Method for electrolytic recovery of waste ternary lithium batteries

Abstract

An electrolytic recovery method of waste ternary lithium battery, comprising manganese lithium recovery process, nickel recovery process and cobalt recovery process in sequence, each recovery process comprising slurry preparation, leaching electrolysis and deposition electrolysis, wherein the leaching electrolysis is responsible for converting the metal from solid state to ionic form to enter the electrolyte, and the deposition electrolysis is responsible for depositing the metal ion into solid metal for recovery, and the three processes are sequentially limited to pH values of 12-14, 6-8 and 2-4, respectively, to realize the individual leaching of each metal, so as to sequentially and hierarchically obtain lithium carbonate, solid electrolytic manganese, solid electrolytic nickel and solid electrolytic cobalt. The design not only can separately recover each metal, has better recovery effect, and has higher production efficiency, and is very suitable for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to a recycling process of waste ternary lithium battery, belonging to the field of battery recycling, especially relates to an electrolytic recycling method of waste ternary lithium battery. BACKGROUND

[0002] The ternary lithium battery refers to the lithium battery using lithium nickel cobalt manganese oxide (Li(NiCoMn)O2) or lithium nickel cobalt aluminum oxide as the positive electrode material. Compared with lithium cobalt oxide battery, the ternary lithium ion battery has higher safety, higher capacity, larger specific energy density, higher working voltage, smaller self-discharge and better cycle performance, so it can be widely used in consumer battery market and occupies a major share of power battery market in electric vehicle field. In addition, waste lithium ion battery contains high-value metals such as nickel, cobalt, manganese and lithium, so recycling lithium, nickel, cobalt and manganese is a very valuable technology.

[0003] The invention patent application with the application number 202111134969.4 and the application date of September 27, 2021 discloses a recycling method of nickel-cobalt-manganese ternary lithium battery, which comprises the following steps: pretreating the nickel-cobalt-manganese ternary lithium battery to obtain a positive electrode powder; dissolving the positive electrode powder in an acid solution and adding a reducing agent to obtain a first mixed solution; adding a complexing agent and a precipitating agent to the first mixed solution, the complexing agent is complexed with aluminum ions, the pH value of the first mixed solution is adjusted, the nickel ions, cobalt ions, manganese ions and aluminum ions are precipitated to obtain a four-element precursor, and a second mixed solution is obtained; adding sodium carbonate to the second mixed solution to precipitate lithium ions, and mixing the precipitated lithium carbonate with the four-element precursor to obtain a mixed precipitate. Although the application can recycle waste ternary lithium battery, and can make nickel ions, cobalt ions, manganese ions and aluminum ions co-precipitate, and finally obtain a mixed precipitate containing nickel, cobalt, manganese and aluminum, it has the following defects:

[0004] The application finally obtains a mixed precipitate containing nickel, cobalt, manganese and aluminum, without separating the valuable metals such as nickel, cobalt and manganese, which is not conducive to subsequent utilization, increases the cost of subsequent utilization, and limits the application range of subsequent utilization, so the recycling effect is poor.

[0005] The information disclosed in this BACKGROUND section is only for the purpose of increasing the understanding of the general background of the application, and should not be considered as acknowledging or implying in any form that this information constitutes prior art known to those of ordinary skill in the art. SUMMARY

[0006] The purpose of the present application is to overcome the defects and problems in the prior art that the metals cannot be recovered separately and the recycling effect is poor, and to provide an electrolytic recycling method of waste ternary lithium battery which can recover the metals separately and has better recycling effect.

[0007] To achieve the above object, the technical solution of the present application is: a waste ternary lithium battery electrolytic recovery method, comprising manganese lithium recovery process, nickel recovery process, cobalt recovery process in turn;

[0008] The manganese lithium recovery process refers to: first, prepare manganese lithium recovery slurry in the anode chamber, then carry out leaching electrolysis by passing electricity, at the same time, stir the manganese lithium recovery slurry to make the slurry contact with the anode stick, then, after the electrolysis is completed, the slurry is extracted and filtered to obtain first filter residue and first filter liquor, then, carbonic acid is introduced into the first filter liquor to obtain lithium carbonate precipitation, then, the remaining liquid except lithium carbonate is added into the cathode chamber, before the addition, the anode chamber is empty or is provided with manganese lithium recovery slurry, then, after the addition, carry out deposition electrolysis to deposit solid electrolytic manganese on the cathode stick;

