely alleviate China and exist at present if high efficiente callback can be realized
The short predicament of the resources such as cobalt, lithium.
Currently, by economic profit incentive, waste and old lithium ion battery recycling focuses on valuable metal member in electrode material
The high efficiente callback of element.Typically Mechanical Crushing will be carried out after old and useless battery electric discharge, dismantling and screening separation obtains electrode activity thing
Matter powder, powder obtain leachate after acidleach, then through adjusting the processes such as acid, filtering, sinker, washing, drying finally to obtain carbonic acid
The persursor material of lithium product and respective electrode material.Above process technical principle is simple, easy to operate, it has also become waste and old at present
The routine operation means of lithium ion battery recycling, however contain the inorganic acid or organic acid of reducing agent in acidleach link generally use
To leach reagent, it is easy to cause serious equipment corrosion and secondary pollution problem is held in the follow-up removal of impurities separation phase of leachate
Colloid is easily formed during adjusting acid preparation hydroxide precursor, and easily causes the entrainment of a large amount of lithium ions in filtering link
Loss, thus causes resource comprehensive utilization rate not high.
To crack above-mentioned technical barrier, many researchers and enterprise respectively change the links such as acidleach, purification, separation
Into research, many modified techniques are proposed.
CN107058742A proposes a kind of method recycling lithium from waste and old lithium ion battery.It is by waste and old lithium ion battery
Dismantling, it is broken obtain battery powder, obtain feed liquid containing lithium after the purified processing of acidic dissolution fluid of battery powder, then through adjust acid, extract,
The processes such as washing, back extraction, oil removing, evaporation, crystallisation by cooling, filtering, drying finally obtain anhydrous lithium salts.This method needs multi-step impurity removal
Operation, process is complicated, is also easy to produce waste residue, waste water, and the links such as purification of leaching liquor, tune acid, extraction can cause lithium different degrees of
Entrainment loss, thus cause the comprehensive recovery of lithium not high.
CN106654437A proposes a kind of method recycling lithium from containing lithium battery.It is by waste and old lithium ion battery through short
Battery material is obtained after road electric discharge, dismantling, Mechanical Crushing, heat treatment, the sodium hydroxide that electrolyte is poured into ethanol as solvent is molten
Mixed solution is obtained in liquid, and it is organic to remove that reduced vacuum rectifying is carried out after mixed solution is mixed with the leachate of battery material
Solvent recrystallizes after sodium carbonate solid is added, obtains lithium carbonate.This method uses the sodium hydroxide containing a large amount of organic solvents molten
Liquid adjusts pickle liquor pH, greatly reduces lithium concentration in pickle liquor, and follow-up lithium carbonate is caused to prepare the sinker rate of link
Lowly, to reduce the recycled in its entirety rate of lithium, and the introducing of organic reagent increase later separation process processing load and
Energy consumption.
CN107394298A proposes lithium resource recovery method on a kind of waste and old lithium ion battery negative plate.It is by negative plate
Fine powder is obtained through ball milling, sieving after the blocky powder stripping on surface, powder is added in dilute hydrochloric acid and carries out Leach reaction, together
When be aided with ultrasonic agitation and form suspension；Filtrate pH is adjusted to 5-8 after filtering, again filter after by filtrate be concentrated by evaporation and
Saturated sodium carbonate solution is added in 80-100 DEG C of temperature range to obtain lithium carbonate precipitation, gained lithium carbonate precipitates washed drying
Obtain pure Lithium Carbonate powder.This method is easy to operate, however this method is used as using hydrochloric acid and leaches reagent, with high concentration ammonium hydroxide
The pH of secondary filtrate is adjusted, causes leaching equipment anti-corrosion and gas purifying equipment to be invested big, and this method is poorly suitable for containing
There are many processing procedures of the anode waste of valuable metal element.
The nitration mixture that CN106848471A proposes a kind of waste lithium ion cell anode material leaches and recovery method.The party
Method be by lithium cobaltate cathode waste material through crush it is dry after carry out in mixed acid restoring pre- leaching, the pre- leached mud of gained is after ball milling
Continue once to leach, obtain the leachate containing cobalt, lithium after secondary leaching, it is dense by being evaporated after leachate tune acid, filtering
Contracting, and saturated sodium carbonate solution is added, finally obtain pure Lithium Carbonate solid through being filtered, washed, drying.This method is employed many times
Ball milling and acidleach operation, it is cumbersome, and subsequently through adjusting acid to remove in the form of cobalt hydroxide cobalt in leachate, lithium can be caused
The a degree of entrainment loss of ion.
CN105742744A is proposed a kind of extracting lithium from the waste liquid containing lithium that waste and old lithium ion battery removal process generates
Method, this method will sodium carbonate be added waste liquid containing lithium in be stirred reaction, after crude lithium carbonate and sinker is obtained by filtration
Liquid, the crude lithium carbonate of gained carry out calcination process with manganese carbonate, obtain lithium manganate having spinel structure containing sodium after mixing；Gained is heavy
Liquid carries out sodium phosphate sinker, finally obtains lithium phosphate after crystallisation by cooling detaches sodium carbonate after lithium.The method achieve useless containing lithium
The high efficiente callback of lithium resource utilizes in water, however process is complicated, complicated for operation and time-consuming, while using high-temperature roasting operation and coming
LiMn2O4 is prepared, process energy consumption is larger.
Therefore, develop a kind of applicability it is wide, without discharge, reaction condition is mild and the selectivity and recovery rate of lithium are high contains
Lithium battery waste material, which puies forward lithium method, has this field important meaning.
