CN108486378A - A kind of processing method of the leachate of waste material containing lithium electrode - Google Patents
A kind of processing method of the leachate of waste material containing lithium electrode Download PDFInfo
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- CN108486378A CN108486378A CN201810208777.5A CN201810208777A CN108486378A CN 108486378 A CN108486378 A CN 108486378A CN 201810208777 A CN201810208777 A CN 201810208777A CN 108486378 A CN108486378 A CN 108486378A
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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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- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention provides a kind of processing methods of the leachate of waste material containing lithium electrode.It the described method comprises the following steps：(1) electrochemical treatments are carried out to containing lithium electrode waste material leachate, obtains primary purification liquid, adjusts the pH to 7 13 of the primary purification liquid, be separated by solid-liquid separation later, obtain double purification liquid；(2) carbonate is added into step (1) the double purification liquid, carries out sinker reaction, is separated by solid-liquid separation after reaction, obtains lithium carbonate product.Method provided by the invention is easy to operate, reaction process controllable precise；It can be operated with whole process low-temperature atmosphere-pressure, whole flow process is discharged without " three wastes "；The consumption of alkaline matter is greatly reduced, overall cost is cheaper, and for the recycling selectivity and single-trial extraction rate of lithium up to 95% or more, gained lithium carbonate product purity reaches battery-level lithium carbonate requirement；In addition the high-valued conversion of short distance of other metal components in waste material containing lithium electrode is also achieved.
Description
Technical field
The present invention relates to the recycling fields of waste and old lithium ion battery, and in particular to a kind of leaching of waste material containing lithium electrode
The processing method of liquid.
Background technology
Lithium ion battery because with energy density height, light weight, have extended cycle life, the outstanding advantages such as memory-less effect it is wide
It is general to be used for the fields such as 3C digital products and electric vehicle, energy storage.Adjoint therewith, the generation of a large amount of waste and old lithium ion batteries is
Stern challenge is proposed to China or even the processing of global electron wastes and environmental protection.One side applying waste lithium ionic electricity
Containing harmful constituents such as toxic inflammable electrolyte, heavy metals in pond, if serious water body and soil pollution can be caused by dealing with improperly,
Even cause the safety accidents such as fire, explosion；Contain a large amount of lithium, cobalt, nickel, manganese, copper, aluminium, iron in another aspect old and useless battery
Equal metals resources not only have considerable economic value, but also can be largely if the high efficiente callback of said components can be realized
Upper alleviation China short predicament in the resources such as cobalt, lithium at present.
Currently, the high efficiente callback for focusing on valuable metal element in electrode material of waste and old lithium ion battery recycling.It is logical
It is often to carry out Mechanical Crushing and screen to detach to obtain electrode active material powder after old and useless battery electric discharge, dismantling, powder is through acid
Leachate is obtained after leaching, then through adjusting the processes such as acid, filtering, sinker, washing, drying finally to obtain lithium carbonate product and respective electrode
The persursor material of material.Above process technical principle is simple, easy to operate, it has also become waste and old lithium ion battery recycling at present is normal
Operational means is advised, however is cleaned the stage in the later separation of leachate, is easy in the process for adjusting acid to prepare hydroxide precursor
Middle formation colloid hinders separation of solid and liquid process to carry out, while the formation of hydroxide can be more tight to lithium ion generation in solution
The package of weight and absorption, in turn result in a large amount of entrainment loss of lithium ion, cause the recycled in its entirety rate of valuable metal element not high.
The processes such as the purification and separation of leachate are changed to crack above-mentioned technical barrier, many researchers and enterprise
Into research, series of optimum method is proposed.
CN106191445A proposes a kind of separation method of lithium ion in lithium ion battery leachate.It is by lithium-ion electric
After pond leachate mixes with acid main extractant, the agent of ferric salt solution auxiliary extraction and hydrochloric acid solution and adjusts pH value of solution,
It is extracted under acid condition, lithium ion is merged at after complex compound with main extractant with auxiliary extraction dosage form, to be contained
The balance water phase of lithium ion.This method although in recyclable leachate 99% or more lithium ion, processing capacity is too low,
And contain main extractant and auxiliary extraction agent in system simultaneously, the separation of extractant and cycle as its further genralrlization bottleneck
Place.
CN107117661A proposes that nickel cobalt manganese prepares ternary hydroxide in the waste and old lithium ion battery using liquid phase method recycling
The method of object is that waste and old lithium ion battery dismantling, broken, screening are obtained electrode active material powder, and powder is through pulp, acidleach
Leachate is obtained, leachate is incorporated nickel sulfate and cobaltous sulfate crystal into filtrate after extraction copper removal, the precipitation method remove ferro-aluminum, and
Sodium hydroxide is added simultaneously and ammonium hydroxide is precipitated, precipitation finally prepares nickel-cobalt-manganese ternary hydroxide through being filtered, washed, drying
Object presoma.This method realizes effectively removing for copper in leachate although with extraction, but not inherently to routine
Operating process carries out any optimization operation.
