CN110451533B - Lithium salt purification device and purification method - Google Patents

Lithium salt purification device and purification method Download PDF

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CN110451533B
CN110451533B CN201810886847.2A CN201810886847A CN110451533B CN 110451533 B CN110451533 B CN 110451533B CN 201810886847 A CN201810886847 A CN 201810886847A CN 110451533 B CN110451533 B CN 110451533B
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lithium
electrolytic cell
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cathode
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CN110451533A (en
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张作泰
王树宾
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Southwest University of Science and Technology
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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
    • 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
    • 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
    • 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
    • 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 invention relates to the technical field of energy and materials, in particular to a lithium salt purification device and a lithium salt purification method. The purification device comprises: an electrolytic cell comprising a layer of anode material, the layer of anode material serving as an anode, the anode being an inert electrode; the cathodes are waste lithium battery electrode materials; and the air inlet pipe is communicated with the bottom wall of the electrolytic cell or the bottom of the side wall of the electrolytic cell. The purification device has the advantage of high treatment efficiency. The purification device skillfully takes the anode material as the electrolytic cell, and can arrange a plurality of cathodes in the electrolytic cell, thereby realizing the recovery of more lithium ions in one electrochemical reaction and greatly improving the recovery efficiency.

Description

Lithium salt purification device and purification method
Technical Field
The invention relates to the technical field of energy and materials, in particular to a lithium salt purification device and a lithium salt purification method.
Background
The lithium battery is applied to the cardiac pacemaker at the earliest time, and is widely used in the fields of electric vehicles, mobile phones, notebook computers, new energy vehicles and the like with the continuous development of science and technology, and the lithium battery becomes the mainstream of the development of the battery technology industry at present. With the annual increase of the market occupancy of lithium batteries, great promotion is inevitably provided for the development of upstream and downstream industries. Such as lithium salt raw materials used for manufacturing lithium ion batteries, the demand for lithium salt raw materials is greatly increased.
For example, chinese patent CN 200910249795.9 discloses a method for preparing high-purity lithium carbonate and other available byproducts from salt lake brine, which comprises the following steps: separating potassium and sodium by drying salt in a salt pan; separating boron by an acidification method; separating magnesium by a precipitation method; separating calcium by precipitation; preparing lithium chloride; the preparation of lithium carbonate has more process steps, and various reagents (hydrochloric acid, ammonia water, ammonium bicarbonate and the like) need to be added in the steps, so that the purification cost is increased, waste water is generated and needs secondary treatment, and the environmental burden is increased.
Disclosure of Invention
The invention aims to provide a lithium salt purification device and a lithium salt purification method, which are used for solving the problems of complex operation process, large reagent dosage, large amount of generated wastewater and the like in the conventional lithium salt purification method.
In a first aspect, the present invention provides a purification apparatus for a lithium salt, the purification apparatus comprising:
an electrolytic cell comprising a layer of anode material, the layer of anode material serving as an anode, the anode being an inert electrode;
the cathodes are waste lithium battery electrode materials;
and the air inlet pipe is communicated with the bottom wall of the electrolytic cell or the bottom of the side wall of the electrolytic cell.
Further, the electrolytic cell also comprises a structure supporting layer arranged outside the anode material layer, wherein the thickness of the anode material layer is 5-12 mm.
Optionally, the material of the structural support layer is selected from concrete, cement, stone, rubber or resin.
Furthermore, a sealing upper cover is arranged above the electrolytic cell, and the sealing upper cover and the electrolytic cell jointly enclose to form a closed cavity.
Furthermore, a reagent feeding port is also arranged on the sealing upper cover.
Furthermore, a grid plate which is arranged along the horizontal direction is detachably arranged in the electrolytic cell, and the grid plate is made of insulating materials.
Preferably, the insulating material is ceramic.
Furthermore, the grid plate is a flat plate arranged along the horizontal direction, and any grid unit of the flat plate is square or frustum-shaped; or the grid plate is an arc plate with an upward bending radian, and any grid unit of the arc plate is in a frustum shape.