Invention content
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide one kind from waste material containing lithium battery
The method that selectivity carries lithium.Method provided by the invention passes through control system in the solution containing Strong oxdiative performance chemicals
Redox characteristic, a step realize waste material containing lithium battery in elemental lithium highly selective extraction.Method provided by the invention is not
But flow is short, easy to operate, and applicability it is wide, without discharge, the selectivity and recovery rate of lithium are high.
In order to achieve the above object, the present invention uses following technical scheme：
The present invention provides a kind of method carrying lithium from waste material containing lithium battery, and described method includes following steps：
(1) pretreated waste material containing lithium battery is mixed with oxide water solution, obtained raw material slurry is soaked
Go out reaction, obtains leaching slurry after reaction；
(2) regulating step (1) pH to 7-13 for leaching slurry, is separated by solid-liquid separation obtained reaction slurry, obtains
To solid slag and scavenging solution containing lithium；
(3) carbonate is added into scavenging solution containing lithium described in step (2), carries out sinker reaction, is separated by solid-liquid separation after reaction
To lithium carbonate product and sinker tail washings, the sinker tail washings is after being adjusted to acidity in the Leach reaction system of return to step (1).
Method provided by the invention is contained by the redox characteristic of control system using the realization of one step of oxide water solution
The highly selective extraction of elemental lithium in lithium battery waste material, and inhibit the leaching process of other valuable metal elements.
Method provided by the invention is in step (1), and the waste material containing lithium battery used with oxide water solution before mixing
Pretreatment is first passed through, pretreated purpose is to remove the aluminium and copper in waste material containing lithium battery in advance, because what the present invention was handled
Waste material containing lithium battery comparison of ingredients is complicated, if not before leaching by waste material aluminium and copper removing, subsequent leaching can be influenced
Go out reaction and separation, impurity removal process.
In the step of method provided by the invention (2), by step (1) it is described leach slurry pH to 7-13, such as 7,8,
8.5,9,9.5,10,10.4,11.1,11.6,12 or 13 etc., it is not limited to cited numerical value, in the numberical range its
His unrequited numerical value is equally applicable.It is to carry out deep impurity-removing that the step, which adjusts pH,.In the present invention, because what is used contains lithium
Battery waste comparison of ingredients is complicated, and preprocessing process is difficult to ensure the complete removing of the heteroions such as aluminium, copper, in the Leach reaction stage
Have a small amount of valuable metal, such as nickel, aluminium, copper enter in solution, thus also need to adjust after the leaching pH to 7-13 with into
Row deep impurity-removing, to obtain purer scavenging solution containing lithium.
In the present invention, after step (3) obtains sinker tail washings, the leaching of return to step (1) after tune acid is carried out to sinker tail washings
In the process, so that it is recycled, further reduced integrated artistic actual consumption amount and operating cost, and fundamentally solve
Discharge of wastewater problem, realizes zero-emission.In addition, this circulate operation also contributes to the lithium synthesis of the method for the invention
The rate of recovery.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, in step (1), the pretreatment include Mechanical Crushing, ball milling, gravity treatment,
In magnetic separation, mechanochemistry processing, organic solvent dissolving, roasting or alkali leaching any one or at least two combination, it is typical but
Being non-limiting combination has：The combination of the combination of Mechanical Crushing and ball milling, gravity treatment and magnetic separation, mechanochemistry processing and it is organic molten
The combination etc. of the combination of agent dissolving, roasting or alkali leaching, the combination that preferably Mechanical Crushing, gravity treatment, roasting and alkali soak are pre- using this
Processing method is advantageous in that can effectively remove copper in waste material, aluminium, organic binder by Mechanical Crushing, gravity treatment and roasting process
Etc. components, by alkali soak can remove waste material in residual aluminum component, these operative combinations are used, can more be filled before leaching operation
Point removing aluminium, the impurity such as copper, be conducive to subsequent leaching operation and finally realize highly selective carry lithium.
As currently preferred technical solution, in step (1), the waste material containing lithium battery include cobalt acid lithium, lithium nickelate,
LiMn2O4, lithium nickel cobalt dioxide, nickel ion doped, cobalt manganic acid lithium, nickel-cobalt-manganese ternary, nickel cobalt aluminium ternary, lithium alloys cathode, lithium titanate are negative
In pole or graphite cathode containing lithium any one or at least two combination, it is typical but be non-limiting combination and have：Cobalt acid lithium
With the combination of lithium nickelate, the combination of LiMn2O4 and lithium nickel cobalt dioxide, the combination of nickel ion doped and cobalt manganic acid lithium, cobalt manganic acid lithium and nickel cobalt
The combination etc. of the combination of manganese ternary, nickel cobalt aluminium ternary and lithium alloys cathode.
Preferably, in step (1), the waste material containing lithium battery comes from waste and old lithium ion battery and is obtained after discharging and being crushed
To full battery powder, obtain after waste and old lithium ion battery dismantling positive electrode, obtain after waste and old lithium ion battery dismantling
The defect ware waste material generated in the positive and negative anodes leftover pieces or Production Process of Lithium Battery that are generated in negative material, Production Process of Lithium Battery
In any one or at least two combination.
As currently preferred technical solution, in step (1), the oxide water solution be perchlorate aqueous solution,
Permanganate water solution, ferrate aqueous solution, Fenton reagent aqueous solution, Fenton-type reagent aqueous solution, persulfate aqueous solution,
In ozone water solution or aqueous hydrogen peroxide solution any one or at least two combination, it is typical but be non-limiting combination
Have：The combination of perchlorate aqueous solution and permanganate water solution, the combination of ferrate aqueous solution and Fenton reagent aqueous solution,
The combination etc. of the combination of Fenton-type reagent aqueous solution and persulfate aqueous solution, ozone water solution and aqueous hydrogen peroxide solution.