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 leachate pH, greatly reduces lithium concentration in leachate, 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.
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, a kind of easy to operate, pollution-free, place of the leachate of waste material containing lithium electrode of the recycling high selectivity of lithium is developed
Reason method has important meaning in this field.
Invention content
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of waste materials containing lithium electrode to leach
The processing method of liquid.Method provided by the invention utilizes electrochemical method, a step to realize valuable metal member in waste material containing lithium electrode
The leaching of element and selective removal, then by adjusting the techniques such as acid, sinker to realize the selective recovery of lithium resource, not only flow is short,
It is easy to operate, it is of low cost, and the selectivity of the recycling with very high lithium and lithium carbonate product purity.
In order to achieve the above object, the present invention uses following technical scheme：
The present invention provides a kind of processing method of the leachate of waste material containing lithium electrode, the described method comprises the following steps：
(1) electrochemical treatments are carried out to containing lithium electrode waste material leachate, obtains primary purification liquid, adjusts the primary purification
The pH to 7-13 of liquid, is separated by solid-liquid separation later, obtains double purification liquid；
(2) carbonate is added into step (1) the double purification liquid, carries out sinker reaction, is separated by solid-liquid separation, obtains after reaction
To lithium carbonate product.
In the present invention, step (1) adjusts the pH to 7-13 of the primary purification liquid, for example, 7.0,8.0,8.4,9.1,9.6,
10.2,10.5,11.0,12.5 or 13 etc., it is not limited to cited numerical value, other interior unrequited numbers of the numberical range
It is worth equally applicable.
Method provided by the invention realizes a step of other valuable metal elements in addition to lithium by electrochemical process for treating
Removal, greatly reduces the consumption of alkaline matter.In electrochemical treatment process, electrode applies electrochemistry in the reaction system
, other metals in addition to lithium can be deposited in the form of metal simple-substance, alloy or metal oxide electrode surface (
High purity metal simple substance or alloy are obtained on cathode, and metal oxide is obtained on anode), and lithium is present in scavenging solution.This
In invention, because the raw material used is the leachate of the waste material containing lithium electrode, compared to the pulp product of the waste material containing lithium electrode, leach
Impurity content in liquid is higher, therefore after electrochemical treatments, and there is also some impurity in primary purification liquid, will also be primary
Scavenging solution tune pH to 7-13 carries out deep impurity-removing, just the purity of finally obtained lithium carbonate product can be made sufficiently high.
Method provided by the invention, has not only been prepared lithium carbonate, realizes the recycling of lithium, and collection step (1)
In be deposited on the deposit of electrode surface, the high-valued conversion of other metal components in waste material containing lithium electrode may be implemented.This hair
The method of bright offer is easy to operate, and the selectivity of the recycling with very high lithium and lithium carbonate product purity.
Method provided by the invention needs the oxidation-reduction potential by controlling electrochemical treatments to prevent lithium to be deposited on electricity
The loss of lithium is caused on extremely.
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 electrochemical treatments are electrolysis.In electrolytic process,
The deposition of the dissolution and dissolution metal of a part of metal in the product after pulp on the electrode is realized simultaneously, can make this hair
The method of bright offer reaches better effect.
Preferably, in step (1), adjust the pH to 8-11 of the primary purification liquid, for example, 8.0,8.4,9.1,9.6,
10.2,10.5 or 11.0 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally suitable
With.In the present invention, the pH of primary purification liquid is adjusted to 8-11, benefit is to be more conducive to micro valuable metal in removal leachate
Ion, while Al (OH) will not be made3It re-dissolves to form meta-aluminic acid root.
As currently preferred technical solution, in step (1), the leachate of waste material containing lithium electrode is applying waste lithium ionic
Cell positive material leachate.
Preferably, in the waste lithium ion cell anode material extract, waste lithium ion cell anode material includes
Waste and old cobalt acid lithium (LiCoO2) material, waste and old lithium nickelate (LiNiO2) material, waste lithium manganese oxide (LiMn2O4) material, waste and old phosphoric acid
Iron lithium (LiFePO4) material or waste and old ternary (LiNixCoyMn1-x-yO2) in material any one or at least two combination,
It is typical but be non-limiting combination and have：The combination of waste and old cobalt acid lithium waste material and waste and old lithium nickelate waste material, waste lithium manganese oxide waste material
With the combination of waste lithium iron phosphate waste material, the combination etc. of waste lithium iron phosphate material and waste and old ternary material.