In one embodiment, a support is fixedly arranged at the bottom of the grid plate, and the support is made of an insulating material.
In one embodiment, the inner wall of the electrolytic cell is provided with a receiving platform extending horizontally towards the inner part of the electrolytic cell, and the grid plate is erected on the receiving platform.
In a second aspect, the present invention provides a purification method of a lithium salt using the above purification apparatus of a lithium salt, the purification method comprising the steps of:
taking the electrode material of the waste lithium battery as a cathode and the inert electrode as an anode;
adding electrolyte into the electrolytic cell, so that the cathode and the anode are immersed into the electrolyte, and performing electrochemical reaction under an applied potential to obtain a solution containing lithium ions;
and opening the air inlet pipe, and introducing carbon dioxide into the solution containing the lithium ions after the reaction to obtain lithium salt precipitate and residual solution.
Further, the purification method further comprises: before introducing carbon dioxide, concentrating the solution containing lithium ions to ensure that the lithium ion concentration in the solution containing lithium ions is more than or equal to 25 g/L.
Further, the purification method further comprises: the solution containing lithium ions is adjusted to be alkaline before the introduction of carbon dioxide.
Further, the solution containing lithium ions further includes at least one of nickel ions, cobalt ions, and manganese ions.
Further, the applied potential for carrying out the electrochemical reaction is 0.2-1.5V, and the time for applying the potential is 1.5-8 h; in the purification method, the solution containing lithium ions further comprises the nickel ions, the cobalt ions and the manganese ions, and when the electrochemical reaction is carried out, the applied potential is adjusted to leach the lithium ions, the nickel ions, the cobalt ions and the manganese ions step by step.
The potential applied for performing the electrochemical reaction is 0.2-1.5V including any potential value within the range, for example, the potential applied for performing the electrochemical reaction is 0.2V, 0.5V, 1.0V, 1.25V or 1.5V. The time for applying the potential is 1.5 to 8 hours includes any point within the range of values, for example, the time for applying the potential is 1.5 hours, 2.5 hours, 4 hours, 5 hours, 6 hours, or 8 hours.
Further, during the electrochemical reaction, the applied potential is adjusted to be 0.9-1.4V to leach the lithium ions, and the applied potential is adjusted to be 0.2-0.5V to leach the cobalt ions and the nickel ions. .
Further, the purification method further comprises: crystallizing, washing and drying the obtained lithium salt precipitate in sequence to obtain purified lithium salt; the residual solution is used as the electrolyte for recycling; or adjusting the molar ratio of the cobalt ions, the nickel ions and the manganese ions in the residual solution to ensure that the molar ratio of cobalt, nickel and manganese is 1:1:1, or 5:2:3, or 8:1: 1; in the purification method, when carbon dioxide is introduced, the carbon dioxide is subjected to pressurization and heating treatment.
Further, the manufacturing method of the cathode comprises the following steps: taking the waste lithium battery electrode material, disassembling, calcining, washing, drying, grinding and pressing to form to obtain the cathode, wherein the electrode thickness of the cathode is 5-10 mm, and the compaction density of the cathode is 5-10 g/cm3。
Wherein, the electrode thickness of the cathode is 5-10 mm including any electrode thickness value within the numerical range, for example, the electrode thickness of the cathode is 5mm, 6mm, 7mm, 8mm, 9mm or 10 mm. Wherein the compacted density of the cathode is 5-10 g/cm3Any compacted density value within this range is included, for example a compacted density of 5g/cm for the cathode3、6g/cm3、7g/cm3、8g/cm3、9g/cm3Or 10g/cm3。
Further, the cathode is selected from a positive electrode material of a waste lithium battery and/or a negative electrode material of the waste lithium battery, and the inert electrode is a graphite electrode or a conductive inert metal electrode.
Preferably, the inert metal electrode capable of conducting electricity is a platinum electrode.
Optionally, the electrolyte contains Na+、NH4 +、K+、Li+、Fe2+、Mn2+、Ni2+、Co2+、Co3+、Al3+At least one kind of inorganic salt of positive ions in the plasma, and the concentration of the inorganic salt in the electrolyte is 0.1-1.0 moL/L.