[0009] The nickel recovery process refers to: first, prepare nickel recovery slurry in the anode chamber, then carry out leaching electrolysis by passing electricity, at the same time, stir the nickel recovery slurry to make the slurry contact with the anode stick, then, after the electrolysis is completed, the slurry is extracted and filtered to obtain second filter residue and second filter liquor, then, the second filter liquor is added into the cathode chamber, before the addition, the anode chamber is empty or is provided with nickel recovery slurry, then, after the addition, carry out deposition electrolysis to deposit solid electrolytic nickel on the cathode stick;

[0010] The cobalt recovery process refers to: first, prepare cobalt recovery slurry in the anode chamber, then carry out leaching electrolysis by passing electricity, at the same time, stir the cobalt recovery slurry to make the slurry contact with the anode stick, then, after the electrolysis is completed, the slurry is extracted and filtered to obtain third filter residue and third filter liquor, then, the third filter liquor is added into the cathode chamber, before the addition, the anode chamber is empty or is provided with cobalt recovery slurry, then, after the addition, carry out deposition electrolysis to deposit solid electrolytic cobalt on the cathode stick;

[0011] The preparation step of the manganese lithium recovery slurry is: first, dissolve sodium hydroxide or ammonia water in pure water at 50g / l-120g / l, the pH value is 12-14, then add battery solid waste powder to obtain manganese lithium recovery slurry, the mass of the battery solid waste powder is 15%-30% of the mass of the manganese lithium recovery slurry;

[0012] The preparation step of the nickel recovery slurry is: first, dissolve nickel recovery solute in pure water at 50g / l-120g / l, the pH value is 6-8, then add first filter residue to obtain nickel recovery slurry, the mass of the first filter residue is 15%-30% of the mass of the nickel recovery slurry; the nickel recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and nickel sulfate;

[0013] The preparation step of the cobalt recovery slurry is: first, the cobalt recovery solute is dissolved in pure water at 50g / l-120g / l, the pH value is 2-4, then the secondary filter residue is added to obtain the cobalt recovery slurry, the mass of the secondary filter residue is 15%-30% of the mass of the cobalt recovery slurry; the cobalt recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and cobalt sulfate;

[0014] The anode chamber is connected with the corresponding cathode chamber through a permeable membrane, an anode rod is inserted into the anode chamber, and a cathode rod is inserted into the cathode chamber.

[0015] The material of the anode rod is graphite or a ruthenium-titanium-coated plate, and the material of the cathode rod is a titanium plate.

[0016] The material of the battery solid waste is a solid waste in a ternary lithium battery, and includes a positive electrode material of the ternary lithium battery.

[0017] In the manganese-lithium recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2.

[0018] In the nickel recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2.

[0019] In the cobalt recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 2.5-4.0v and a current of 100-200A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 2.5-4.0v and a current of 100-200A / m2.

[0020] The reaction time of leaching electrolysis and deposition electrolysis in the manganese-lithium recovery process, the nickel recovery process and the cobalt recovery process is 48 hours, and the current efficiency is 75%-85%.

[0021] The electrolytic recovery method has any one or any combination of the following three limitations:

[0022] In the manganese-lithium recovery process, the leaching rate of manganese-lithium after leaching electrolysis is greater than or equal to 99.9%, in the nickel recovery process, the leaching rate of nickel after leaching electrolysis is greater than or equal to 99.9%, and in the cobalt recovery process, the leaching rate of cobalt after leaching electrolysis is greater than or equal to 99.9%.

[0023] The agitating blades are arranged in the anode chamber, and the agitating of the manganese-lithium recovery slurry, the agitating of the nickel recovery slurry and the agitating of the cobalt recovery slurry are all realized by the rotation of the agitating blades, and the agitating time is 10-30 min.

[0024] In the preparation step of the manganese-lithium recovery slurry, the pH value is 13; in the preparation step of the nickel recovery slurry, the pH value is 7; and in the preparation step of the cobalt recovery slurry, the pH value is 3.

[0025] The anode chamber and the cathode chamber are arranged in the structure that at least two electrolytic device groups are independently arranged, each electrolytic device group comprises three electrolytic devices A, B and C which are independently arranged, and the electrolytic devices A, B and C all comprise anode chambers and cathode chambers which are communicated through permeable membranes; the leaching electrolysis and the deposition electrolysis in the manganese-lithium recovery process are carried out in the electrolytic device A, the leaching electrolysis and the deposition electrolysis in the nickel recovery process are carried out in the electrolytic device B, and the leaching electrolysis and the deposition electrolysis in the cobalt recovery process are carried out in the electrolytic device C.

