CN110451533A - The purifying plant and method of purification of lithium salts - Google Patents
The purifying plant and method of purification of lithium salts Download PDFInfo
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- CN110451533A CN110451533A CN201810886847.2A CN201810886847A CN110451533A CN 110451533 A CN110451533 A CN 110451533A CN 201810886847 A CN201810886847 A CN 201810886847A CN 110451533 A CN110451533 A CN 110451533A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to the energy and field of material technology more particularly to the purifying plants and method of purification of a kind of lithium salts.The purifying plant includes: electrolytic cell, and the electrolytic cell includes anode material layer, and the anode material layer is used as anode, and the anode is inert electrode；Several cathodes, the cathode are waste lithium cell electrode material；Air inlet pipe, the air inlet pipe are connected to the bottom wall of the electrolytic cell or are connected to the sidewall bottom of the electrolytic cell.The purifying plant has the advantages that treatment effeciency is high.Multiple cathodes can be arranged dexterously using anode material as electrolytic cell in the purifying plant in electrolytic cell, to greatly improve recovery efficiency, it can be achieved that more lithium ion recycles in primary electrochemical reaction.
Description
Technical field
The present invention relates to the energy and field of material technology more particularly to the purifying plants and method of purification of a kind of lithium salts.
Background technique
Lithium battery is used in pacemaker earliest, later with the continuous development of science and technology, in electric vehicle, hand
There is extensive use in the fields such as machine, laptop, new-energy automobile, and lithium battery has become battery technology industry development
Mainstream.As occupation rate increases lithium battery year by year in the market, necessarily there is great promotion to the development of its vertical industry
Effect.For example the lithium salts raw material used needed for production lithium ion battery, demand will increase dramatically.
The method of purification of lithium salts is mainly realized from salt lake bittern by a series of complex technique at present, such as China
Patent CN 200910249795.9 disclose a kind of high purity lithium carbonate from salt lake bittern and other using by-product
The step of method, this method includes: that salt pan is evaporated brine separating potassium and sodium；Acidization separating boron；Precipitation method separating magnesium；Precipitation method separation
Calcium；Lithium chloride is produced；Lithium carbonate is produced, and not only processing step is more, and need to be added in above-mentioned steps various reagents (hydrochloric acid,
Ammonium hydroxide, ammonium hydrogen carbonate etc.), cause cost for purification to increase, and waste water can be generated and need secondary treatment, increases environmental pressure.
Summary of the invention
The purpose of the present invention is to provide a kind of purifying plant of lithium salts and methods of purification, to solve existing purification lithium salts side
Operating process present in method is complicated, reagent dosage is big, generates the problems such as a large amount of waste water.
First aspect, the present invention provide a kind of purifying plant of lithium salts, and the purifying plant includes:
Electrolytic cell, the electrolytic cell include anode material layer, and the anode material layer is used as anode, and the anode is
Inert electrode；
Several cathodes, the cathode are waste lithium cell electrode material；
Air inlet pipe, the air inlet pipe is connected on the bottom wall of the electrolytic cell or the sidewall bottom of the electrolytic cell.
Further, the electrolytic cell further includes the structural support layers outside the anode material layer, wherein described
Anode material layer with a thickness of 5~12mm.
Optionally, the material of the structural support layers is selected from concrete, cement, stone material, rubber or resin.
Further, the top of the electrolytic cell is equipped with sealing upper cover, and the sealing upper cover is enclosed jointly with the electrolytic cell
Conjunction forms closed cavity.
Further, reagent is additionally provided in the sealing on lid and mouth is added.
Further, the inside of the electrolytic cell is detachably arranged the waffle slab being arranged generally in a horizontal direction, institute
Waffle slab is stated using insulating materials.
Preferably, the insulating materials is ceramics.
Further, the waffle slab is horizontally disposed plate, the shape of any grid cell of the plate
Shape is rectangular or taper type；Alternatively, the waffle slab is with the arc panel for being bent upwards radian, any net of the arc panel
The shape of lattice unit is taper type.
As an implementation, the waffle slab bottom is installed with bracket, and the bracket uses insulating materials.
As an implementation, the inner wall of the electrolytic cell is equipped with the undertaking formed towards therein horizontal extension
Platform, the waffle slab are erected on the adapting table.