Preferably, in the leachate of waste material containing lithium electrode described in step (1), waste material containing lithium electrode comes from applying waste lithium ionic electricity
The lithium that contains of pond and/or cell production companies produces waste material.In the present invention, the waste and old lithium ion battery and/or battery production factory
The production waste material containing lithium of family refers to that can contain lithium electrode waste material to can come from waste and old lithium ion battery, can be from battery production
Producer produces waste material containing lithium, and the lithium that contains that could also be from waste and old lithium ion battery and cell production companies produces waste material.
Preferably, in step (1), the preparation method of the leachate of waste material containing lithium electrode includes the following steps：Containing lithium electricity
Pole waste material is separated by solid-liquid separation after being leached in leaching bottom liquid and removes solid, obtains leachate.
Preferably, in the preparation method of the leachate of waste material containing lithium electrode, leach bottom liquid include acid solution, alkalinity it is molten
In liquid or biological leaching liquor any one or at least two combination, it is typical but be non-limiting combination and have：Acid solution
With the combination of alkaline solution, the combination of acid solution and biology leaching liquor, the combination etc. of alkaline solution and biological leaching liquor, preferably
For acid solution.
Preferably, in the preparation method of the leachate of waste material containing lithium electrode, the method for separation of solid and liquid be separated by filtration and/
Or centrifuge, preferably it is separated by filtration.In the present invention, it is described be separated by filtration and/or centrifuge refer to can be filtering point
From, or it centrifuges, can also be the combination for being separated by filtration and centrifuging.
Preferably, further include being carried out in advance to containing lithium electrode waste material in the preparation method of the leachate of waste material containing lithium electrode
Processing.After pretreatment, waste material containing lithium electrode is easier to be leached.
Preferably, the pretreatment includes Mechanical Crushing, ball milling, sorting, mechanochemistry processing, organic solvent extraction, heat
In processing or alkali leaching dealuminzation any one or at least two combination, it is typical but be non-limiting combination and have：Mechanical Crushing
With the combination of ball milling, sorts and the combination of mechanochemistry processing, organic solvent extraction, heat treatment and alkali soak the combination etc. of dealuminzation.
As currently preferred technical solution, in step (1), the electrochemical treatments carry out in a cell.
Preferably, the electrolytic cell is open electrolytic cell or closed cell, preferably closed cell.Use closed electricity
When solving slot, the liquid phase substance in reaction system will not be caused to volatilize because of heating, because adding solvent without midway, improved
The operability of the method for the invention.
Preferably, the closed cell is atmospheric closed electrolytic cell.
As currently preferred technical solution, in step (1), the time of the electrochemical treatments is 0.5-72h, such as
0.5h, 2h, 2.8h, 3.4h, 4.2h, 5.1h, 6.3h, 7.2h, 8.0h, 10h, 20h, 30h, 40h, 50h, 60h, 70h or 72h
Deng, it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable, preferably 2-8h.
Preferably, in step (1), further include：Before carrying out electrochemical treatments, first to the leachate of waste material containing lithium electrode
It is preheated.
Preferably, the temperature of the preheating is at 25 DEG C or more, for example, 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 64 DEG C, 68
DEG C, 72 DEG C, 75 DEG C, 79 DEG C, 83 DEG C, 88 DEG C, 94 DEG C, 97 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C or 200 DEG C etc..
Preferably, the temperature of the preheating be 40-200 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C, 64 DEG C, 68 DEG C, 72 DEG C, 75
DEG C, 79 DEG C, 83 DEG C, 88 DEG C, 94 DEG C, 97 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C or 200 DEG C etc., it is not limited to listed
The numerical value of act, other interior unrequited numerical value of the numberical range are equally applicable, preferably 60-100 DEG C.
As currently preferred technical solution, in step (1), the current density of the electrochemical treatments is in 5A/m2With
On, such as 50A/m2、100A/m2、127A/m2、136A/m2、140A/m2、182A/m2、226A/m2、300A/m2、387A/m2、
460A/m2、532A/m2、643A/m2、742A/m2、800A/m2、1000A/m2、1600A/m2Or 2000A/m2Deng preferably 50-
2000A/m2, further preferably 100-800A/m2.Because also needing to adjust pH progress deeply after electrochemical treatments in the present invention
Degree removal of impurities will can not detach net impurity and remove, so without applying very high electricity in electrochemical treatments in electrochemical treatments
Current density.
Preferably, in step (1), with stirring during the electrochemical treatments.
Preferably, the stirring is any one in magnetic agitation, mechanical agitation or Gas Stirring or at least two
Combination, preferably mechanical agitation.
As currently preferred technical solution, in step (1), the electrode used in the electrochemical treatments is stainless steel
It is any one in electrode, nickel electrode, copper electrode, Ti electrode, platinum electrode, gold electrode, pure iron electrode, cast iron electrode, carbon or glass carbon
Kind or at least two combination, it is typical but be non-limiting combination and have：The combination of stainless steel electrode and carbon electrode, copper electrode and
The combination etc. of the combination of glass-carbon electrode, carbon electrode and Ti electrode, preferably carbon electrode.