Preferably, contain activated carbon in the ozone water solution.
As currently preferred technical solution, in step (1), further include：Before carrying out Leach reaction, to raw material slurry
It is preheated.
Preferably, the raw material slurry be preheated to temperature be 25-200 DEG C, such as 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C,
66 DEG C, 72 DEG C, 78 DEG C, 82 DEG C, 94 DEG C, 96 DEG C, 100 DEG C, 150 DEG C or 200 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the numberical range, preferably 50-150 DEG C, further preferably 60-100 DEG C.
Preferably, in step (1), the Leach reaction carries out in the reactor.
Preferably, the reactor is open reactor or closed reactor, preferably atmospheric closed reactor.The present invention
In, when using closed reactor, the liquid phase substance in reaction system will not be caused to volatilize because of heating, because without adding halfway
Solubilizer improves the operability of the method for the invention.And atmospheric closed reactor can obtain better effect.
Preferably, in step (1), the Leach reaction is with stirring.
Preferably, the stirring is any one in magnetic agitation, mechanical agitation or Gas Stirring or at least two
Combination, preferably mechanical agitation.
Preferably, in step (1), time of the Leach reaction is 0.5-48h, for example, 0.5h, 1h, 2h, 2.5h,
3.2h, 4.3h, 5.6h, 6.2h, 7.7h, 8.0h, 8.4h, 9.2h, 9.6h, 10.0h, 20h, 35h, 46h or 48h etc., but not
It is only limitted to cited numerical value, other unrequited numerical value are equally applicable in the numberical range, preferably 1-12h, further excellent
It is selected as 2-12h.
As currently preferred technical solution, in step (2), regulating step (1) pH to 8-11 for leaching slurry.
In the present invention, micro valuable metal ions in pH to the 8-11 more conducively removal leachates for leach slurry are adjusted, while will not make
Al(OH)3It re-dissolves to form meta-aluminic acid root.
Preferably, in step (2), with alkaline matter regulating step (1) pH for leaching slurry.
Preferably, the alkaline matter include in sodium hydroxide, potassium hydroxide, ammonium hydroxide or ammonium salt any one or at least
Two kinds of combination.It is typical but be non-limiting combination and have：The combination of sodium hydroxide and potassium hydroxide, potassium hydroxide and ammonium hydroxide
Combination, the combination etc. of ammonium hydroxide and ammonium salt.
Preferably, described to be separated by solid-liquid separation to be separated by filtration and/or centrifuging in step (2), preferably it is separated by filtration.
In the present invention, it is described be separated by filtration and/or centrifuge refer to can be to be separated by filtration, or centrifuge, can be with
For the combination for being separated by filtration and centrifuging.
As currently preferred technical solution, in step (3), the carbonate includes sodium carbonate and/or potassium carbonate, excellent
It is selected as sodium carbonate.In the present invention, the sodium carbonate and/or potassium carbonate refer to can be sodium carbonate, or potassium carbonate may be used also
Think the combination of sodium carbonate and potassium carbonate.
As currently preferred technical solution, in step (3), the temperature of the sinker reaction at 25 DEG C or more, such as
25 DEG C, 50 DEG C, 75 DEG C, 81 DEG C, 86 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 98 DEG C, 100 DEG C or 150 DEG C etc., preferably 80-100
℃。
Preferably, in step (3), time of sinker reaction is 1-10h, for example, 1.0h, 2.0h, 2.3h, 3.1h,
3.5h, 4.6h, 5.1h, 5.8h, 6.0h, 7.5h, 8.3h, 9.1h or 10.0h etc., preferably 2-6h.
Preferably, described to be separated by solid-liquid separation to be separated by filtration and/or centrifuging in step (3), preferably it is separated by filtration.
In the present invention, it is described be separated by filtration and/or centrifuge refer to can be to be separated by filtration, or centrifuge, can be with
For the combination for being separated by filtration and centrifuging.
As currently preferred technical solution, in step (3), the acid-base property of sinker tail washings is adjusted with acidic materials.
Preferably, the acidic materials include in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or strong acid weak base salt any one or
At least two combination, typical but unrestricted combination have：The combination of the combination of sulfuric acid and hydrochloric acid, hydrochloric acid and nitric acid, nitric acid
With the combination of phosphoric acid, the combination etc. of phosphoric acid and strong acid weak base salt.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) pretreated waste material containing lithium battery is mixed with oxide water solution, obtains raw material slurry, by raw material slurry
It is preheated to 60-100 DEG C, is subsequently placed in atmospheric closed reactor, Leach reaction is carried out under mechanical agitation, the reaction time is
2-12h obtains leaching slurry after reaction；Wherein, the pretreatment is the combination that Mechanical Crushing, gravity treatment, roasting and alkali soak；
(2) alkaline matter regulating step (1) pH to 8-11 for leaching slurry is used, obtained reaction slurry was carried out
Filter separation, obtains solid slag and scavenging solution containing lithium；
(3) sodium carbonate is added into scavenging solution containing lithium described in step (2), sinker reaction, reaction is carried out at 80-100 DEG C
Time is 2-6h, is separated by filtration to obtain lithium carbonate product and sinker tail washings after reaction, and the sinker tail washings is with acidic materials tune
In Leach reaction system of the section for return to step (1) after acidity.