Preferably, the electrolyte is selected from an ammonium carbonate electrolyte, a sodium phosphate electrolyte or an ammonium sulfate electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
on the one hand, the purification device has the advantage of high treatment efficiency. The purification device takes the anode material as an electrolytic cell, and a plurality of cathodes can be arranged in the electrolytic cell, so that more lithium ions can be recovered in one electrochemical reaction, and the recovery efficiency is greatly improved; and then carbon dioxide is introduced to purify the lithium salt. Moreover, the invention also aims at the purification device to carry out a series of optimization, so that the lithium ion purification device not only can efficiently recover lithium ions, but also can promote the gas-liquid contact area of carbon dioxide and a solution containing lithium ions, thereby improving the purification efficiency, obtaining lithium salt with higher purity and being beneficial to the subsequent application in the production of lithium batteries.
On the other hand, the purification method of the invention has the advantages of simple process, environmental protection and no pollution. Since lithium ions in the solution containing lithium ions obtained by the electrochemical reaction are still in an ionic state, and other impurities may be doped in the mixed solution, it is necessary to purify the lithium ions. According to the invention, lithium carbonate lithium salt precipitate can be obtained only by introducing carbon dioxide, and then purified lithium salt is obtained by crystallization. When the purification method is adopted to purify the lithium salt, no additional reagent is needed to be added, and the residual solution except the lithium salt precipitate can be used as the electrolyte for recycling, so that the whole method is more green and environment-friendly, and new waste liquid to be treated can not be generated. Moreover, the invention also improves the effect of converting carbon dioxide into carbonate ions by concentrating the solution containing lithium ions, adjusting the solution containing lithium ions to be alkaline and the like before introducing carbon dioxide, thereby achieving better precipitation and purification effects.
In addition, the invention can effectively recover metals with high utilization value, such as lithium, nickel, cobalt, manganese and the like from waste battery electrode materials by utilizing electrochemical reaction. Moreover, the potential of the electrochemical reaction is controlled to gradually decrease from large to small, so that the recovered metal is controlled to be leached step by step according to the sequence of lithium, nickel, cobalt and manganese, the separation procedure of the recovered different metal ions is simplified, and the energy consumption for separating the different metal ions is reduced.
Drawings
Fig. 1 is a schematic view of a lithium salt purification apparatus according to an embodiment.
Fig. 2 is a schematic structural diagram of a grid plate according to a first embodiment.
Fig. 3 is one of the modified structures of the grid plate in the first embodiment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "comprises" and "comprising," and any variations thereof, of embodiments of the present invention are intended to cover non-exclusive inclusions, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example one
This example provides a purification apparatus for lithium salt, which, as shown in fig. 1, comprises an electrolytic cell 1 and three cathodes 2 connected in series. Wherein, electrolytic cell 1 is including locating inlayer and the anode material layer 11 that thickness is 10mm and locating outer structure supporting layer 12, and anode material layer 11 uses as the positive pole, and anode material layer 11 adopts graphite, and the positive pole is graphite electrode promptly, and structure supporting layer 12 is the cement layer for play the effect of supporting purification device structural strength. Because this embodiment combines the structure of positive pole and the structure of electrolytic bath into one ingeniously, so under the same electrolytic bath volume, can save the space that originally need set up the positive pole, can place more negative poles 2 in making the electrolytic bath simultaneously to improve electrochemical reaction's efficiency. Wherein, the cathode 2 is a positive electrode material of a waste lithium battery. It will be understood that the electrolytic cell 1 of the present embodiment may also be used with only the anode material layer 11 without additionally providing the structural support layer 2, so as to simplify the structure of the entire purification apparatus. In this embodiment, after the ammonium carbonate electrolyte is added to the electrolytic cell of the purification apparatus, an external potential is applied to the cathode and the anode, respectively, to perform an electrochemical reaction, so as to obtain a solution containing lithium ions.