The second aspect, the present invention provide a kind of method of purification of lithium salts, and the method for purification is mentioned using above-mentioned lithium salts
Pure device, the method for purification the following steps are included:
Using the waste lithium cell electrode material as cathode, using the inert electrode as anode；
Electrolyte is added into the electrolytic cell, immerses the cathode and the anode in electrolyte, in applying electrical potential
Under be electrochemically reacted, obtain the solution containing lithium ion；
Open the air inlet pipe, to reaction after described in be passed through carbon dioxide in the solution containing lithium ion, obtain lithium salts
Precipitating and surplus solution.
Further, the method for purification further include: before being passed through carbon dioxide, first contain the molten of lithium ion to described
Liquid is concentrated, and the lithium concentration in the solution containing lithium ion is made to be greater than or equal to 25g/L.
Further, the method for purification further include: before being passed through carbon dioxide, first adjusting is described to contain lithium ion
Solution is to alkalinity.
Further, the solution containing lithium ion further includes at least one of nickel ion, cobalt ions, manganese ion.
Further, be electrochemically reacted applied potential be 0.2~1.5V, apply potential time be 1.5~
8h；In the method for purification, the solution containing lithium ion further include the nickel ion, the cobalt ions and the manganese from
Son when being electrochemically reacted, adjusts the potential of application, makes the lithium ion, the nickel ion, the cobalt ions, the manganese
Ion substep leaches.
Wherein, it includes any electricity in the numberical range that be electrochemically reacted applied potential, which be 0.2~1.5V,
Gesture value, such as being electrochemically reacted applied potential is 0.2V, 0.5V, 1.0V, 1.25V or 1.5V.Apply potential when
Between for 1.5~8h include any point value in the numberical range, such as apply the time of potential be 1.5h, 2.5h, 4h, 5h,
6h or 8h.
Further, when being electrochemically reacted, the potential for adjusting application is 0.9~1.4V, leaches the lithium ion,
Adjusting the potential applied is 0.2~0.5V, leaches the cobalt ions and the nickel ion.
Further, the method for purification further include: obtained lithium salts precipitating is successively crystallized, wash, is done
Lithium salts that is dry, being purified；The surplus solution is recycled as the electrolyte；Or adjust institute in the surplus solution
The molar ratio for stating cobalt ions, the nickel ion and the manganese ion, makes the molar ratio 1:1:1 of cobalt nickel manganese, or makes cobalt nickel manganese
Molar ratio be 5:2:3, or make the molar ratio 8:1:1 of cobalt nickel manganese；The method of purification is described when being passed through carbon dioxide
Carbon dioxide is overpressurized, is heated.
Further, the production method of the cathode are as follows: the waste lithium cell electrode material is taken, disassembled, calcined,
Washing, dry, grinding, compression moulding, obtain the cathode, and the thickness of electrode of the cathode is 5~10mm, the pressure of the cathode
Real density is 5~10g/cm3。
Wherein, it includes any thickness of electrode value in the numberical range, example that the thickness of electrode of the cathode, which is 5~10mm,
If the thickness of electrode of the cathode is 5mm, 6mm, 7mm, 8mm, 9mm or 10mm.Wherein, the compacted density of the cathode be 5~
10g/cm3It include any compacted density value in the numberical range, such as the compacted density of the cathode is 5g/cm3、6g/
cm3、7g/cm3、8g/cm3、9g/cm3Or 10g/cm3。
Further, the cathode is selected from waste lithium cell positive electrode and/or waste lithium cell negative electrode material, described lazy
Property electrode use graphite electrode or conductive inert metal electrode.
Preferably, the conductive inert metal electrode is platinum electrode.
Optionally, the electrolyte is to contain Na+、NH4 +、K+、Li+、Fe2+、Mn2+、Ni2+、Co2+、Co3+、Al3+Plasma
At least one of cation inorganic salts, and the concentration of the inorganic salts in the electrolyte be 0.1~1.0moL/L.
Preferably, the electrolyte is selected from ammonium carbonate electrolyte, sodium phosphate electrolyte or ammonium sulfate electrolyte.
Compared with prior art, the present invention have it is following the utility model has the advantages that
On the one hand, purifying plant of the invention has the advantages that treatment effeciency is high.The purifying plant using anode material as
Electrolytic cell, and multiple cathodes can be set in electrolytic cell, thus, it can be achieved that more lithium ion returns in primary electrochemical reaction
It receives, greatly improves recovery efficiency；Then it is passed through carbon dioxide again to purify lithium salts.Moreover, it is mentioned present invention is alternatively directed to above-mentioned
Pure device carries out series of optimum, make its can not only high efficiente callback lithium ion, but also can promote carbon dioxide with containing lithium from
The gas liquid interfacial area of the solution of son obtains the lithium salts of higher degree to improve purification efficiency, is conducive to subsequent in lithium battery production
In application.