Preferably, in step (1), the shape of the anode used in the electrochemical treatments is plate and/or rodlike.This hair
In bright, the plate and/or it is rodlike refer to the anode in the electrode used in electrochemical treatments shape can be plate, also may be used
With rodlike, it can also be plate and rodlike combination, i.e., use plate-shaped anode and rod anode simultaneously.
As currently preferred technical solution, in step (1), the pH of the primary purification liquid is adjusted with alkaline matter.
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 (1), 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.
Preferably, the preparation that obtained solid is used for the leachate of waste material containing lithium electrode is separated by solid-liquid separation in step (1).
As currently preferred technical solution, in step (2), the carbonate includes sodium carbonate, potassium carbonate or carbonic acid
In ammonium any one or at least two combination, it is typical but be non-limiting combination and have：The combination of sodium carbonate and potassium carbonate,
The combination of potassium carbonate and ammonium carbonate, the combination etc. of sodium carbonate, potassium carbonate and ammonium carbonate, preferably sodium carbonate.
Preferably, in step (2), the reaction temperature of sinker reaction at 25 DEG C or more, such as 25 DEG C, 50 DEG C, 57 DEG C,
63 DEG C, 38 DEG C, 75 DEG C, 80 DEG C, 84 DEG C, 86 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C, 100 DEG C or 150 DEG C etc., preferably 80-100
℃；
Preferably, in step (2), reaction time of sinker reaction is 1-10h, for example, 2.0h, 2.6h, 3.2h,
3.8h, 4.3h, 4.9h, 5.2h, 5.5h, 5.9h, 6.0h, 7h, 8h, 9h or 10 etc., it is not limited to cited numerical value, it should
Other unrequited numerical value are equally applicable in numberical range, preferably 2-6h.
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.
Preferably, the preparation that obtained liquid is used for the leachate of waste material containing lithium electrode is separated by solid-liquid separation in step (2).
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) it is filtered to remove solid after leaching pretreated waste lithium ion cell anode material in an acidic solution,
Obtain waste lithium ion cell anode material extract；After the leachate is preheated to 60-100 DEG C, it is electrolysed in atmospheric closed
With 100-800A/m in slot2Current density be electrolysed, with mechanical agitation during electrolysis, the electrode of electrolysis is carbon electricity
Pole, the shape of Anodic are plate and/or rodlike, and electrolysis time 2-8h obtains primary purification liquid, adjusted with alkaline matter
The pH to 8-11 of the primary purification liquid, is separated by filtration later, obtains double purification liquid；Primary purification liquid is separated by filtration
Solid is used for the preparation of waste lithium ion cell anode material extract；
(2) sodium carbonate is added into step (1) the double purification liquid, sinker reaction is carried out at a temperature of 80-100 DEG C,
Reaction time is 2-6h, is separated by filtration after reaction, obtains lithium carbonate product；The liquid being separated by filtration is used for applying waste lithium ionic
The preparation of cell positive material leachate.
Compared with the prior art, the present invention has the advantages that：
(1) processing method of the leachate of waste material containing lithium electrode provided by the invention is easy to operate, reaction process controllable precise；
(2) processing method of the leachate of waste material containing lithium electrode provided by the invention can be operated with whole process low-temperature atmosphere-pressure, whole
A flow is discharged without " three wastes "；
(3) processing method of the leachate of waste material containing lithium electrode provided by the invention is realized by the introducing of electrochemical treatments
The step removal of the leachate of waste material containing lithium electrode other valuable metal elements in addition to lithium, greatly reduces the consumption of alkaline matter
Amount, overall cost is cheaper, and realizes the highly selective extraction of lithium component in leachate, the recycling selectivity and list of lithium
For secondary recovery rate up to 95% or more, gained lithium carbonate product purity reaches battery-level lithium carbonate requirement；
(4) processing method of the leachate of waste material containing lithium electrode provided by the invention can not only realize that the highly selective of lithium carries
It takes, additionally it is possible to which the surface of the cathode used in electrochemical treatments obtains high purity metal simple substance or alloy, realizes and contains lithium electrode
The high-valued conversion of the short distance of other metal components in waste material.