Compared with the prior art, the present invention has the advantages that：
(1) method provided by the invention that lithium is selectively carried from waste material containing lithium battery has broad applicability, can be used for
Cobalt acid lithium, LiMn2O4, lithium nickelate, binary, ternary material, the multiple batteries waste material containing lithium titanate cathode material etc. selectivity put forward lithium mistake
Journey；
(2) method flow provided by the invention that lithium is selectively carried from waste material containing lithium battery is short, easy to operate, reacts item
Part is mild, and reaction raw materials are of low cost, nontoxic, and ammonium acetate is simple, convenient for processing；
(3) the method whole process provided by the invention that lithium is selectively carried from waste material containing lithium battery is grasped using low-temperature atmosphere-pressure
Make, and realize cycle in medium, greatly reduces the consumption of reaction reagent, and whole flow process without waste water, exhaust gas or is given up
Slag discharges；
(4) method provided by the invention that lithium is selectively carried from waste material containing lithium battery realizes lithium in waste material containing lithium battery
The highly selective recycling of resource, the extraction selectivity of lithium is up to 95% or more, and single-trial extraction rate reaches 90% or more, by using following
Ring operates, and the comprehensive recovery of lithium also plays richness up to 99.9% or more further for other valuable metals in positive electrode
Collection acts on.
Description of the drawings
Fig. 1 is the process flow chart for the method that lithium is selectively carried from waste material containing lithium battery that the embodiment of the present invention 1 provides.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
It is present invention typical case but non-limiting embodiment below：
Embodiment 1
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) potassium ferrate that mechanical crushing pretreatment is added to 12wt.% for 100 mesh NCM523 positive electrodes below is molten
In liquid, raw material slurry is made, and be preheated to 95 DEG C, solid-to-liquid ratio 25g/L；Matched raw material slurry is placed in atmospheric closed reactor
It is interior, it carries out Leach reaction and lithium is carried with selectivity, ensure positive electrode even suspension in solution using mechanical agitation, speed of agitator
400rpm, reacts 5.5h, and reaction terminates to obtain leaching slurry.
(2) KOH is added to leaching in slurry obtained by step (1), pH value of solution is adjusted to 11.0, the deep impurity-removing of progress,
Reaction slurry is obtained, gained reaction slurry is directly filtered, obtains the enrichment slag rich in nickel cobalt manganese and leachate containing lithium.
(3) 5mol/L K are slowly added into leachate containing lithium obtained by step (2)2CO3Solution, it is mechanical under the conditions of 89 DEG C
It is stirred to react 5.5h, is separated by filtration acquisition lithium carbonate product.The sinker tail washings being separated by filtration is adjusted with acidic materials
In Leach reaction system for return to step after acidity (1), realization recycles, and ensures three-waste free discharge.
The process flow chart of the method provided in this embodiment that lithium is selectively carried from waste material containing lithium battery is as shown in Figure 1.
In the present embodiment, each metal element content in leachate containing lithium, test are measured using Atomic Emission Spectrometer AES (ICP)
The result shows that lithium leaching rate, up to 96.26%, nickel, aluminium element content are respectively 0.13 and 0.24mg/L in leachate, are not detected
Cobalt, manganese element exist；The content of wherein lithium will be measured after the washing of gained lithium carbonate product, drying using ICP, calculates to obtain lithium carbonate
Product purity is 99.43%.In the present embodiment, the extraction of lithium is selectively 98.25%, and the single-trial extraction rate of lithium is 92.41%,
By using circulate operation, the comprehensive recovery of lithium is 99.94%.
Embodiment 2
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) the Fenton solution of 20wt.% is added in the cobalt acid lithium full battery powder of removal aluminium foil after being roasted in advance at 500 DEG C
In, raw material slurry is made, and be preheated to 75 DEG C, solid-to-liquid ratio 10g/L；Matched raw material slurry is placed in atmospheric closed reactor
It is interior, Leach reaction is carried out, ensures positive electrode even suspension speed of agitator 300rpm in solution using mechanical agitation, is reacted
4.2h, reaction terminate to obtain leaching slurry.
(2) NaOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 10.5, obtains reaction slurry；It will
Gained reaction slurry directly filters, and obtains the enrichment slag rich in cobalt and leachate containing lithium.
(3) it is slowly added to Na into leachate containing lithium obtained by step (2)2CO3Solid particle, machinery stirs under the conditions of 100 DEG C
Reaction 5h is mixed, acquisition lithium carbonate product is separated by filtration.The sinker tail washings being separated by filtration is being adjusted to acid with acidic materials
After property in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
96.35%, the presence of cobalt, aluminium, copper, iron plasma is not detected in leachate；By profit after the washing of gained lithium carbonate product, drying
The content that wherein lithium is measured with ICP, calculate lithium carbonate product purity is 99.68%.In the present embodiment, the extraction selectivity of lithium
It is 99.48%, the single-trial extraction rate of lithium is 92.50%, and by using circulate operation, the comprehensive recovery of lithium is 99.92%.
Embodiment 3
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) hydrogen peroxide containing 5v/v% is added in the lithium manganate cathode powder for removing aluminium foil in NaOH solution in advance
In, raw material slurry is made, and be preheated to 60 DEG C, solid-to-liquid ratio 10g/L；Matched raw material slurry is placed in atmospheric closed reactor
It is interior, Leach reaction is carried out, O is persistently blasted into solution by ozone generator3, ensure that positive electrode is uniform using mechanical agitation
It is suspended in solution, speed of agitator 150rpm, reacts 12h, reaction terminates to obtain leaching slurry.
(2) NaOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 9.8, obtains reaction slurry；It will
Gained reaction slurry directly filters, and obtains the enrichment slag rich in manganese and leachate containing lithium.