On the other hand, method of purification of the invention has the advantages that simple process, environment friendly and pollution-free.Due to electrochemical reaction
In the obtained solution containing lithium ion, lithium ion is still ionic condition, and is also possible in the mixed solution mixed with other impurities,
Therefore it is really necessary to purify to it.The present invention only needs to be passed through carbon dioxide, this lithium salts precipitating of lithium carbonate can be obtained, then lead to
Cross the lithium salts that crystallization is purified.When purifying lithium salts using the method for purification, any reagent is added without additional, and except lithium salts is heavy
Surplus solution outside shallow lake then can be used as electrolyte recycling, so that entire method is more green, environmentally friendly, will not generate
New waste liquid to be processed.Moreover, the present invention is also by carrying out the solution containing lithium ion before being passed through carbon dioxide
Concentration first adjusts the solution containing lithium ion to modes such as alkalinity, and Lai Tigao carbon dioxide transitions are carbanion
Effect reaches preferably precipitating, refining effect.
In addition, the present invention utilize electrochemical reaction, can effectively be recycled from old and useless battery electrode material lithium, nickel, cobalt,
Manganese etc. has the metal of high utility value.Moreover, additionally it is possible to by controlling the potential of electrochemical reaction from large to small gradually
Successively decrease, leach above-mentioned recycling metal according to the sequence substep of lithium, nickel, cobalt, manganese to control, to simplify the difference gold of recycling
Energy consumption needed for belonging to the separation program of ion, reducing separation different metal ions.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the purifying plant of one lithium salts of embodiment.
Fig. 2 is the structural schematic diagram of waffle slab in embodiment one.
Fig. 3 is one of the distressed structure of waffle slab in embodiment one.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
It should be noted that the term " includes " of the embodiment of the present invention and " having " and their any deformation, it is intended that
Be to cover it is non-exclusive include, for example, containing the process, method, system, product or equipment of a series of steps or units not
Those of be necessarily limited to be clearly listed step or unit, but may include be not clearly listed or for these processes, side
The intrinsic other step or units of method, product or equipment.
Embodiment one
The present embodiment provides a kind of purifying plants of lithium salts, as shown in Figure 1, the purifying plant includes electrolytic cell 1 and three
Concatenated cathode 2.Wherein, electrolytic cell 1 includes set on internal layer and with a thickness of the anode material layer of 10mm 11 and set on the knot of outer layer
Structure supporting layer 12, anode material layer 11 are used as anode, and anode material layer 11 is graphite electrode using graphite namely anode,
Structural support layers 12 are cement layer, support purifying plant structural strength for playing the role of.Since the present embodiment dexterously will
The structure of anode and the structure of electrolytic cell are combined into one, therefore under identical electrolytic cell volume, can save need to be arranged sun originally
The space of pole makes that more cathodes 2 can be placed in electrolytic cell simultaneously, to improve the efficiency of electrochemical reaction.Wherein, cathode 2 is
Waste lithium cell positive electrode.It is understood that the electrolytic cell 1 of the present embodiment can also only with anode material layer 11, and
Not other setting structure supporting layer 2, so that the structure of entire purifying plant more simplifies.In the present embodiment, filled to above-mentioned purification
After ammonium carbonate electrolyte is added in the electrolytic cell set, applies applying electrical potential respectively to cathode and anode and be electrochemically reacted, i.e.,
It can obtain the solution containing lithium ion.
But since the solution containing lithium ion needs further purification, therefore the purifying plant is also at the side wall bottom of electrolytic cell 1
Portion is equipped with the air inlet pipe 3 of belt controling valve 31, for being passed through carbon dioxide, by carbon dioxide and electrolytic cell containing lithium ion
The effect of solution forms lithium salts precipitating, lithium salts is purified out.In the present embodiment, in order to improve carbon dioxide containing lithium from
Multiple air inlets 3 can be arranged in the sidewall bottom of electrolytic cell 1 in dissolution rate in the solution of son.In addition, in order to improve titanium dioxide
Dissolution rate of the carbon in mixed solution, makes it more be converted into carbanion, which further includes being set to electrolytic cell 1
The sealing upper cover 4 of top, sealing upper cover 4 and electrolytic cell 1 are enclosed closed cavity jointly, therefore can be by adding into closed cavity
It presses to improve the dissolution rate of carbon dioxide.In addition, being additionally provided with reagent in sealing upper cover 4 is added mouth 5, which is added mouth 5 and uses
Made in acid reagent or alkaline reagent are added into the solution containing lithium ion with adjusting the solution alkaline containing lithium ion
Carbon dioxide is easier to be converted to carbonate.