Description of the drawings
Fig. 1 is the process flow chart of the processing method for the leachate of waste material containing lithium electrode 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 processing method of the leachate of waste material containing lithium electrode, specific method is：
(1) sulphuric leachate of cobalt acid lithium waste material is preheated to 80 DEG C to be placed in atmospheric closed electrolytic cell, is with carbon-point
Anode and cathode is electrolysed (electrochemical treatments), electrode current density 600A/m2, apply mechanical agitation, rotating speed is
500rpm reacts 5h, obtains primary purification liquid；NaOH solid particles are added into primary purification liquid, pH value of solution is adjusted to 9.5
(adjusting acid) obtains double purification liquid, a small amount of cobalt hydroxide precipitation through filtering, deposit is obtained in cathode surface, using atom
Emission spectrometer (ICP) and X-ray diffraction (XRD) analyze deposit chemical constituent and phase structure；It is obtained by filtration
Preparation (leach process) of the solid for the sulphuric leachate of cobalt acid lithium waste material；
(2) sodium carbonate solid particle is added into double purification liquid obtained by step (1), reacts 6h under the conditions of 90 DEG C, passes through
Be separated by filtration acquisition lithium carbonate, products obtained therefrom is washed, it is dry after the content of wherein lithium is measured with ICP.It is separated by filtration
Preparation (leach process) of the liquid for the sulphuric leachate of cobalt acid lithium waste material.
In the present embodiment, the sulphuric leachate of the cobalt acid lithium waste material is obtained by leaching process, and the leaching process is：
It is separated by filtration removing solid after pretreated cobalt acid lithium waste material is leached in sulfuric acid solution, obtains the sulfuric acid of cobalt acid lithium waste material
Leachate.
The technological process of the processing method of the leachate of waste material containing lithium electrode provided in this embodiment is as shown in Figure 1.
In the present embodiment, the single-trial extraction rate of lithium is 97.98%, and the recycling of lithium is selectively 99.79%, and deposit is height
Pure cobalt simple substance, the electro-deposition rate of cobalt reaches 99.42% in solution, and lithium carbonate product purity is 99.79%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 2
The present embodiment provides a kind of processing method of the leachate of waste material containing lithium electrode, specific method is：
(1) sulphuric leachate of LiMn2O4 waste material is preheated to 60 DEG C to be placed in atmospheric closed electrolytic cell, is with titanium plate
Anode is electrolysed by cathode of carbon-point, electrode current density 300A/m2, application mechanical agitation, rotating speed 700rpm, instead
8h is answered, primary purification liquid is obtained；Ammonium hydroxide is added into primary purification liquid, pH value of solution is adjusted to 8.0, secondary purifying is obtained through filtering
Change liquid, a small amount of manganous hydroxide precipitation, solid adhesion obtained in anode surface, using ICP and XRD to attachment chemical constituent and
Phase structure is analyzed；Preparation of the solid being obtained by filtration for the sulphuric leachate of LiMn2O4 waste material；
(2) 1mol/L sodium carbonate liquors are added into double purification liquid obtained by step (1), are reacted under the conditions of 85 DEG C
4.5h, is separated by filtration acquisition lithium carbonate, products obtained therefrom is washed, it is dry after the content of wherein lithium is measured with ICP；It is separated by filtration
Preparation of the obtained liquid for the sulphuric leachate of LiMn2O4 waste material.
In the present embodiment, the preparation method of the sulphuric leachate of the LiMn2O4 waste material is：By pretreated LiMn2O4
Waste material is separated by filtration removing solid after being leached in sulfuric acid solution, obtain the sulphuric leachate of LiMn2O4 waste material.
In the present embodiment, the single-trial extraction rate of lithium is 95.24%, and the recycling of lithium is selectively 99.83%, and deposit is height
Pure manganese dioxide, the conversion ratio of manganese reaches 99.38% in solution, and lithium carbonate product purity is 99.68%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 3
The present embodiment provides a kind of processing method of the leachate of waste material containing lithium electrode, specific method is：
(1) by LiNi0.5Co0.2Mn0.3O2(NCM523) the salt leachate of waste material is preheated to 90 DEG C and is placed on atmospheric closed electricity
It solves in slot, using titanium plate as anode, is electrolysed by cathode of carbon-point, electrode current density 400A/m2, apply mechanical agitation,
Rotating speed is 400rpm, reacts 8h, obtains primary purification liquid；1mol/L KOH solutions are added into primary purification liquid by pH value of solution tune
Section is 10.5, and through double purification liquid is obtained by filtration, hydroxide precipitates, and obtains deposit simultaneously in cathode and anode surface,
Gained cathode and anode surface deposit are analyzed using ICP and XRD；The solid being obtained by filtration is for NCM523 waste materials
The preparation of salt leachate；
(2) potash solid particle is added into double purification liquid obtained by step (1), reacts 4h under the conditions of 90 DEG C, passes through
It is separated by solid-liquid separation and obtains lithium carbonate, measure the content of wherein lithium after products obtained therefrom is washed, dry with ICP.It is separated by filtration to obtain
Liquid for NCM523 waste materials salt leachate preparation.
In the present embodiment, the LiNi0.5Co0.2Mn0.3O2(NCM523) preparation method of the salt leachate of waste material is：It will
NCM523 waste materials are separated by filtration removing solid after being leached in salting liquid, obtain the salt leachate of NCM523 waste materials.