(3) it is slowly added to Na into leachate containing lithium obtained by step (2)2CO3Solid particle, machinery stirs under the conditions of 87 DEG C
Reaction 4.3h is mixed, acquisition lithium carbonate product is separated by filtration.The sinker tail washings being separated by filtration is adjusted to acidic materials
After acidity in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
97.63%, the presence of manganese, aluminium plasma is not detected in leachate；ICP will be utilized after the washing of gained lithium carbonate product, drying
The content for measuring wherein lithium, calculate lithium carbonate product purity is 99.14%.In the present embodiment, the extraction of lithium is selectively
99.85%, the single-trial extraction rate of lithium is 93.72%, and by using circulate operation, the comprehensive recovery of lithium is 99.93%.
Embodiment 4
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) by 600 DEG C, the persulfuric acid of 15wt.% is added in the lithium nickelate full battery powder of removal aluminium foil after roasting 3h in advance
In ammonium salt solution, raw material slurry is made, and be preheated to 100 DEG C, solid-to-liquid ratio 15g/L；Matched raw material slurry is placed in atmospheric closed
In reactor, Leach reaction is carried out, ensures positive electrode even suspension in solution using mechanical agitation, speed of agitator
450rpm, reacts 2.0h, and reaction terminates to obtain leaching slurry.
(2) ammonium hydroxide is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 8.0, obtains reaction slurry；It will
Gained reaction slurry directly filters, and obtains the enrichment slag rich in nickel and leachate containing lithium.(3) are adopted to soak containing lithium to obtained by step (2)
Go out and is slowly added to Na in liquid2CO3Solid particle, mechanic whirl-nett reaction 2.8h under the conditions of 93 DEG C, is separated by filtration acquisition lithium carbonate
Product.The Leach reaction system of the sinker tail washings being separated by filtration return to step (1) after being adjusted to acidity with acidic materials
In, realization recycles, and ensures three-waste free discharge.
In the present embodiment, with ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
95.89%, nickel ion content is 0.52mg/L in leachate, and the presence of aluminium, copper plasma is not detected；Gained lithium carbonate is produced
Product washing, it is dry after the content of wherein lithium is measured using ICP, calculate lithium carbonate product purity is 99.08%.The present embodiment
In, the extraction of lithium is selectively 99.56%, and the single-trial extraction rate of lithium is 92.05%, by using circulate operation, the synthesis of lithium
The rate of recovery is 99.97%.
Embodiment 5
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) perchloric acid solution of 15wt.% is added in the NCM111 positive mixs of removal aluminium foil after being roasted in advance at 500 DEG C
In, raw material slurry is made, and be preheated to 65 DEG C, solid-to-liquid ratio 15g/L；Matched raw material slurry is placed in atmospheric closed reactor
It is interior, Leach reaction is carried out, ensures positive electrode even suspension in solution using mechanical agitation, speed of agitator 350rpm, reaction
10.5h, reaction terminate to obtain leaching slurry.
(2) KOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 9.6, obtains reaction slurry；By institute
It obtains reaction slurry directly to filter, obtains the enrichment slag rich in nickel cobalt manganese and leachate containing lithium.
(3) it is slowly added to K into leachate containing lithium obtained by step (2)2CO3Solid particle, mechanical agitation under the conditions of 91 DEG C
3.4h is reacted, acquisition lithium carbonate product is separated by filtration.The sinker tail washings being separated by filtration is being adjusted to acid with acidic materials
After property in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
97.64%, nickel ion and aluminium composition are respectively 0.14 and 0.09mg/L in leachate, and cobalt, manganese plasma is not detected
In the presence of；The content of wherein lithium will be measured after the washing of gained lithium carbonate product, drying using ICP, calculates to obtain lithium carbonate product purity
It is 98.95%.In the present embodiment, the extraction of lithium is selectively 99.28%, and the single-trial extraction rate of lithium is 93.73%, by using
The comprehensive recovery of circulate operation, lithium is 99.68%.
Embodiment 6
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) by advance in KOH solution alkali leaching removal aluminium foil NCM811 positive mixs be added 20wt.% potassium permanganate
In solution, raw material slurry is made, and be preheated to 80 DEG C, solid-to-liquid ratio 20g/L；Matched raw material slurry is placed in atmospheric closed reaction
In device, Leach reaction is carried out, ensures positive electrode even suspension in solution using mechanical agitation, speed of agitator 380rpm, instead
7.5h, reaction is answered to terminate to obtain leaching slurry.
(2) KOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 10.6, obtains reaction slurry；It will
Gained reaction slurry directly filters, and obtains the enrichment slag rich in nickel cobalt manganese and leachate containing lithium.
(3) it is slowly added to K into leachate containing lithium obtained by step (2)2CO3Solid particle, mechanical agitation under the conditions of 85 DEG C
6h is reacted, lithium carbonate product is obtained through being separated by solid-liquid separation.It is separated by solid-liquid separation obtained sinker tail washings and is being adjusted to acidity with acidic materials
Afterwards in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
98.15%, the presence of cobalt, nickel, manganese, aluminium, copper, iron plasma is not detected in leachate；By the washing of gained lithium carbonate product, do
The content for measuring wherein lithium after dry using ICP, calculate lithium carbonate product purity is 99.62%.In the present embodiment, the extraction of lithium
Selectivity is 99.09%, and the single-trial extraction rate of lithium is 94.22%, and by using circulate operation, the comprehensive recovery of lithium is
99.89%.