It further, is the gas liquid interfacial area for improving carbon dioxide and the solution containing lithium ion, the present embodiment also exists
Waffle slab 6 is removably installed in electrolytic cell 1, as shown in connection with fig. 2, the waffle slab 6 in the present embodiment is to set in the horizontal direction
The plate set, and the shape of any grid cell of the plate be it is rectangular, by setting waffle slab can by originally biggish two
Carbonoxide bubble cutting is more minute bubbles.The waffle slab of the present embodiment can there are many modes of texturing, such as shown in Fig. 3, should
Waffle slab 6 is horizontally disposed plate, and the shape of any grid cell of the plate for bottom surface aperture, open by big, top surface
The small taper type in hole.When the shape of grid cell any in waffle slab is the taper type that bottom surface aperture is big, top surface aperture is small, energy
So that carbon dioxide bubble is become smaller, can further improve vapour-liquid contact area.In order to facilitate being mounted and taken out for waffle slab,
(the specifically inner wall of anode material layer 11) is equipped with towards electrolytic cell inner horizontal and extends on the opposite sides inner wall of electrolytic cell 1
The adapting table 7 of formation, waffle slab 6 ride upon on adapting table 7.It is understood that the present embodiment can also use other modes
It realizes being mounted and taken out for waffle slab, such as is installed with bracket 7 in the bottom of waffle slab 6, installed waffle slab 6 by bracket 7
In electrolytic cell 1.
The purifying plant of the present embodiment have the characteristics that it is dynamical, the purifying plant dexterously using anode material as electrolysis
Pond, and multiple cathodes can be set in electrolytic cell, thus, it can be achieved that more old and useless battery electrode in primary electrochemical reaction
Metal recovery in material, greatly improves recovery efficiency.Moreover, present invention is alternatively directed to above-mentioned purifying plants to optimize,
So that it is not only able to achieve the effect of high efficiente callback metal, but also can further to the obtained solution containing lithium ion into
Row purification is conducive to subsequent applications to obtain the lithium salts of higher degree.
The present embodiment also provides a kind of method of purification of lithium salts, which uses above-mentioned purifying plant, the purification side
Method the following steps are included:
Using waste lithium cell positive electrode as cathode, using graphite electrode as anode；Wherein, the production method of cathode
Are as follows: waste lithium cell positive electrode is taken, disassembled, calcined, washed, dried, ground, compression moulding, cathode is obtained, cathode
Thickness of electrode is 5mm, and the compacted density of cathode is 5g/cm3。
The ammonium carbonate electrolyte that concentration is 0.1moL/L is added into electrolytic cell, cathode and anode is made to immerse ammonium carbonate electrolysis
In liquid, be electrochemically reacted, the potential that electrochemical reaction is applied be 0.2~1.5V, and it is descending adjust apply electricity
Gesture value, the time for applying potential is 2h, obtains the solution containing lithium ion, and should also contain other in the solution containing lithium ion
Metal ion, each metal ion substep leach, leach sequencing and be respectively as follows: lithium ion, nickel ion, cobalt ions, manganese ion.
The solution containing lithium ion obtained by above-mentioned electrochemical reaction is concentrated, so as to it is subsequent to lithium ion into
Row purification, makes lithium concentration to be purified be greater than or equal to 25g/L；Then, the solution containing lithium ion after concentration is adjusted
To alkalinity.
Air inlet pipe is opened, is passed through two for being overpressurized, being heated into the solution containing lithium ion for being adjusted to alkalinity
Carbonoxide improves the solubility of carbon dioxide using the processing mode of pressurised air jet, heating carbon dioxide, and passes through heating
The processing mode of carbon dioxide promotes the concentration of the solution containing lithium ion, is obtained by filtration lithium salts precipitating and surplus solution；It is right
Lithium salts precipitating is successively crystallized, is washed, being dried, the lithium salts purified；Surplus solution is then used as electrolyte to be recycled.