However, since the solution containing lithium ions needs to be further purified, the purifying device is further provided with an air inlet pipe 3 with a control valve 31 at the bottom of the side wall of the electrolytic cell 1 for introducing carbon dioxide, and lithium salt is formed and precipitated through the action of the carbon dioxide and the solution containing lithium ions in the electrolytic cell to purify the lithium salt. . In the present embodiment, in order to increase the dissolution rate of carbon dioxide in the lithium ion-containing solution, a plurality of air inlet holes 3 may be provided at the bottom of the sidewall of the electrolytic cell 1. In addition, in order to improve the dissolution rate of the carbon dioxide in the mixed solution and convert the carbon dioxide into more carbonate ions, the purification device further comprises a sealing upper cover 4 arranged above the electrolytic cell 1, and the sealing upper cover 4 and the electrolytic cell 1 jointly enclose to form a closed cavity, so that the dissolution rate of the carbon dioxide can be improved by pressurizing the closed cavity. In addition, a reagent inlet 5 is provided on the sealing upper cover 4, and the reagent inlet 5 is used for adding an acidic reagent or an alkaline reagent to the solution containing lithium ions to adjust the solution containing lithium ions to be alkaline, so that carbon dioxide is more easily converted into carbonate.
Further, in order to increase the gas-liquid contact area between the carbon dioxide and the solution containing lithium ions, in this embodiment, a grid plate 6 is detachably mounted in the electrolytic cell 1, as shown in fig. 2, the grid plate 6 in this embodiment is a flat plate arranged in the horizontal direction, and any grid unit of the flat plate is square, so that the originally large carbon dioxide bubbles can be divided into more small bubbles by the grid plate. The grid plate of the present embodiment can be modified in various ways, for example, as shown in fig. 3, the grid plate 6 is a flat plate disposed along the horizontal direction, and any grid cell of the flat plate has a frustum shape with a large bottom surface opening and a small top surface opening. When any grid unit in the grid plate is in a frustum shape with large bottom surface open pores and small top surface open pores, carbon dioxide bubbles can be made smaller, and the vapor-liquid contact area can be further increased. In order to facilitate the installation and removal of the grid plate, the inner walls of the two opposite sides of the electrolytic cell 1 (specifically, the inner wall of the anode material layer 11) are provided with a receiving platform 7 which extends horizontally towards the inside of the electrolytic cell, and the grid plate 6 is erected on the receiving platform 7. It will be understood that the present embodiment may also adopt other manners to implement the installation and removal of the grid plate, for example, a bracket 7 is fixedly arranged at the bottom of the grid plate 6, and the grid plate 6 is supported in the electrolytic cell 1 through the bracket 7.
The purification device of this embodiment has high-efficient characteristics, and this purification device is ingenious with anode material as the electrolytic bath, and can set up a plurality of cathodes in the electrolytic bath to in an electrochemical reaction, can realize the metal recovery in more old and useless battery electrode material, improve recovery efficiency by a wide margin. Moreover, the invention also optimizes the purification device, so that the purification device not only can realize the effect of efficiently recovering metals, but also can further purify the obtained solution containing lithium ions to obtain lithium salts with higher purity, thereby being beneficial to subsequent application.
The present embodiment also provides a purification method of a lithium salt, the purification method using the above purification apparatus, the purification method comprising the steps of:
taking a positive electrode material of a waste lithium battery as a cathode and a graphite electrode as an anode; the manufacturing method of the cathode comprises the following steps: taking the anode material of the waste lithium battery, disassembling, calcining, washing, drying, grinding and pressing to form to obtain the cathode, wherein the thickness of the cathode is 5mm, and the compaction density of the cathode is 5g/cm3。
Adding ammonium carbonate electrolyte with the concentration of 0.1moL/L into an electrolytic cell, immersing a cathode and an anode into the ammonium carbonate electrolyte, carrying out electrochemical reaction, wherein the applied potential of the electrochemical reaction is 0.2-1.5V, the applied potential value is adjusted from large to small, the time of applying the potential is 2h, so as to obtain a solution containing lithium ions, the solution containing the lithium ions also contains other metal ions, and the leaching sequence of the metal ions is as follows: lithium ion, nickel ion, cobalt ion, manganese ion.