[0026] In the manganese-lithium recovery process, the manganese-lithium recovery slurry is arranged in the anode chamber before the residual liquid except lithium carbonate is added into the cathode chamber, and the operation is cross carried out in all electrolytic devices A; in the nickel recovery process, the nickel recovery slurry is arranged in the anode chamber before the secondary filtrate is added into the cathode chamber, and the operation is cross carried out in all electrolytic devices B; and in the cobalt recovery process, the cobalt recovery slurry is arranged in the anode chamber before the tertiary filtrate is added into the cathode chamber, and the operation is cross carried out in all electrolytic devices C.

[0027] The number of the electrolytic device groups is three.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] 1. The electrolytic recovery method of the waste ternary lithium battery, mainly includes manganese lithium recovery process, nickel recovery process and cobalt recovery process which are sequentially performed, and each recovery process includes slurry preparation, leaching electrolysis and deposition electrolysis, wherein the leaching electrolysis is responsible for the conversion of metal from solid state to ionic form and into the electrolyte, and the deposition electrolysis is responsible for the deposition of ionic metal ions into solid metal for recovery, the pH value is sequentially limited to 12-14, 6-8 and 2-4 to realize the step-by-step leaching of each metal, and then the corresponding deposition electrolysis is sequentially performed to obtain lithium carbonate, solid electrolytic manganese, solid electrolytic nickel and solid electrolytic cobalt in sequence and in stages, thereby realizing the separate recovery of lithium, manganese, nickel and cobalt, which is beneficial to subsequent reuse and presents a staged and sequential operation sequence as a whole, has high work efficiency and is suitable for industrial production. Therefore, the present application can not only recover each metal separately, but also has high production efficiency.

[0030] 2. In the electrolytic recovery method of the waste ternary lithium battery, when preparing the manganese lithium recovery slurry, the nickel recovery slurry and the cobalt recovery slurry, the nickel recovery slurry and the cobalt recovery slurry both use the filter residue obtained in the previous step, i.e. primary filter residue and secondary filter residue, except that the manganese lithium recovery slurry uses battery solid waste powder. This technology can not only realize the separate recovery of various metals in stages, but also presents a sequence of connection between the front and rear in the operation sequence, which is beneficial to form a flow line type operation, improves work efficiency, and can maximize the recovery of metals and improve the recovery rate. Therefore, the present application can not only recover each metal separately, but also has high work efficiency.

[0031] 3. In the electrolytic recovery method of the waste ternary lithium battery, the material of the battery solid waste is preferably the solid waste in the ternary lithium battery, and includes the positive electrode material of the ternary lithium battery. This technical feature makes the present application not limited to the recovery and treatment of the positive electrode material in the waste lithium battery, but can directly treat the positive electrode material and the remaining materials combined together, which not only saves the operation steps, but also expands the application range of the present application. Therefore, the application field of the present application is wide.

[0032] 4、The electrolytic recovery method of the waste ternary lithium battery can improve the overall work efficiency, at least two independent electrolytic device groups can be arranged, each electrolytic device group includes three independent electrolytic device A, electrolytic device B and electrolytic device C, wherein the slurry preparation, leaching electrolysis and deposition electrolysis in the manganese lithium recovery process are carried out in the electrolytic device A, the slurry preparation, leaching electrolysis and deposition electrolysis in the nickel recovery process are carried out in the electrolytic device B, and the slurry preparation, leaching electrolysis and deposition electrolysis in the cobalt recovery process are carried out in the electrolytic device C, in application, with the sequential performance of the three recovery processes, the slurry is continuously prepared, leached and deposited, the filter residue is continuously used to prepare the slurry in the next process, and the electrolyte can be continuously injected into the cathode chamber to perform electrolysis reaction with the slurry in the anode chamber, so that the deposition electrolysis and leaching electrolysis are performed at the same time, the energy utilization rate during electrolysis is improved, the production cost is reduced, all processes and the slurry preparation, leaching electrolysis and deposition electrolysis in each process are continuously performed, the flow line operation is realized, and the work efficiency is maximally improved. Therefore, the present application has low production cost and high work efficiency, and is very suitable for large-scale production. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is the operation flowchart of the present application.

[0034] Figure 2 is the structural schematic view of the anode chamber and the cathode chamber in the present application.