Embodiment two
The present embodiment provides a kind of purifying plant of lithium salts, the purifying plant of the present embodiment and the difference of embodiment one
It is only that, anode material layer selects metal platinum, i.e. anode is platinum electrode.
The present embodiment also provides a kind of method of purification of lithium salts, which uses above-mentioned purifying plant, the purification side
Method the following steps are included:
Using waste lithium cell positive electrode as cathode, using platinum electrode as anode；Wherein, the production method of cathode are as follows:
Waste lithium cell positive electrode is taken, successively disassembled, calcined, washed, dried, ground, compression moulding, cathode, cathode are obtained
Thickness of electrode be 10mm, the compacted density of cathode is 10g/mL.
The ammonium sulfate electrolyte that concentration is 1.0moL/L is added into electrolytic cell, cathode and anode is made to immerse ammonium carbonate electrolysis
It in liquid, is electrochemically reacted, the potential that electrochemical reaction is applied is 0.2~1.5V, and the time for applying potential is 8h, is obtained
Solution containing lithium ion, and metal ion therein substep leaches.It is specifically descending to adjust the potential value applied, first adjust
The potential that section applies is 0.9~1.4V, leaches lithium ion, then adjusting the potential of application is 0.2~0.5V, makes cobalt ions and nickel
Ion leaches.
The solution containing lithium ion obtained by above-mentioned electrochemical reaction is concentrated, so as to it is subsequent to lithium ion into
Row purification, makes lithium concentration to be purified be greater than or equal to 30g/L；Then, the solution containing lithium ion after concentration is adjusted
To alkalinity.
Air inlet pipe is opened, is passed through two for being overpressurized, being heated into the solution containing lithium ion for being adjusted to alkalinity
Carbonoxide improves the solubility of carbon dioxide using the processing mode of pressurised air jet, heating carbon dioxide, and passes through heating
The processing mode of carbon dioxide promotes the concentration of the solution containing lithium ion, is obtained by filtration lithium salts precipitating and surplus solution；It is right
Lithium salts precipitating is successively crystallized, is washed, being dried, the lithium salts purified；Surplus solution is then used as electrolyte to be recycled.
Embodiment three
The present embodiment provides a kind of purifying plant of lithium salts, the purifying plant of the present embodiment and the difference of embodiment one
It is only that, waffle slab is with the arc panel for being bent upwards radian, and the shape of any grid cell of arc panel in the present embodiment
Shape is the taper type that bottom surface aperture is big, top surface aperture is small.The bending degree of the arc panel is simultaneously little, therefore generally still substantially along water
Square to being mounted in electrolytic cell.
The present embodiment also provides a kind of method of purification of lithium salts, which uses above-mentioned purifying plant, the purification side
Method the following steps are included:
Using waste lithium cell positive electrode as cathode, using graphite electrode as anode；Wherein, the production method of cathode
Are as follows: waste lithium cell positive electrode is taken, successively disassembled, calcined, washed, dried, ground, compression moulding, cathode is obtained, yin
The thickness of electrode of pole is 7mm, and the compacted density of cathode is 7g/cm3。
The ammonium carbonate electrolyte that concentration is 0.5moL/L is added into electrolytic cell, cathode and anode is made to immerse ammonium carbonate electrolysis
In liquid, be electrochemically reacted, the potential that electrochemical reaction is applied be 0.2~1.5V, and it is descending adjust apply electricity
Gesture value, the time for applying potential is 4h, obtains the solution containing lithium ion, and should also contain other in the solution containing lithium ion
Metal ion, each metal ion substep leach, leach sequencing and be respectively as follows: lithium ion, nickel ion, cobalt ions, manganese ion.
The solution containing lithium ion obtained by above-mentioned electrochemical reaction is concentrated, so as to it is subsequent to lithium ion into
Row purification, makes lithium concentration to be purified be greater than or equal to 25g/L；Then, the solution containing lithium ion after concentration is adjusted
To alkalinity.
Air inlet pipe is opened, is passed through two for being overpressurized, being heated into the solution containing lithium ion for being adjusted to alkalinity
Carbonoxide improves the solubility of carbon dioxide using the processing mode of pressurised air jet, heating carbon dioxide, and passes through heating
The processing mode of carbon dioxide promotes the concentration of the solution containing lithium ion, it is obtained by filtration lithium salts precipitating and surplus solution；It is right
Lithium salts precipitating is successively crystallized, is washed, being dried, the lithium salts purified；Surplus solution is then used as electrolyte to be recycled.