Concentrating the solution containing lithium ions obtained through the electrochemical reaction so as to purify the lithium ions subsequently, wherein the concentration of the lithium ions to be purified is more than or equal to 25 g/L; then, the concentrated solution containing lithium ions is adjusted to be alkaline.
Opening an air inlet pipe, introducing pressurized and heated carbon dioxide into the solution containing the lithium ions and adjusted to be alkaline, improving the solubility of the carbon dioxide by utilizing a pressurized air injection and carbon dioxide heating treatment mode, promoting the concentration of the solution containing the lithium ions by utilizing a carbon dioxide heating treatment mode, and filtering to obtain lithium salt precipitates and a residual solution; crystallizing, washing and drying the lithium salt precipitate in sequence to obtain purified lithium salt; the residual solution is used as electrolyte for recycling.
Example two
The present embodiment provides a lithium salt purifying apparatus, which is different from the first embodiment only in that the anode material layer is made of platinum, i.e. the anode is a platinum electrode.
The present embodiment also provides a purification method of a lithium salt, the purification method using the above purification apparatus, the purification method comprising the steps of:
taking a positive electrode material of a waste lithium battery as a cathode and a platinum electrode as an anode; the manufacturing method of the cathode comprises the following steps: taking the waste lithium battery positive electrode material, sequentially disassembling, calcining, washing, drying, grinding and pressing to form to obtain the cathode, wherein the electrode thickness of the cathode is 10mm, and the compaction density of the cathode is 10 g/mL.
Adding ammonium sulfate electrolyte with the concentration of 1.0moL/L into an electrolytic cell, immersing a cathode and an anode into the ammonium carbonate electrolyte, carrying out electrochemical reaction, wherein the applied potential of the electrochemical reaction is 0.2-1.5V, the time of the applied potential is 8h, obtaining a solution containing lithium ions, and leaching the metal ions in the solution step by step. Specifically, the applied potential value is adjusted from large to small, the applied potential is adjusted to be 0.9-1.4V firstly, so that lithium ions are leached out, and then the applied potential is adjusted to be 0.2-0.5V, so that cobalt ions and nickel ions are leached out.
Concentrating the solution containing lithium ions obtained through the electrochemical reaction so as to purify the lithium ions subsequently, wherein the concentration of the lithium ions to be purified is more than or equal to 30 g/L; then, the concentrated solution containing lithium ions is adjusted to be alkaline.
Opening an air inlet pipe, introducing pressurized and heated carbon dioxide into the solution containing the lithium ions and adjusted to be alkaline, improving the solubility of the carbon dioxide by utilizing a pressurized air injection and carbon dioxide heating treatment mode, promoting the concentration of the solution containing the lithium ions by utilizing a carbon dioxide heating treatment mode, and filtering to obtain lithium salt precipitates and a residual solution; crystallizing, washing and drying the lithium salt precipitate in sequence to obtain purified lithium salt; the residual solution is used as electrolyte for recycling.
EXAMPLE III
The present embodiment provides a lithium salt purifying device, which is different from the first embodiment only in that the grid plate in the present embodiment is an arc plate having an upward curved arc, and each grid unit of the arc plate is in a frustum shape with a large bottom opening and a small top opening. The curved plates are not bent to a great extent and are therefore still mounted in the electrolytic cell generally in a substantially horizontal direction.
The present embodiment also provides a purification method of a lithium salt, the purification method using the above purification apparatus, the purification method comprising the steps of:
taking a positive electrode material of a waste lithium battery as a cathode and a graphite electrode as an anode; the manufacturing method of the cathode comprises the following steps: taking the anode material of the waste lithium battery, sequentially disassembling, calcining, washing, drying and grindingGrinding and pressing to obtain cathode with electrode thickness of 7mm and compacted density of 7g/cm3。
Adding ammonium carbonate electrolyte with the concentration of 0.5moL/L into an electrolytic cell, immersing a cathode and an anode into the ammonium carbonate electrolyte, carrying out electrochemical reaction, wherein the applied potential of the electrochemical reaction is 0.2-1.5V, the applied potential value is adjusted from large to small, the time of applying the potential is 4h, so as to obtain a solution containing lithium ions, the solution containing the lithium ions also contains other metal ions, and the leaching sequence of the metal ions is as follows: lithium ion, nickel ion, cobalt ion, manganese ion.