[0035] Figure 3 is the arrangement schematic view of the anode chamber and the cathode chamber in Example 4 of the present application.

[0036] In the figure: permeable membrane 1, anode chamber 2, anode rod 21, stirring blade 22, cathode chamber 3, cathode rod 31, electrolytic device group 4, electrolytic device A 41, electrolytic device B 42, electrolytic device C 43. DETAILED DESCRIPTION

[0037] The present application will be further described in detail in combination with the description of the drawings and specific embodiments.

[0038] Referring to Figure 1 — Figure 3 An electrolytic recovery method of waste ternary lithium battery, including manganese lithium recovery process, nickel recovery process and cobalt recovery process performed in sequence;

[0039] The manganese lithium recovery process refers to: first, preparing manganese lithium recovery slurry in the anode chamber 2, then conducting leaching electrolysis by power supply, at the same time, stirring the manganese lithium recovery slurry to make the slurry contact with the anode stick 21, then pumping out the slurry after electrolysis and filtering to obtain primary filter residue and primary filtrate, then introducing carbonic acid into the primary filtrate to obtain lithium carbonate precipitation, then adding the remaining liquid except lithium carbonate into the cathode chamber 3, before the addition, the anode chamber 2 is empty or is provided with manganese lithium recovery slurry, then conducting deposition electrolysis after the addition to deposit solid electrolytic manganese on the cathode stick 31;

[0040] The nickel recovery process refers to: first, preparing nickel recovery slurry in the anode chamber 2, then conducting leaching electrolysis by power supply, at the same time, stirring the nickel recovery slurry to make the slurry contact with the anode stick 21, then pumping out the slurry after electrolysis and filtering to obtain secondary filter residue and secondary filtrate, then adding the secondary filtrate into the cathode chamber 3, before the addition, the anode chamber 2 is empty or is provided with nickel recovery slurry, then conducting deposition electrolysis after the addition to deposit solid electrolytic nickel on the cathode stick 31;

[0041] The cobalt recovery process refers to: first, preparing cobalt recovery slurry in the anode chamber 2, then conducting leaching electrolysis by power supply, at the same time, stirring the cobalt recovery slurry to make the slurry contact with the anode stick 21, then pumping out the slurry after electrolysis and filtering to obtain tertiary filter residue and tertiary filtrate, then adding the tertiary filtrate into the cathode chamber 3, before the addition, the anode chamber 2 is empty or is provided with cobalt recovery slurry, then conducting deposition electrolysis after the addition to deposit solid electrolytic cobalt on the cathode stick 31;

[0042] The preparation step of the manganese lithium recovery slurry is: first, dissolving sodium hydroxide or ammonia water in pure water at 50g / l-120g / l, the pH value is 12-14, then adding battery solid waste powder to obtain manganese lithium recovery slurry, the mass of the battery solid waste powder is 15%-30% of the mass of the manganese lithium recovery slurry;

[0043] The preparation step of the nickel recovery slurry is: first, dissolving nickel recovery solute in pure water at 50g / l-120g / l, the pH value is 6-8, then adding primary filter residue to obtain nickel recovery slurry, the mass of the primary filter residue is 15%-30% of the mass of the nickel recovery slurry; the nickel recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and nickel sulfate;

[0044] The preparation step of the cobalt recovery slurry is: first, dissolving cobalt recovery solute in pure water at 50g / l-120g / l, the pH value is 2-4, then adding secondary filter residue to obtain cobalt recovery slurry, the mass of the secondary filter residue is 15%-30% of the mass of the cobalt recovery slurry; the cobalt recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and cobalt sulfate.

[0045] The anode chamber 2 is connected with the corresponding cathode chamber 3 through the permeable membrane 1, the anode rod 21 is inserted in the anode chamber 2, and the cathode rod 31 is inserted in the cathode chamber 3.

[0046] The material of the anode rod 21 is graphite or a ruthenium titanium coated plate, and the material of the cathode rod 31 is a titanium plate.

[0047] The material of the battery solid waste is a solid waste in a ternary lithium battery, and includes a positive electrode material of the ternary lithium battery.

[0048] In the manganese lithium recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2.

[0049] In the nickel recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 3.5-4.5v and a current of 200-400A / m2.

[0050] In the cobalt recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 2.5-4.0v and a current of 100-200A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 2.5-4.0v and a current of 100-200A / m2.