Example IV
The present embodiment provides a kind of purifying plants of lithium salts, and the purifying plant is identical as the purifying plant in embodiment one,
Therefore details are not described herein.
The present embodiment also provides a kind of method of purification of lithium salts, which uses above-mentioned purifying plant, the purification side
Method the following steps are included:
Using waste lithium cell positive electrode as cathode, using graphite electrode as anode；Wherein, the production method of cathode
Are as follows: waste lithium cell positive electrode is taken, disassembled, calcined, washed, dried, ground, compression moulding, cathode is obtained, cathode
Thickness of electrode is 5mm, and the compacted density of cathode is 5g/cm3。
The ammonium carbonate electrolyte that concentration is 0.1moL/L is added into electrolytic cell, cathode and anode is made to immerse ammonium carbonate electrolysis
In liquid, be electrochemically reacted, the potential that electrochemical reaction is applied be 0.2~1.5V, and it is descending adjust apply electricity
Gesture value, the time for applying potential is 2h, obtains the solution containing lithium ion, and should also contain other in the solution containing lithium ion
Metal ion, each metal ion substep leach, leach sequencing and be respectively as follows: lithium ion, nickel ion, cobalt ions, manganese ion.
The solution containing lithium ion obtained by above-mentioned electrochemical reaction is concentrated, so as to it is subsequent to lithium ion into
Row purification, makes lithium concentration to be purified be greater than or equal to 25g/L；Then, the solution containing lithium ion after concentration is adjusted
To alkalinity.
Air inlet pipe is opened, is passed through two for being overpressurized, being heated into the solution containing lithium ion for being adjusted to alkalinity
Carbonoxide improves the solubility of carbon dioxide using the processing mode of pressurised air jet, heating carbon dioxide, and passes through heating
The processing mode of carbon dioxide promotes the concentration of the solution containing lithium ion, is obtained by filtration lithium salts precipitating and surplus solution；It is right
Lithium salts precipitating is successively crystallized, is washed, being dried, the lithium salts purified；Surplus solution then recycle cobalt ions therein, nickel from
Son and manganese ion, make three be advantageously used in the production of subsequent lithium cell electrodes material.
Specifically: adjusting the molar ratio of cobalt ions in remaining mixed solution, nickel ion and manganese ion, make cobalt nickel manganese
Molar ratio is 1:1:1, and the cobalt nickel manganese of the molar ratio can be directly used for preparing corresponding battery raw material.Compared with respectively extract cobalt,
Then nickel, manganese adjust the proportion of three again, to meet corresponding battery electrode material production, using the method for the present embodiment, directly
The molar ratio for adjusting cobalt nickel manganese in the remaining mixed solution without lithium ion is connect, it is made to can be directly used for battery electrode material
Production, this method is more succinct, simultaneously because without additionally adding other chemical reagent in whole process, so that entirely
Method is also more environmentally friendly.
It is understood that rubbing for the molar ratio 5:2:3 or cobalt nickel manganese for making cobalt nickel manganese can also be adjusted in the present embodiment
Your ratio is 8:1:1, and the cobalt nickel manganese of both ratios also can be directly used for preparing corresponding battery raw material.
In above-described embodiment one to four, the present invention utilizes electrochemical reaction, can have from old and useless battery electrode material
Effect recycles the metal with high utility value such as lithium, nickel, cobalt, manganese.Moreover, additionally it is possible to pass through control electrochemical reaction
Potential is gradually incremented by from small to large, leaches above-mentioned recycling metal according to the sequence substep of lithium, nickel, cobalt, manganese to control, thus simple
Energy consumption needed for having changed the separation program of the different metal ions of recycling, having reduced separation different metal ions.Further, above-mentioned
In the method for embodiment, also anticathode thickness of electrode is defined, and will affect ion transmission efficiency since electrode is blocked up, because
The thickness of electrode of cathode is 5~10mm in this above-described embodiment.