Embodiment 7
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) Fe (III)-oxalic acid of the NCA111 powders addition 20wt.% of removal aluminium foil is molten after being roasted in advance at 500 DEG C
In liquid, raw material slurry is made, and be preheated to 70 DEG C, solid-to-liquid ratio 5g/L；Matched raw material slurry is placed in normal pressure open reactor
It is interior, Leach reaction is carried out, ensures positive electrode even suspension in solution using mechanical agitation, speed of agitator 320rpm, reaction
8h, to the slow moisturizing of system to make up evaporation loss in reaction process, reaction terminates to obtain leaching slurry.
(2) NaOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 10.2, obtains reaction slurry；It will
Gained reaction slurry directly filters, and obtains the enrichment slag rich in nickel cobalt aluminium and leachate containing lithium.
(3) it is slowly added to Na into leachate containing lithium obtained by step (2)2CO3Solid particle, machinery stirs under the conditions of 95 DEG C
Reaction 2h is mixed, lithium carbonate product is obtained through being separated by solid-liquid separation.It is separated by solid-liquid separation obtained sinker tail washings and is being adjusted to acid with acidic materials
After property in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
97.93%, the presence of cobalt, nickel, aluminium plasma is not detected in leachate；It will be utilized after the washing of gained lithium carbonate product, drying
ICP measures the content of wherein lithium, calculate lithium carbonate product purity is 98.46%.In the present embodiment, the extraction of lithium is selectively
99.67%, the single-trial extraction rate of lithium is 94.01%, and by using circulate operation, the comprehensive recovery of lithium is 99.35%.
Embodiment 8
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) by advance in KOH solution alkali leaching removal aluminium foil NCM811 positive mixs be added 20wt.% potassium permanganate
In solution, raw material slurry is made, and be preheated to 25 DEG C, solid-to-liquid ratio 20g/L；Matched raw material slurry is placed in atmospheric closed reaction
In device, Leach reaction is carried out, ensures positive electrode even suspension in solution using mechanical agitation, speed of agitator 380rpm, instead
48h, reaction is answered to terminate to obtain leaching slurry.
(2) KOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 13, obtains reaction slurry；By institute
It obtains reaction slurry directly to filter, obtains the enrichment slag rich in nickel cobalt manganese and leachate containing lithium.
(3) it is slowly added to K into leachate containing lithium obtained by step (2)2CO3Solid particle, mechanical agitation under the conditions of 80 DEG C
1h is reacted, lithium carbonate product is obtained through being separated by solid-liquid separation.It is separated by solid-liquid separation obtained sinker tail washings and is being adjusted to acidity with acidic materials
Afterwards in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
95.69%, the presence of cobalt, nickel, manganese, aluminium, copper, iron plasma is not detected in leachate；By the washing of gained lithium carbonate product, do
The content for measuring wherein lithium after dry using ICP, calculate lithium carbonate product purity is 98.76%.In the present embodiment, the extraction of lithium
Selectivity is 99.19%, and the single-trial extraction rate of lithium is 91.86%, and by using circulate operation, the comprehensive recovery of lithium is
99.28%.
Embodiment 9
The present embodiment provides a kind of method selectively carrying lithium from waste material containing lithium battery, specific method is：
(1) Fe (III)-oxalic acid of the NCA111 powders addition 20wt.% of removal aluminium foil is molten after being roasted in advance at 500 DEG C
In liquid, raw material slurry is made, and be preheated to 200 DEG C, solid-to-liquid ratio 5g/L；Matched raw material slurry is placed in normal pressure open reactor
It is interior, Leach reaction is carried out, ensures positive electrode even suspension in solution using mechanical agitation, speed of agitator 320rpm, reaction
0.5h, to the slow moisturizing of system to make up evaporation loss in reaction process, reaction terminates to obtain leaching slurry.
(2) NaOH is added into leaching slurry obtained by step (1), pH value of solution is adjusted to 7, obtains reaction slurry；By institute
It obtains reaction slurry directly to filter, obtains the enrichment slag rich in nickel cobalt aluminium and leachate containing lithium.
(3) it is slowly added to Na into leachate containing lithium obtained by step (2)2CO3Solid particle, machinery stirs under the conditions of 25 DEG C
Reaction 10h is mixed, lithium carbonate product is obtained through being separated by solid-liquid separation.It is separated by solid-liquid separation obtained sinker tail washings and is being adjusted to acid with acidic materials
After property in the Leach reaction system of return to step (1), realization recycles, and ensures three-waste free discharge.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
96.43%, the presence of cobalt, nickel, aluminium plasma is not detected in leachate；It will be utilized after the washing of gained lithium carbonate product, drying
ICP measures the content of wherein lithium, calculate lithium carbonate product purity is 98.16%.In the present embodiment, the extraction of lithium is selectively
99.51%, the single-trial extraction rate of lithium is 36.42%, and by using circulate operation, the comprehensive recovery of lithium is 76.43%.
Embodiment 10
A kind of method selectively carrying lithium from waste material containing lithium battery of this implementation offer, specific method reference embodiment 4,
Difference lies in step (1), the preheating temperature of raw material slurry is 150 DEG C, and the time of Leach reaction is 1h；In step (3), sink
The lithium reaction time is 1h.
In the present embodiment, with ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
98.47%, nickel ion content is 0.41mg/L in leachate, and the presence of aluminium, copper plasma is not detected；Gained lithium carbonate is produced
Product washing, it is dry after the content of wherein lithium is measured using ICP, calculate lithium carbonate product purity is 99.08%.The present embodiment
In, the extraction of lithium is selectively 99.82%, and the single-trial extraction rate of lithium is 94.53%, by using circulate operation, the synthesis of lithium
The rate of recovery is 99.92%.