[0051] The reaction time of leaching electrolysis and deposition electrolysis in the manganese lithium recovery process, the nickel recovery process and the cobalt recovery process is 48 hours, and the current efficiency is 75%-85%.

[0052] The electrolytic recovery method has any one or any combination of the following three limitations.

[0053] In the manganese lithium recovery process, the leaching rate of manganese lithium after the end of leaching electrolysis is greater than or equal to 99.9%, in the nickel recovery process, the leaching rate of nickel after the end of leaching electrolysis is greater than or equal to 99.9%, and in the cobalt recovery process, the leaching rate of cobalt after the end of leaching electrolysis is greater than or equal to 99.9%.

[0054] The anode chamber 2 is provided with stirring blades 22, and the stirring of the manganese lithium recovery slurry, the stirring of the nickel recovery slurry and the stirring of the cobalt recovery slurry are all performed through the rotation of the stirring blades 22, and the stirring time is 10-30min.

[0055] In the preparation step of the manganese lithium recovery slurry, the pH value is 13; in the preparation step of the nickel recovery slurry, the pH value is 7; and in the preparation step of the cobalt recovery slurry, the pH value is 3.

[0056] The anode chamber 2 and the cathode chamber 3 are arranged in a structure comprising at least two independent electrolytic device groups 4, each electrolytic device group 4 comprising three independent electrolytic devices A 41, B 42 and C 43, each of the electrolytic devices A 41, B 42 and C 43 comprising an anode chamber 2 and a cathode chamber 3 in communication with each other through a permeable membrane 1; the leaching electrolysis and deposition electrolysis in the manganese and lithium recovery process are carried out in the electrolytic device A 41, the leaching electrolysis and deposition electrolysis in the nickel recovery process are carried out in the electrolytic device B 42, and the leaching electrolysis and deposition electrolysis in the cobalt recovery process are carried out in the electrolytic device C 43;

[0057] In the manganese and lithium recovery process, before the remaining liquid except lithium carbonate is added to the cathode chamber 3, a manganese and lithium recovery slurry is arranged in the anode chamber 2, and this operation is cross-performed in all electrolytic devices A 41; in the nickel recovery process, before the secondary filtrate is added to the cathode chamber 3, a nickel recovery slurry is arranged in the anode chamber 2, and this operation is cross-performed in all electrolytic devices B 42; in the cobalt recovery process, before the tertiary filtrate is added to the cathode chamber 3, a cobalt recovery slurry is arranged in the anode chamber 2, and this operation is cross-performed in all electrolytic devices C 43.

[0058] The number of the electrolytic device groups 4 is three.

[0059] The principle of the present application is explained as follows:

[0060] The "stirring to make the slurry contact with the anode rod" in the present application refers to: through the mode of stirring, the slurry is fully contacted with the anode rod, so that the probability of collision between the powder in the slurry and the anode rod is large, so that the probability of electrolysis of the powder is large, avoiding the phenomenon of anode oxygen evolution, reducing the current efficiency. In addition, in the state of stirring, the electrolysis is carried out, so that the powder or filter residue and other solid substances in the slurry are in a suspended state, which can collide with the anode rod with a larger probability, thereby improving the electrolysis effect.

[0061] The permeable membrane 1 in the present application does not hinder the flow of liquid between the anode chamber 2 and the cathode chamber 3, but only blocks the flow of solid substances such as powder in the slurry, avoiding the flow of powder from the anode chamber 2 to the cathode chamber 3.

[0062] Example 1:

[0063] An electrolytic recovery method of waste ternary lithium battery, comprising a manganese and lithium recovery process, a nickel recovery process and a cobalt recovery process performed in sequence; the anode chamber 2 used in all processes is in communication with the corresponding cathode chamber 3 through a permeable membrane 1, an anode rod 21 is inserted into the anode chamber 2, and a cathode rod 31 is inserted into the cathode chamber 3;

[0064] The manganese lithium recovery process refers to: first, preparing manganese lithium recovery slurry in the anode chamber 2, then conducting immersion electrolysis by power supply, at the same time, stirring the manganese lithium recovery slurry to make the slurry contact with the anode rod 21, then pumping out the slurry after electrolysis and filtering to obtain primary filter residue and primary filter liquor, then introducing carbonic acid into the primary filter liquor to obtain lithium carbonate precipitation, then adding the remaining liquid except lithium carbonate into the cathode chamber 3, before the addition, the anode chamber 2 is empty or is provided with manganese lithium recovery slurry, then conducting deposition electrolysis after the addition to deposit solid electrolytic manganese on the cathode rod 31; the preparation step of the manganese lithium recovery slurry is: first, dissolving sodium hydroxide or ammonia water in pure water at 50g / l-120g / l, the pH value is 12-14, then adding battery solid waste powder to obtain manganese lithium recovery slurry, the mass of the battery solid waste powder is 15%-30% of the mass of the manganese lithium recovery slurry; the operation parameters of the immersion electrolysis are power supply voltage 3.5-4.5v and current 200-400A / m2, the operation parameters of the deposition electrolysis are power supply voltage 3.5-4.5v and current 200-400A / m2;