Importantly, lithium ion is still ionic condition in the solution containing lithium ion obtained due to electrochemical reaction,
And be also possible in the solution mixed with other impurities, therefore it is really necessary to purify to it.Therefore, in the method for above-described embodiment,
The purification scheme for also having advanced optimized recycling lithium ion, specifically only needs to be passed through carbon dioxide, it is this that lithium carbonate can be obtained
Lithium salts precipitating, then respectively by crystallization, washing, the dry lithium salts for finally obtaining purification, due to having obtained the higher lithium salts of purity,
Therefore can be used for following process production battery material etc., there is extensive use.When purifying lithium salts using this method, it is added without additional
Any reagent, and the remaining mixed solution in addition to lithium salts precipitating then can be used as electrolyte and be recycled, so that entirely
Method is more green, environmentally friendly, will not generate new waste liquid to be processed.Moreover, the present invention is also by passing through carbon dioxide
Before, the solution containing lithium ion is concentrated and is contained described in the reaction efficiency of carbonate and lithium ion, first adjusting with improving
The solution of lithium ion, to improve effect of the carbon dioxide transitions as carbanion, reaches preferably precipitating, purification effect to alkalinity
Fruit.
Further, in example IV, also by adjusting mole between the cobalt nickel manganese in remaining mixed solution
Than, so that the cobalt nickel manganese with special ratios is can be directly used for the preparation of associated batteries raw material, without extraction cobalt nickel manganese respectively, then
Proportion is readjusted, multiple links are saved, keeps entire method more convenient, more environmentally-friendly.
The purifying plant and method of purification of a kind of lithium salts disclosed by the embodiments of the present invention are described in detail above, this
Apply that a specific example illustrates the principle and implementation of the invention in text, the explanation of above example is only intended to
It facilitates the understanding of the method and its core concept of the invention；At the same time, for those skilled in the art, think of according to the present invention
Think, there will be changes in the specific implementation manner and application range, in conclusion the content of the present specification should not be construed as pair
Limitation of the invention.
Claims (10)
1. a kind of purifying plant of lithium salts, which is characterized in that the purifying plant includes:
Electrolytic cell, the electrolytic cell include anode material layer, and the anode material layer is used as anode, and the anode is inertia
Electrode；
Several cathodes, the cathode are waste lithium cell electrode material；
Air inlet pipe, the air inlet pipe are connected to the bottom wall of the electrolytic cell or are connected to the sidewall bottom of the electrolytic cell.
2. purifying plant according to claim 1, which is characterized in that the electrolytic cell further includes being set to the anode material
Layer outside structural support layers, wherein the anode material layer with a thickness of 5~12mm；The material of the structural support layers is selected from
Concrete, cement, stone material, rubber or resin；The top of the electrolytic cell is equipped with sealing upper cover, the sealing upper cover and the electricity
Xie Chi is enclosed closed cavity jointly；Reagent is additionally provided in the sealing on lid, mouth is added.
3. purifying plant according to claim 1, which is characterized in that the inside of the electrolytic cell has been detachably arranged greatly
Horizontally disposed waffle slab is caused, the waffle slab uses insulating materials；The waffle slab is horizontally disposed
Plate, the shape of any grid cell of the plate are rectangular or taper type；Alternatively, the waffle slab is with being bent upwards
The arc panel of radian, the shape of any grid cell of the arc panel are taper type；The waffle slab bottom is fixedly provided with branch
Frame, and the bracket uses insulating materials；It is formed alternatively, the inner wall of the electrolytic cell is equipped with towards therein horizontal extension
Adapting table, the waffle slab are erected on the adapting table.
4. a kind of method of purification of lithium salts, the method for purification uses the purification of lithium salts as described in any one of claims 1 to 3
Device, which is characterized in that the method for purification the following steps are included:
Using the waste lithium cell electrode material as cathode, using the inert electrode as anode；
Electrolyte is added into the electrolytic cell, immerses the cathode and the anode in electrolyte, under applying electrical potential into
Row electrochemical reaction obtains the solution containing lithium ion；
Open the air inlet pipe, to reaction after described in be passed through carbon dioxide in the solution containing lithium ion, obtain lithium salts precipitating
And surplus solution.
5. method of purification according to claim 4, which is characterized in that the method for purification further include: be passed through titanium dioxide
Before carbon, first the solution containing lithium ion is concentrated, makes the lithium concentration in the solution containing lithium ion
More than or equal to 25g/L；And/or before being passed through carbon dioxide, the solution containing lithium ion is first adjusted to alkalinity.
6. according to the described in any item methods of purification of claim 4 or 5, which is characterized in that the solution containing lithium ion is also
Including at least one of nickel ion, cobalt ions, manganese ion.