Concentrating the solution containing lithium ions obtained through the electrochemical reaction so as to purify the lithium ions subsequently, wherein the concentration of the lithium ions to be purified is more than or equal to 25 g/L; then, the concentrated solution containing lithium ions is adjusted to be alkaline.
Opening an air inlet pipe, introducing pressurized and heated carbon dioxide into the solution containing the lithium ions and adjusted to be alkaline, improving the solubility of the carbon dioxide by utilizing a pressurized air injection and carbon dioxide heating treatment mode, promoting the concentration of the solution containing the lithium ions by utilizing a carbon dioxide heating treatment mode, and filtering to obtain lithium salt precipitates and a residual solution; crystallizing, washing and drying the lithium salt precipitate in sequence to obtain purified lithium salt; the residual solution is used as electrolyte for recycling.
Example four
This embodiment provides a lithium salt purification apparatus, which is the same as the purification apparatus in the first embodiment, and therefore, the detailed description thereof is omitted.
The present embodiment also provides a purification method of a lithium salt, the purification method using the above purification apparatus, the purification method comprising the steps of:
taking a positive electrode material of a waste lithium battery as a cathode and a graphite electrode as an anode; the manufacturing method of the cathode comprises the following steps: taking the anode material of the waste lithium battery, disassembling, calcining, washing, drying, grinding and pressing to form to obtain a cathode, wherein the thickness of the cathode is 5mm, and the cathode is formedHas a compacted density of 5g/cm3。
Adding ammonium carbonate electrolyte with the concentration of 0.1moL/L into an electrolytic cell, immersing a cathode and an anode into the ammonium carbonate electrolyte, carrying out electrochemical reaction, wherein the applied potential of the electrochemical reaction is 0.2-1.5V, the applied potential value is adjusted from large to small, the time of applying the potential is 2h, so as to obtain a solution containing lithium ions, the solution containing the lithium ions also contains other metal ions, and the leaching sequence of the metal ions is as follows: lithium ion, nickel ion, cobalt ion, manganese ion.
Concentrating the solution containing lithium ions obtained through the electrochemical reaction so as to purify the lithium ions subsequently, wherein the concentration of the lithium ions to be purified is more than or equal to 25 g/L; then, the concentrated solution containing lithium ions is adjusted to be alkaline.
Opening an air inlet pipe, introducing pressurized and heated carbon dioxide into the solution containing the lithium ions and adjusted to be alkaline, improving the solubility of the carbon dioxide by utilizing a pressurized air injection and carbon dioxide heating treatment mode, promoting the concentration of the solution containing the lithium ions by utilizing a carbon dioxide heating treatment mode, and filtering to obtain lithium salt precipitates and a residual solution; crystallizing, washing and drying the lithium salt precipitate in sequence to obtain purified lithium salt; the residual solution recovers the cobalt ions, the nickel ions and the manganese ions, so that the three are conveniently used for the subsequent production of the lithium electronic electrode material.
The method comprises the following steps: and adjusting the molar ratio of the cobalt ions, the nickel ions and the manganese ions in the residual mixed solution to ensure that the molar ratio of the cobalt, the nickel and the manganese is 1:1:1, wherein the cobalt, the nickel and the manganese with the molar ratio can be directly used for preparing corresponding battery raw materials. Compared with the method of extracting cobalt, nickel and manganese respectively and then adjusting the mixture ratio of the cobalt, the nickel and the manganese to accord with the manufacture of corresponding battery electrode materials, the method of the embodiment is adopted to directly adjust the molar ratio of the cobalt, the nickel and the manganese in the residual mixed solution without lithium ions, so that the method can be directly used for the production of the battery electrode materials, the method is simpler, and simultaneously, the whole method is more environment-friendly because other chemical reagents are not required to be additionally added in the whole process.