[0065] The nickel recovery process refers to: first, preparing nickel recovery slurry in the anode chamber 2, then conducting immersion electrolysis by power supply, at the same time, stirring the nickel recovery slurry to make the slurry contact with the anode rod 21, then pumping out the slurry after electrolysis and filtering to obtain secondary filter residue and secondary filter liquor, then adding the secondary filter liquor into the cathode chamber 3, before the addition, the anode chamber 2 is empty or is provided with nickel recovery slurry, then conducting deposition electrolysis after the addition to deposit solid electrolytic nickel on the cathode rod 31; the preparation step of the nickel recovery slurry is: first, dissolving nickel recovery solute in pure water at 50g / l-120g / l, the pH value is 6-8, then adding primary filter residue to obtain nickel recovery slurry, the mass of the primary filter residue is 15%-30% of the mass of the nickel recovery slurry; the nickel recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and nickel sulfate; the operation parameters of the immersion electrolysis are power supply voltage 3.5-4.5v and current 200-400A / m2, the operation parameters of the deposition electrolysis are power supply voltage 3.5-4.5v and current 200-400A / m2;

[0066] The cobalt recovery process refers to: first, preparing cobalt recovery slurry in the anode chamber 2, then conducting electrolysis, at the same time, stirring the cobalt recovery slurry to make the slurry contact with the anode rod 21, then extracting the slurry after electrolysis and filtering to obtain the third filter residue and the third filter liquor, then adding the third filter liquor into the cathode chamber 3, before adding, the anode chamber 2 is empty or is provided with cobalt recovery slurry, then after adding, depositing electrolysis is conducted to deposit solid electrolytic cobalt on the cathode rod 31; the preparation step of the cobalt recovery slurry is: first, dissolving cobalt recovery solute in pure water at 50g / l-120g / l, pH value is 2-4, then adding secondary filter residue to obtain cobalt recovery slurry, the mass of the secondary filter residue is 15%-30% of the mass of the cobalt recovery slurry; the cobalt recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and cobalt sulfate; the operating parameters of the leaching electrolysis are power voltage 2.5-4.0v and current 100-200A / m2, and the operating parameters of the depositing electrolysis are power voltage 2.5-4.0v and current 100-200A / m2.

[0067] Example 2:

[0068] The basic content is the same as that of example 1, except that:

[0069] In the preparation step of the manganese lithium recovery slurry, the pH value is 13; in the preparation step of the nickel recovery slurry, the pH value is 7; in the preparation step of the cobalt recovery slurry, the pH value is 3.

[0070] Example 3:

[0071] The basic content is the same as that of example 1, except that:

[0072] In the manganese lithium recovery process, after the leaching electrolysis is completed, the leaching rate of manganese lithium is greater than or equal to 99.9%, in the nickel recovery process, after the leaching electrolysis is completed, the leaching rate of nickel is greater than or equal to 99.9%, and in the cobalt recovery process, after the leaching electrolysis is completed, the leaching rate of cobalt is greater than or equal to 99.9%.

[0073] Example 4:

[0074] The basic content is the same as that of example 1, except that:

[0075] See Figure 3There are three independent electrolytic device groups 4 in total, each of which comprises three independent electrolytic device A 41, electrolytic device B 42 and electrolytic device C 43, and each of the electrolytic device A 41, electrolytic device B 42 and electrolytic device C 43 comprises an anode chamber 2 and a cathode chamber 3 which are in communication with each other through a permeable membrane 1; the leaching electrolysis and deposition electrolysis in the manganese and lithium recovery process are carried out in the electrolytic device A 41, the leaching electrolysis and deposition electrolysis in the nickel recovery process are carried out in the electrolytic device B 42, and the leaching electrolysis and deposition electrolysis in the cobalt recovery process are carried out in the electrolytic device C 43.