Embodiment 11
The present embodiment provides a kind of methods selectively carrying lithium from waste material containing lithium battery, and specific method is with reference to embodiment
3, difference lies in step (1), the preheating temperature of raw material slurry is 50 DEG C.
In the present embodiment, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
95.86%, the presence of manganese, aluminium plasma is not detected in leachate；ICP will be utilized after the washing of gained lithium carbonate product, drying
The content for measuring wherein lithium, calculate lithium carbonate product purity is 99.18%.In the present embodiment, the extraction of lithium is selectively
99.83%, the single-trial extraction rate of lithium is 92.03%, and by using circulate operation, the comprehensive recovery of lithium is 99.75%.
Embodiment 12
The present embodiment provides a kind of methods selectively carrying lithium from waste material containing lithium battery, and specific method is with reference to embodiment
1, difference lies in step (1), pretreated method is first to carry out Mechanical Crushing, then carries out gravity treatment, roasts again later, alkali
Leaching.
In the present embodiment, each metal element content in leachate containing lithium is measured using ICP, test result shows lithium leaching rate
Up to 97.28%, nickel, aluminium element content are respectively 0.16 and 0.08mg/L in leachate, cobalt are not detected, manganese element exists；It will
The washing of gained lithium carbonate product, it is dry after the content of wherein lithium is measured using ICP, calculate lithium carbonate product purity is
99.51%.In the present embodiment, the extraction of lithium is selectively 99.45%, and the single-trial extraction rate of lithium is 93.39%, by using following
Ring operates, and the comprehensive recovery of lithium is 99.96%.
Comparative example 1
For the specific method of this comparative example with reference to embodiment 3, difference lies in step (2), adjust the pH to 5 for leaching slurry.
In this comparative example, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
97.75%, the presence of manganese, aluminium plasma is not detected in leachate；ICP will be utilized after the washing of gained lithium carbonate product, drying
The content for measuring wherein lithium, calculate lithium carbonate product purity is 99.06%.In this comparative example, the extraction of lithium is selectively
99.81%, the single-trial extraction rate of lithium is 28.41%, and by using circulate operation, the comprehensive recovery of lithium is 46.19%.
Comparative example 2
The specific method of this comparative example is with reference to embodiment 2, and difference lies in step (1), not to cobalt acid lithium full battery powder
The pretreatment that aluminium foil is removed after 500 DEG C of roastings of progress, is directly added 20wt.% by not pretreated cobalt acid lithium full battery powder
Fenton solution in, be made raw material slurry.
In this comparative example, using ICP measure leachate containing lithium in each metal element content, calculate lithium dissolution rate reaches
95.69%, aluminium composition is up to 80mg/L in leachate；After the washing of gained lithium carbonate product, drying it will be measured using ICP
The content of middle lithium, calculate lithium carbonate product purity be 99.72%.In this comparative example, the extraction of lithium is selectively 40.83%,
The single-trial extraction rate of lithium is 89.17%, and by using circulate operation, the comprehensive recovery of lithium is 92.15%.
Based on the above embodiments with comparative example it is found that invention offer is selectively carried from waste material containing lithium battery
There is the method for lithium broad applicability, the selectivity that can be used for multiple battery waste material to put forward lithium process；Flow is short, easy to operate, instead
Mild condition is answered, reaction raw materials are of low cost, nontoxic, and ammonium acetate is simple, convenient for processing；It realizes in medium and follows
Ring greatly reduces the consumption of reaction reagent, and whole flow process is without waste water, exhaust gas or waste sludge discharge；It realizes and contains lithium battery
The highly selective recycling of lithium resource in waste material.Comparative example does not have scheme using the present invention, thus can not obtain the effect of the present invention
Fruit.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of method carrying lithium from waste material containing lithium battery, which is characterized in that described method includes following steps：
(1) pretreated waste material containing lithium battery is mixed with oxide water solution, obtained raw material slurry leach anti-
It answers, obtains leaching slurry after reaction；
(2) regulating step (1) pH to 7-13 for leaching slurry, is separated by solid-liquid separation obtained reaction slurry, consolidate
Body slag and scavenging solution containing lithium；
(3) carbonate is added into scavenging solution containing lithium described in step (2), carries out sinker reaction, is separated by solid-liquid separation after reaction and obtains carbon
Sour lithium product and sinker tail washings, the sinker tail washings is after being adjusted to acidity in the Leach reaction system of return to step (1).
2. according to the method described in claim 1, it is characterized in that, in step (1), the pretreatment includes Mechanical Crushing, ball
Mill, gravity treatment, magnetic separation, mechanochemistry processing, organic solvent dissolving, roasting or alkali leaching in any one or at least two group
It closes, the combination that preferably Mechanical Crushing, gravity treatment, roasting and alkali soak.
3. method according to claim 1 or 2, which is characterized in that in step (1), the waste material containing lithium battery includes cobalt
Sour lithium, lithium nickelate, LiMn2O4, lithium nickel cobalt dioxide, nickel ion doped, cobalt manganic acid lithium, nickel-cobalt-manganese ternary, nickel cobalt aluminium ternary, lithium alloys
In cathode, lithium titanate anode or graphite cathode containing lithium any one or at least two combination；
Preferably, in step (1), the waste material containing lithium battery comes from what waste and old lithium ion battery obtained after discharging and being crushed
The cathode that positive electrode, the waste and old lithium ion battery obtained after full battery powder, waste and old lithium ion battery dismantling obtains after disassembling
In the defect ware waste material generated in the positive and negative anodes leftover pieces or Production Process of Lithium Battery that are generated in material, Production Process of Lithium Battery
Any one or at least two combination.