In the present embodiment, the single-trial extraction rate of lithium is 98.15%, and the recycling of lithium is selectively 98.69%, cathode deposition
For high-purity nickel cobalt (alloy), anode surface attachment is high-purity manganese dioxide, the electrochemistry removal rate difference of nickel, cobalt, manganese in solution
It is 99.42,99.35 and 98.28%, lithium carbonate product purity is 99.71%, reaches battery-level lithium carbonate requirement.The present embodiment
The method alkaline matter consumption of offer is very low.
Embodiment 4
The present embodiment provides a kind of processing method of the leachate of waste material containing lithium electrode, specific method is：
(1) sulphuric leachate of cobalt acid lithium waste material is preheated to 100 DEG C to be placed in atmospheric closed electrolytic cell, is with carbon-point
Anode and cathode is electrolysed, electrode current density 800A/m2, apply mechanical agitation, rotating speed 500rpm reacts 2h, obtains
To primary purification liquid；NaOH solid particles are added into primary purification liquid, pH value of solution is adjusted to 13, secondary purifying is obtained through filtering
Change liquid, a small amount of cobalt hydroxide precipitation, deposit is obtained in cathode surface, using Atomic Emission Spectrometer AES (ICP) and X-ray diffraction
(XRD) deposit chemical constituent and phase structure are analyzed；Sulfuric acid of the solid being obtained by filtration for cobalt acid lithium waste material soaks
Go out the preparation of liquid；
(2) sodium carbonate solid particle is added into double purification liquid obtained by step (1), reacts 10h under the conditions of 80 DEG C, passes through
Be separated by filtration acquisition lithium carbonate, products obtained therefrom is washed, it is dry after the content of wherein lithium is measured with ICP.It is separated by filtration
Preparation of the liquid for the sulphuric leachate of cobalt acid lithium waste material.
In the present embodiment, the preparation method of the sulphuric leachate of the cobalt acid lithium waste material is：By pretreated cobalt acid lithium
Waste material is separated by filtration removing solid after being leached in sulfuric acid solution, obtain the sulphuric leachate of cobalt acid lithium waste material.
In the present embodiment, the single-trial extraction rate of lithium is 97.46%, and the recycling of lithium is selectively 98.95%, and deposit is height
Pure cobalt simple substance, the electro-deposition rate of cobalt reaches 99.14% in solution, and lithium carbonate product purity is 99.96%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 5
The present embodiment provides a kind of processing method of the leachate of waste material containing lithium electrode, specific method is：
(1) sulphuric leachate of LiMn2O4 waste material is preheated to 40 DEG C to be placed in atmospheric closed electrolytic cell, is with titanium plate
Anode is electrolysed by cathode of carbon-point, electrode current density 50A/m2, apply mechanical agitation, rotating speed 700rpm, reaction
72h obtains primary purification liquid；Ammonium hydroxide is added into primary purification liquid, pH value of solution is adjusted to 7.0, double purification is obtained through filtering
Liquid, a small amount of manganous hydroxide precipitation obtain solid adhesion, using ICP and XRD to attachment chemical constituent and object in anode surface
Phase structure is analyzed；Preparation of the solid being obtained by filtration for the sulphuric leachate of LiMn2O4 waste material；
(2) 1mol/L sodium carbonate liquors are added into double purification liquid obtained by step (1), react 1h under the conditions of 100 DEG C,
Be separated by filtration acquisition lithium carbonate, products obtained therefrom is washed, it is dry after the content of wherein lithium is measured with ICP；It is separated by filtration to obtain
Liquid for LiMn2O4 waste material sulphuric leachate preparation.
In the present embodiment, the preparation method of the sulphuric leachate of the LiMn2O4 waste material is：By pretreated LiMn2O4
Waste material is separated by filtration removing solid after being leached in sulfuric acid solution, obtain the sulphuric leachate of LiMn2O4 waste material.
In the present embodiment, the single-trial extraction rate of lithium is 96.13%, and the recycling of lithium is selectively 99.368%, and deposit is
High-purity manganese dioxide, the conversion ratio of manganese reaches 99.43% in solution, and lithium carbonate product purity is 99.51%, reaches LITHIUM BATTERY carbon
Sour lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 6
The present embodiment provides a kind of processing method of the leachate of waste material containing lithium electrode, specific method is：
(1) sulphuric leachate of cobalt acid lithium waste material is preheated to 200 DEG C to be placed in atmospheric closed electrolytic cell, is with carbon-point
Anode and cathode is electrolysed, electrode current density 100A/m2, apply mechanical agitation, rotating speed 500rpm reacts 8h, obtains
To primary purification liquid；NaOH solid particles are added into primary purification liquid, pH value of solution is adjusted to 11, secondary purifying is obtained through filtering
Change liquid, a small amount of cobalt hydroxide precipitation, deposit is obtained in cathode surface, using Atomic Emission Spectrometer AES (ICP) and X-ray diffraction
(XRD) deposit chemical constituent and phase structure are analyzed；Sulfuric acid of the solid being obtained by filtration for cobalt acid lithium waste material soaks
Go out the preparation of liquid；
(2) sodium carbonate solid particle is added into double purification liquid obtained by step (1), reacts 2h under the conditions of 100 DEG C, passes through
Be separated by filtration acquisition lithium carbonate, products obtained therefrom is washed, it is dry after the content of wherein lithium is measured with ICP.It is separated by filtration
Preparation of the liquid for the sulphuric leachate of cobalt acid lithium waste material.