7. method of purification according to claim 6, which is characterized in that being electrochemically reacted applied potential is 0.2
~1.5V, the time for applying potential is 1.5~8h；In the method for purification, the solution containing lithium ion further includes institute
State nickel ion, the cobalt ions and the manganese ion, when being electrochemically reacted, adjust the potential of application, make the lithium ion,
The nickel ion, the cobalt ions, manganese ion substep leach.
8. method of purification according to claim 7, which is characterized in that when being electrochemically reacted, adjust the potential of application
For 0.9~1.4V, leach the lithium ion, the potential for adjusting application is 0.2~0.5V, make the cobalt ions and the nickel from
Son leaches.
9. method of purification according to claim 7, which is characterized in that the method for purification further include: described in obtaining
Lithium salts precipitating is successively crystallized, is washed, being dried, the lithium salts purified；The surplus solution is recycled as the electrolyte
It uses, or adjusts the molar ratio of cobalt ions described in the surplus solution, the nickel ion and the manganese ion, make cobalt nickel manganese
Molar ratio be 1:1:1, perhaps make the molar ratio 5:2:3 of cobalt nickel manganese or make the molar ratio 8:1:1 of cobalt nickel manganese；It is described
When being passed through carbon dioxide, the carbon dioxide is overpressurized, is heated method of purification.
10. according to the described in any item methods of purification of claim 4 or 5, which is characterized in that the production method of the cathode are as follows:
The waste lithium cell electrode material is taken, successively disassembled, calcined, washed, dried, ground, compression moulding, the yin is obtained
Pole, the thickness of electrode of the cathode are 5~10mm, and the compacted density of the cathode is 5~10g/cm3；The cathode is selected from useless
Old lithium pond positive electrode and/or waste lithium cell negative electrode material, the inert electrode use graphite electrode or conductive lazy
Property metal electrode；The electrolyte is to contain Na+、NH4 +、K+、Li+、Fe2+、Mn2+、Ni2+、Co2+、Co3+、Al3+In ion at least
A kind of inorganic salts of cation, and the concentration of the inorganic salts in the electrolyte is 0.1~1.0moL/L.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201525894U (en) * | 2009-11-02 | 2010-07-14 | 新郑市东升炭素有限公司 | Combined type multi-cathode and multi-anode graphite electrolytic tank |
| CN102947225A (en) * | 2010-02-17 | 2013-02-27 | 辛博尔股份有限公司 | Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds |
| CN103972526A (en) * | 2014-05-12 | 2014-08-06 | 清华大学 | Generating and energy storage integrated device based on direct carbon fuel cells (DCFCs) with liquid metal positive electrode |
| US20160111712A1 (en) * | 2014-10-20 | 2016-04-21 | Sumitomo Osaka Cement Co., Ltd. | Cathode material and lithium ion battery |
| CN106785174A (en) * | 2017-02-24 | 2017-05-31 | 中南大学 | A kind of method for being leached from lithium ion cell anode waste based on electrochemical process and reclaiming metal |
| CN106976894A (en) * | 2017-05-10 | 2017-07-25 | 东北大学 | A kind of method that lithium chloride electricity conversion directly prepares lithium carbonate |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
-
2018
- 2018-08-06 CN CN201810886847.2A patent/CN110451533B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201525894U (en) * | 2009-11-02 | 2010-07-14 | 新郑市东升炭素有限公司 | Combined type multi-cathode and multi-anode graphite electrolytic tank |
| CN102947225A (en) * | 2010-02-17 | 2013-02-27 | 辛博尔股份有限公司 | Processes for preparing highly pure lithium carbonate and other highly pure lithium containing compounds |
| CN103972526A (en) * | 2014-05-12 | 2014-08-06 | 清华大学 | Generating and energy storage integrated device based on direct carbon fuel cells (DCFCs) with liquid metal positive electrode |
| US20160111712A1 (en) * | 2014-10-20 | 2016-04-21 | Sumitomo Osaka Cement Co., Ltd. | Cathode material and lithium ion battery |
| CN106785174A (en) * | 2017-02-24 | 2017-05-31 | 中南大学 | A kind of method for being leached from lithium ion cell anode waste based on electrochemical process and reclaiming metal |
| CN106976894A (en) * | 2017-05-10 | 2017-07-25 | 东北大学 | A kind of method that lithium chloride electricity conversion directly prepares lithium carbonate |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
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