[0076] In use, in the manganese and lithium recovery process, the manganese and lithium recovery slurry is arranged in the anode chamber 2 before the remaining liquid except lithium carbonate is added into the cathode chamber 3, and this operation is carried out in all electrolytic device A 41 crosswise, i.e. selected in the three electrolytic device A 41 according to the respective progress; in the nickel recovery process, the nickel recovery slurry is arranged in the anode chamber 2 before the secondary filtrate is added into the cathode chamber 3, and this operation is carried out in all electrolytic device B 42 crosswise, i.e. selected in the three electrolytic device B 42 according to the respective progress; in the cobalt recovery process, the cobalt recovery slurry is arranged in the anode chamber 2 before the tertiary filtrate is added into the cathode chamber 3, and this operation is carried out in all electrolytic device C 43 crosswise, i.e. selected in the three electrolytic device C 43 according to the respective progress.

[0077] The above description is only the preferred embodiment of the present application, and the protection scope of the present application is not limited to the above embodiment, but any equivalent modification or change made by those skilled in the art according to the disclosed content of the present application shall be included in the protection scope recorded in the claims.

Claims

1. A method for electrolytic recovery of spent ternary lithium batteries, characterized in that: The electrolytic recovery method comprises a manganese-lithium recovery process, a nickel recovery process and a cobalt recovery process which are sequentially performed. The manganese-lithium recovery process refers to that manganese-lithium recovery slurry is prepared in the anode chamber (2), then electrolysis leaching is performed, while the manganese-lithium recovery slurry is stirred to make the slurry contact with the anode rod (21), then the slurry after electrolysis is extracted and filtered to obtain primary filter residue and primary filtrate, carbonic acid is introduced into the primary filtrate to obtain lithium carbonate precipitate, then the remaining liquid except lithium carbonate is added into the cathode chamber (3), before the addition, the anode chamber (2) is empty or is provided with manganese-lithium recovery slurry, then deposition electrolysis is performed after the addition to deposit solid electrolytic manganese on the cathode rod (31); The nickel recovery process refers to that nickel recovery slurry is prepared in the anode chamber (2), then electrolysis leaching is performed, while the nickel recovery slurry is stirred to make the slurry contact with the anode rod (21), then the slurry after electrolysis is extracted and filtered to obtain secondary filter residue and secondary filtrate, then the secondary filtrate is added into the cathode chamber (3), before the addition, the anode chamber (2) is empty or is provided with nickel recovery slurry, then deposition electrolysis is performed after the addition to deposit solid electrolytic nickel on the cathode rod (31); The cobalt recovery process refers to that cobalt recovery slurry is prepared in the anode chamber (2), then electrolysis leaching is performed, while the cobalt recovery slurry is stirred to make the slurry contact with the anode rod (21), then the slurry after electrolysis is extracted and filtered to obtain tertiary filter residue and tertiary filtrate, then the tertiary filtrate is added into the cathode chamber (3), before the addition, the anode chamber (2) is empty or is provided with cobalt recovery slurry, then deposition electrolysis is performed after the addition to deposit solid electrolytic cobalt on the cathode rod (31); The preparation step of the manganese-lithium recovery slurry is that sodium hydroxide or ammonia water is dissolved in pure water at 50g / l-120g / l, the pH value is 12-14, then battery solid waste powder is added to obtain manganese-lithium recovery slurry, the mass of the battery solid waste powder is 15%-30% of the mass of the manganese-lithium recovery slurry; The preparation step of the nickel recovery slurry is that nickel recovery solute is dissolved in pure water at 50g / l-120g / l, the pH value is 6-8, then primary filter residue is added to obtain nickel recovery slurry, the mass of the primary filter residue is 15%-30% of the mass of the nickel recovery slurry; the nickel recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and nickel sulfate; The preparation step of the cobalt recovery slurry is that cobalt recovery solute is dissolved in pure water at 50g / l-120g / l, the pH value is 2-4, then secondary filter residue is added to obtain cobalt recovery slurry, the mass of the secondary filter residue is 15%-30% of the mass of the cobalt recovery slurry; the cobalt recovery solute is any one or any combination of sodium sulfate, sodium sulfamate, sodium methanesulfonate and cobalt sulfate; The anode chamber (2) is connected with the corresponding cathode chamber (3) through the permeable membrane (1), the anode rod (21) is inserted into the anode chamber (2), and the cathode rod (31) is inserted into the cathode chamber (3); The liquid in the anode chamber (2) and the cathode chamber (3) flows through the permeable membrane (1), and the powder in the anode chamber (2) is blocked by the permeable membrane (1).