In the present embodiment, the preparation method of the sulphuric leachate of the cobalt acid lithium waste material is：By pretreated cobalt acid lithium
Waste material is separated by filtration removing solid after being leached in sulfuric acid solution, obtain the sulphuric leachate of cobalt acid lithium waste material.
In the present embodiment, the single-trial extraction rate of lithium is 97.42%, and the recycling of lithium is selectively 98.97%, and deposit is height
Pure cobalt simple substance, the electro-deposition rate of cobalt reaches 99.92% in solution, and lithium carbonate product purity is 99.87%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 7
The present embodiment provides a kind of processing methods of the leachate of waste material containing lithium electrode, and specific method is with reference to embodiment 2, area
It is not：In step (1), electrode current density 2000A/m2, the reaction time for being electrolysed processing is 0.5h.
In the present embodiment, the single-trial extraction rate of lithium is 96.83%, and the recycling of lithium is selectively 97.64%, and deposit is height
Pure manganese dioxide, the conversion ratio of manganese reaches 97.62% in solution, and lithium carbonate product purity is 99.52%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 8
The present embodiment provides a kind of processing methods of the leachate of waste material containing lithium electrode, and specific method is with reference to embodiment 1, area
It is not：In step (1), the pH for adjusting primary purification liquid is 13.
In the present embodiment, the single-trial extraction rate of lithium is 97.88%, and the recycling of lithium is selectively 98.72%, and deposit is height
Pure cobalt simple substance, the electro-deposition rate of cobalt reaches 99.75% in solution, and lithium carbonate product purity is 99.82%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Embodiment 9
The present embodiment provides a kind of processing methods of the leachate of waste material containing lithium electrode, and specific method is with reference to embodiment 2, area
It is not：In step (1), the pH for adjusting primary purification liquid is 7.
In the present embodiment, the single-trial extraction rate of lithium is 95.36%, and the recycling of lithium is selectively 99.81%, and deposit is height
Pure manganese dioxide, the conversion ratio of manganese reaches 99.95% in solution, and lithium carbonate product purity is 99.60%, reaches LITHIUM BATTERY carbonic acid
Lithium requirement.Method alkaline matter consumption provided in this embodiment is very low.
Comparative example 1
For this comparative example with reference to embodiment 2, difference lies in step (1), ammonium hydroxide is added into primary purification liquid by pH value of solution
It adjusts to 5.
In this comparative example, the single-trial extraction rate of lithium is 95.46%, and the recycling of lithium is selectively 99.76%, deposit two
Manganese oxide, the conversion ratio of manganese reaches 99.87% in solution, and lithium carbonate product purity is 92.41%.
Based on the above embodiments with comparative example it is found that the processing method behaviour of waste material containing lithium electrode provided by the invention leachate
Make simply, to operate with whole process low-temperature atmosphere-pressure, whole flow process is discharged without " three wastes ", the recovery rate and high selectivity of lithium, gained
Lithium carbonate product purity is high.Comparative example does not have scheme using the present invention, thus can not obtain the effect of the present invention.
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 processing method of the leachate of waste material containing lithium electrode, which is characterized in that the described method comprises the following steps：
(1) electrochemical treatments are carried out to containing lithium electrode waste material leachate, obtains primary purification liquid, adjusts the primary purification liquid
PH to 7-13, is separated by solid-liquid separation later, obtains double purification liquid；
(2) carbonate is added into step (1) the double purification liquid, carries out sinker reaction, is separated by solid-liquid separation after reaction, obtains carbon
Sour lithium product.
2. processing method according to claim 1, which is characterized in that in step (1), the electrochemical treatments are electrolysis；
Preferably, in step (1), the pH to 8-11 of the primary purification liquid is adjusted.