It is understood that, in this embodiment, the molar ratio of cobalt, nickel and manganese can be adjusted to 5:2:3 or 8:1:1, and the two ratios of cobalt, nickel and manganese can also be directly used for preparing corresponding battery raw materials.
In the first to fourth embodiments, the present invention can effectively recover metals with high utility value, such as lithium, nickel, cobalt, manganese, etc., from waste battery electrode materials by using electrochemical reaction. Moreover, the potential of the electrochemical reaction is controlled to gradually increase from small to large, so that the recovered metal is controlled to be leached step by step according to the sequence of lithium, nickel, cobalt and manganese, the separation procedure of the recovered different metal ions is simplified, and the energy consumption for separating the different metal ions is reduced. Furthermore, in the method of the above embodiment, the thickness of the cathode electrode is also limited, and since the ion transmission efficiency is affected by the excessive thickness of the cathode electrode, the thickness of the cathode electrode in the above embodiment is 5-10 mm.
More importantly, since lithium ions in the solution containing lithium ions obtained by the electrochemical reaction are still in an ionic state, and other impurities may be doped in the solution, it is necessary to purify the solution. Therefore, in the method of the embodiment, the purification scheme for recovering lithium ions is further optimized, specifically, only carbon dioxide is needed to be introduced, lithium carbonate, which is a lithium salt precipitate, can be obtained, and then the purified lithium salt is finally obtained through crystallization, washing and drying. When the method is used for purifying the lithium salt, no additional reagent is needed to be added, and the rest mixed solution except the lithium salt precipitate can be used as the electrolyte for recycling, so that the whole method is more green and environment-friendly, and new waste liquid to be treated can not be generated. Moreover, the invention also improves the reaction efficiency of carbonate and lithium ions by concentrating the solution containing lithium ions before carbon dioxide passes through, and improves the effect of converting carbon dioxide into carbonate ions by adjusting the solution containing lithium ions to be alkaline, thereby achieving better precipitation and purification effects.
Furthermore, in the fourth embodiment, the mole ratio of cobalt, nickel and manganese in the remaining mixed solution is adjusted, so that cobalt, nickel and manganese with a specific proportion can be directly used for preparing related battery raw materials, cobalt, nickel and manganese do not need to be extracted respectively, the proportion is adjusted again, a plurality of links are omitted, and the whole method is more convenient and more environment-friendly.
The above detailed description is provided for the lithium salt purification device and purification method disclosed in the embodiments of the present invention, and the principle and embodiments of the present invention are explained in detail herein by using specific examples, and the above description of the embodiments is only provided to help understanding the method and core ideas of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims (13)

1. A purification apparatus of a lithium salt, comprising:
an electrolytic cell comprising a layer of anode material, the layer of anode material serving as an anode, the anode being an inert electrode;
the cathodes are waste lithium battery electrode materials;
the gas inlet pipe is communicated with the bottom wall of the electrolytic cell or the bottom of the side wall of the electrolytic cell;
the purification method for purifying a lithium salt using the purification apparatus includes the steps of:
taking the electrode material of the waste lithium battery as a cathode and the inert electrode as an anode;
adding electrolyte into the electrolytic cell, so that the cathode and the anode are immersed into the electrolyte, and performing electrochemical reaction under an applied potential to obtain a solution containing lithium ions; wherein the electrolyte contains Na+、NH4 +、K+、Li+、Fe2+、Mn2 +、Ni2+、Co2+、Co3+、Al3+Ion(s)An inorganic salt of at least one cation;
wherein, during the electrochemical reaction, the applied potential is adjusted to be 0.9-1.4V to leach the lithium ions, and the applied potential is adjusted to be 0.2-0.5V to leach the cobalt ions and the nickel ions in the solution containing the lithium ions;
and opening the air inlet pipe, and introducing carbon dioxide into the solution containing the lithium ions after the reaction to obtain lithium salt precipitate and residual solution.