2. The electrolytic recovery method of waste ternary lithium batteries according to claim 1, characterized in that: The material of the anode rod (21) is graphite or a ruthenium titanium coated plate, and the material of the cathode rod (31) is a titanium plate.

3. The electrolytic recycling method of waste ternary lithium batteries according to claim 1 or 2, characterized in that: The material of the battery solid waste is a solid waste in a ternary lithium battery, and the battery solid waste includes a positive electrode material of the ternary lithium battery.

4. The electrolytic recovery method of the waste ternary lithium battery according to claim 1 or 2, characterized in that: In the manganese lithium recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 3.5-4.5 V and a current of 200-400 A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 3.5-4.5 V and a current of 200-400 A / m2; In the nickel recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 3.5-4.5 V and a current of 200-400 A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 3.5-4.5 V and a current of 200-400 A / m2; In the cobalt recovery process, the operating parameters of leaching electrolysis are a power-on voltage of 2.5-4.0 V and a current of 100-200 A / m2, and the operating parameters of deposition electrolysis are a power-on voltage of 2.5-4.0 V and a current of 100-200 A / m2.

5. The electrolytic recycling method of waste ternary lithium batteries according to claim 1 or 2, characterized in that: The reaction time of leaching electrolysis and deposition electrolysis in the manganese lithium recovery process, the nickel recovery process, and the cobalt recovery process is 48 hours, and the current efficiency is 75%-85%.

6. The electrolytic recycling method of waste ternary lithium batteries according to claim 1 or 2, characterized in that: The electrolytic recovery method has any one or any combination of the following three limitations: In the manganese lithium recovery process, the leaching rate of manganese lithium is greater than or equal to 99.9% after leaching electrolysis is completed, in the nickel recovery process, the leaching rate of nickel is greater than or equal to 99.9% after leaching electrolysis is completed, and in the cobalt recovery process, the leaching rate of cobalt is greater than or equal to 99.9% after leaching electrolysis is completed.

7. The electrolytic recycling method of waste ternary lithium batteries according to claim 1 or 2, characterized in that: The anode chamber (2) is provided with stirring blades (22), and the stirring of the manganese lithium recovery slurry, the stirring of the nickel recovery slurry, and the stirring of the cobalt recovery slurry are all performed by the rotation of the stirring blades (22), and the stirring time is 10-30 min.

8. The electrolytic recycling method of waste ternary lithium batteries according to claim 1 or 2, characterized in that: In the preparation step of the manganese lithium recovery slurry, the pH value is 13; in the preparation step of the nickel recovery slurry, the pH value is 7; and in the preparation step of the cobalt recovery slurry, the pH value is 3.

9. The electrolytic recycling method of waste ternary lithium batteries according to claim 1 or 2, characterized in that: The anode chamber (2) and the cathode chamber (3) are provided in a structure comprising at least two independent electrolytic device groups (4), each electrolytic device group (4) comprising three independent electrolytic device alpha (41), electrolytic device beta (42), and electrolytic device gamma (43), and each of the electrolytic device alpha (41), the electrolytic device beta (42), and the electrolytic device gamma (43) comprises an anode chamber (2) and a cathode chamber (3) that are in communication through a permeable membrane (1); the leaching electrolysis and the deposition electrolysis in the manganese lithium recovery process are performed in the electrolytic device alpha (41), the leaching electrolysis and the deposition electrolysis in the nickel recovery process are performed in the electrolytic device beta (42), and the leaching electrolysis and the deposition electrolysis in the cobalt recovery process are performed in the electrolytic device gamma (43); In the manganese and lithium recovery process, the manganese and lithium recovery slurry is arranged in the anode chamber (2) before the remaining liquid except lithium carbonate is added into the cathode chamber (3), and the operation is cross conducted in all electrolytic devices a (41); in the nickel recovery process, the nickel recovery slurry is arranged in the anode chamber (2) before the secondary filtrate is added into the cathode chamber (3), and the operation is cross conducted in all electrolytic devices b (42); in the cobalt recovery process, the cobalt recovery slurry is arranged in the anode chamber (2) before the tertiary filtrate is added into the cathode chamber (3), and the operation is cross conducted in all electrolytic devices c (43).

10. The electrolytic recycling method of waste ternary lithium batteries according to claim 9, characterized in that: The number of the electrolytic device groups (4) is three.

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