3. processing method according to claim 1 or 2, which is characterized in that in step (1), the leaching of waste material containing lithium electrode
It is waste lithium ion cell anode material extract to go out liquid；
Preferably, in the waste lithium ion cell anode material extract, waste lithium ion cell anode material includes waste and old
Appointing in cobalt acid lithium material, waste nickel acid lithium material, waste lithium manganese oxide material, waste lithium iron phosphate material or waste and old ternary material
It anticipates a kind of or at least two combinations；
Preferably, in the leachate of waste material containing lithium electrode described in step (1), waste material containing lithium electrode comes from waste and old lithium ion battery
And/or the lithium that contains of cell production companies produces waste material；
Preferably, in step (1), the preparation method of the leachate of waste material containing lithium electrode includes the following steps：It is useless containing lithium electrode
Material is separated by solid-liquid separation after being leached in leaching bottom liquid and removes solid, obtains leachate；
Preferably, in the preparation method of the leachate of waste material containing lithium electrode, leach bottom liquid include acid solution, alkaline solution or
In biological leaching liquor any one or at least two combination, preferably acid solution；
Preferably, in the preparation method of the leachate of waste material containing lithium electrode, the method for separation of solid and liquid be separated by filtration and/or from
The heart detaches, and is preferably separated by filtration；
Preferably, further include being pre-processed to containing lithium electrode waste material in the preparation method of the leachate of waste material containing lithium electrode；
Preferably, the pretreatment includes Mechanical Crushing, ball milling, sorting, mechanochemistry processing, organic solvent extraction, heat treatment
Alkali leaching dealuminzation in any one or at least two combination.
4. according to claim 1-3 any one of them processing methods, which is characterized in that in step (1), the electrochemical treatments
It carries out in a cell；
Preferably, the electrolytic cell is open electrolytic cell or closed cell, preferably closed cell；
Preferably, the closed cell is atmospheric closed electrolytic cell.
5. according to claim 1-4 any one of them processing methods, which is characterized in that in step (1), the electrochemical treatments
Time be 0.5-72h, preferably 2-8h；
Preferably, in step (1), further include：Before carrying out electrochemical treatments, first the leachate of waste material containing lithium electrode is carried out
Preheating；
Preferably, the temperature of the preheating is at 25 DEG C or more；
Preferably, the temperature of the preheating is 40-200 DEG C, preferably 60-100 DEG C.
6. according to claim 1-5 any one of them processing methods, which is characterized in that in step (1), the electrochemical treatments
Current density in 5A/m2More than, preferably 50-2000A/m2, further preferably 100-800A/m2；
Preferably, in step (1), with stirring during the electrochemical treatments；
Preferably, it is described stirring be magnetic agitation, mechanical agitation or Gas Stirring in any one or at least two combination,
Preferably mechanical agitation.
7. according to claim 1-6 any one of them processing methods, which is characterized in that in step (1), the electrochemical treatments
The middle electrode used is stainless steel electrode, nickel electrode, copper electrode, Ti electrode, platinum electrode, gold electrode, pure iron electrode, cast iron electric
In pole, carbon or glass carbon any one or at least two combination, preferably carbon electrode；
Preferably, in step (1), the shape of the anode used in the electrochemical treatments is plate and/or rodlike.
8. according to claim 1-7 any one of them processing methods, which is characterized in that in step (1), adjusted with alkaline matter
The pH of the primary purification liquid；
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 (1), preferably it is separated by filtration；
Preferably, the preparation that obtained solid is used for the leachate of waste material containing lithium electrode is separated by solid-liquid separation in step (1).
9. according to claim 1-8 any one of them processing methods, which is characterized in that in step (2), the carbonate includes
In sodium carbonate, potassium carbonate or ammonium carbonate any one or at least two combination, preferably sodium carbonate；
Preferably, in step (2), the reaction temperature of the sinker reaction is in 25 DEG C or more, preferably 80-100 DEG C；
Preferably, in step (2), the reaction 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 (2), preferably it is separated by filtration；
Preferably, the preparation that obtained liquid is used for the leachate of waste material containing lithium electrode is separated by solid-liquid separation in step (2).
10. according to claim 1-9 any one of them processing methods, which is characterized in that the described method comprises the following steps：
(1) it is filtered to remove solid after leaching pretreated waste lithium ion cell anode material in an acidic solution, is obtained
Waste lithium ion cell anode material extract；After the leachate is preheated to 60-100 DEG C, in atmospheric closed electrolytic cell
With 100-800A/m2Current density be electrolysed, with mechanical agitation during electrolysis, the electrode of electrolysis is carbon electrode,
The shape of its Anodic is plate and/or rodlike, and electrolysis time 2-8h obtains primary purification liquid, and institute is adjusted with alkaline matter
The pH to 8-11 for stating primary purification liquid, is separated by filtration later, obtains double purification liquid；What primary purification liquid was separated by filtration consolidates
Body is used for the preparation of waste lithium ion cell anode material extract；
(2) sodium carbonate is added into step (1) the double purification liquid, sinker reaction, reaction is carried out at a temperature of 80-100 DEG C
Time is 2-6h, is separated by filtration after reaction, obtains lithium carbonate product；The liquid being separated by filtration is used for waste and old lithium ion battery
The preparation of positive electrode leachate.
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