2. The purifying apparatus of claim 1, wherein the electrolytic cell further comprises a structural support layer disposed outside the anode material layer, wherein the thickness of the anode material layer is 5-12 mm; the material of the structure supporting layer is selected from concrete, cement, stone, rubber or resin; a sealing upper cover is arranged above the electrolytic cell, and the sealing upper cover and the electrolytic cell jointly enclose to form a closed cavity; the sealed upper cover is also provided with a reagent feeding port.
3. The purifying apparatus of claim 1, wherein a grid plate is detachably installed in the electrolytic cell in a horizontal direction, and the grid plate is made of an insulating material; the grid plate is a flat plate arranged along the horizontal direction, and any grid unit of the flat plate is square or frustum-shaped.
4. The purifying apparatus of claim 1, wherein a grid plate is detachably installed inside the electrolytic cell, and the grid plate is made of an insulating material; the grid plate is an arc plate with an upward bending radian, and any grid unit of the arc plate is frustum-shaped.
5. The purifying apparatus of claim 3 or 4, wherein a support is further fixed to the bottom of the grid plate, and the support is made of an insulating material.
6. The purifying apparatus as claimed in claim 3 or 4, wherein the inner wall of the electrolytic cell is provided with a receiving platform extending horizontally toward the inside of the electrolytic cell, and the grid plate is erected on the receiving platform.
7. A purification method of a lithium salt using the purification apparatus of a lithium salt according to any one of claims 1 to 6, comprising the steps of:
taking the electrode material of the waste lithium battery as a cathode and the inert electrode as an anode;
adding electrolyte into the electrolytic cell, so that the cathode and the anode are immersed into the electrolyte, and performing electrochemical reaction under an applied potential to obtain a solution containing lithium ions;
and opening the air inlet pipe, and introducing carbon dioxide into the solution containing the lithium ions after the reaction to obtain lithium salt precipitate and residual solution.
8. The purification method according to claim 7, further comprising: before introducing carbon dioxide, concentrating the solution containing lithium ions to ensure that the concentration of the lithium ions in the solution containing lithium ions is more than or equal to 25 g/L; and/or, the solution containing lithium ions is adjusted to be alkaline before the carbon dioxide is introduced.
9. The purification method according to any one of claims 7 or 8, wherein the solution containing lithium ions further comprises at least one of nickel ions, cobalt ions, and manganese ions.
10. The purification method according to claim 9, wherein the electrochemical reaction is carried out at a potential of 0.2 to 1.5V for 1.5 to 8 hours; in the purification method, the solution containing lithium ions further comprises the nickel ions, the cobalt ions and the manganese ions, and when the electrochemical reaction is carried out, the applied potential is adjusted to leach the lithium ions, the nickel ions, the cobalt ions and the manganese ions step by step.
11. The purification method as claimed in claim 9, wherein the electrochemical reaction is carried out by adjusting the applied potential to 0.9 to 1.4V to leach out the lithium ions and adjusting the applied potential to 0.2 to 0.5V to leach out the cobalt ions and the nickel ions.
12. The purification method according to claim 9, further comprising: crystallizing, washing and drying the obtained lithium salt precipitate in sequence to obtain purified lithium salt; the residual solution is used as the electrolyte for recycling, or the molar ratio of the cobalt ions, the nickel ions and the manganese ions in the residual solution is adjusted to be 1:1:1, or 5:2:3, or 8:1: 1; in the purification method, when carbon dioxide is introduced, the carbon dioxide is subjected to pressurization and heating treatment.
13. The purification method according to any one of claims 7 or 8, wherein the cathode is fabricated by: taking the waste lithium battery electrode material, sequentially disassembling, calcining, washing, drying, grinding and pressing to form to obtain the cathode, wherein the electrode thickness of the cathode is 5-10 mm, and the compaction density of the cathode is 5-10 g/cm3(ii) a The cathode is selected from a positive electrode material and/or a negative electrode material of the waste lithium battery, and the inert electrode is a graphite electrode or a conductive inert metal electrode; the electrolyte contains Na+、NH4 +、K+、Li+、Fe2+、Mn2+、Ni2+、Co2+、Co3+、Al3+At least one kind of cation inorganic salt in the ions, and the concentration of the inorganic salt in the electrolyte is 0.1-1.0 moL/L.
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