4. according to claim 1-3 any one of them methods, which is characterized in that in step (1), the oxide water solution is
Perchlorate aqueous solution, permanganate water solution, ferrate aqueous solution, Fenton reagent aqueous solution, Fenton-type reagent aqueous solution,
In persulfate aqueous solution, ozone water solution or aqueous hydrogen peroxide solution any one or at least two combination；
Preferably, contain activated carbon in the ozone water solution.
5. according to claim 1-4 any one of them methods, which is characterized in that in step (1), further include：It is being leached
Before reaction, raw material slurry is preheated；
Preferably, it is 25-200 DEG C that the raw material slurry, which is preheated to temperature, preferably 50-150 DEG C, further preferably 60-100
℃；
Preferably, in step (1), the Leach reaction carries out in the reactor；
Preferably, the reactor is open reactor or closed reactor, preferably atmospheric closed reactor；
Preferably, in step (1), the Leach reaction is with stirring；
Preferably, it is described stirring be magnetic agitation, mechanical agitation or Gas Stirring in any one or at least two combination,
Preferably mechanical agitation；
Preferably, in step (1), the time of the Leach reaction is 0.5-48h, preferably 1-12h, further preferably 2-
12h。
6. according to claim 1-5 any one of them methods, which is characterized in that in step (2), regulating step (1) described leaching
Go out the pH to 8-11 of slurry；
Preferably, in step (2), with alkaline matter regulating step (1) pH for leaching slurry；
Preferably, the alkaline matter includes any one in sodium hydroxide, potassium hydroxide, ammonium hydroxide or ammonium salt or at least two
Combination；
Preferably, described to be separated by solid-liquid separation to be separated by filtration and/or centrifuging in step (2), preferably it is separated by filtration.
7. according to claim 1-6 any one of them methods, which is characterized in that in step (3), the carbonate includes carbonic acid
Sodium and/or potassium carbonate, preferably sodium carbonate.
8. according to claim 1-7 any one of them methods, which is characterized in that in step (3), the temperature of the sinker reaction
In 25 DEG C or more, preferably 80-100 DEG C；
Preferably, in step (3), the time of the sinker reaction is 1-10h, preferably 2-6h；
Preferably, described to be separated by solid-liquid separation to be separated by filtration and/or centrifuging in step (3), preferably it is separated by filtration.
9. according to claim 1-8 any one of them methods, which is characterized in that in step (3), sinker is adjusted with acidic materials
The acid-base property of tail washings；
Preferably, the acidic materials include in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or strong acid weak base salt any one or at least
Two kinds of combination.
10. according to claim 1-9 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) pretreated waste material containing lithium battery is mixed with oxide water solution, obtains raw material slurry, raw material slurry is preheated
To 60-100 DEG C, it is subsequently placed in atmospheric closed reactor, Leach reaction, reaction time 2- are carried out under mechanical agitation
12h obtains leaching slurry after reaction；Wherein, the pretreatment is the combination that Mechanical Crushing, gravity treatment, roasting and alkali soak；
(2) alkaline matter regulating step (1) pH to 8-11 for leaching slurry is used, obtained reaction slurry is filtered point
From obtaining solid slag and scavenging solution containing lithium；
(3) sodium carbonate is added into scavenging solution containing lithium described in step (2), sinker reaction, reaction time is carried out at 80-100 DEG C
For 2-6h, it is separated by filtration to obtain lithium carbonate product and sinker tail washings after reaction, the sinker tail washings is adjusted to acidic materials
After acidity in the Leach reaction system of return to step (1).
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| CN109439914A (en) * | 2019-01-08 | 2019-03-08 | 安徽工业大学 | A method of the Selective Separation lithium from waste lithium ion cell anode material extract |
| CN109852807A (en) * | 2019-03-18 | 2019-06-07 | 中国科学院过程工程研究所 | A kind of oxidation treatment method of waste and old lithium ion battery |
| CN111549229A (en) * | 2020-05-11 | 2020-08-18 | 赣州有色冶金研究所 | Method for extracting lithium from positive electrode material of waste lithium ion battery through pre-reduction preferential dissolution |
| CN111621643A (en) * | 2020-05-29 | 2020-09-04 | 江苏大学 | Method for selectively extracting lithium from waste lithium battery powder |
| WO2022127117A1 (en) * | 2020-12-15 | 2022-06-23 | 中南大学 | Method for treating positive electrode material of waste lithium battery |
| CN112952230A (en) * | 2021-03-01 | 2021-06-11 | 芜湖天弋能源科技有限公司 | Recovery method of waste lithium ion battery |
| CN113584309A (en) * | 2021-07-05 | 2021-11-02 | 广东佳纳能源科技有限公司 | Method for separating manganese in ternary lithium ion battery anode leachate |
| CN113584312A (en) * | 2021-07-28 | 2021-11-02 | 南昌航空大学 | Method for preferentially extracting lithium from anode plate of waste lithium battery in electrochemistry manner |
| CN114606398A (en) * | 2022-03-22 | 2022-06-10 | 昆明理工大学 | Method for recovering lithium from leaching waste liquid of waste lithium ion battery anode material |
| CN114606398B (en) * | 2022-03-22 | 2023-09-08 | 昆明理工大学 | Method for recycling lithium from waste lithium ion battery anode material leaching waste liquid |
| CN114682191A (en) * | 2022-05-10 | 2022-07-01 | 西安西热锅炉环保工程有限公司 | Equipment and method for preparing lithium carbonate by continuously recycling waste lithium batteries |
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