CN111321298A - Method for leaching waste ternary LNCM lithium ion battery and recovering valuable metal - Google Patents
Method for leaching waste ternary LNCM lithium ion battery and recovering valuable metal Download PDFInfo
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- CN111321298A CN111321298A CN201811542133.6A CN201811542133A CN111321298A CN 111321298 A CN111321298 A CN 111321298A CN 201811542133 A CN201811542133 A CN 201811542133A CN 111321298 A CN111321298 A CN 111321298A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to the field of recovery of valuable materials of waste lithium ion batteries; particularly discloses a two-stage countercurrent leaching method for leaching valuable metals from waste lithium ion batteries: a two-stage countercurrent leaching method for waste ternary LNCM lithium ion batteries is characterized in that electrode active materials are recovered from the waste ternary LNCM lithium ion batteries; sequentially carrying out first-stage countercurrent leaching and second-stage countercurrent leaching on the second-stage countercurrent leaching electrode active material in N batches; will NiTaking a second-stage countercurrent leaching solution obtained by performing first-stage countercurrent leaching and second-stage countercurrent leaching on the batch of electrode active materials as the Nthi+1 batch of electrode active material leaching agent by one-stage countercurrent leaching; i is an integer of 1, 2, 3.. N-1; and collecting a section of countercurrent leaching liquid of each batch of electrode active materials, namely the total leaching liquid of the waste lithium ion battery. The method provided by the invention creatively adopts a two-stage countercurrent leaching method, so that the ion concentration of effective components in the leaching solution is efficiently increased, and the utilization rate of the leaching acid is remarkably increased.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, in particular to high-valued recovery of a waste ternary nickel cobalt lithium manganate lithium ion battery, belonging to the field of waste lithium ion battery recovery.
Background
With the rapid development of modern technology, the pollution problem of social energy and environment ecology becomes more and more prominent, and the pollution problem of various waste batteries to the environment and the ecology becomes the focus of social attention. The nickel cobalt lithium manganate ion battery is widely applied to power batteries and energy storage batteries due to the characteristics of high capacity, stable cycle performance, high working platform voltage and the like, and the requirements of the power batteries and the energy storage batteries on battery materials are generally greater than those of conventional small batteries. Therefore, in the future 3-5 years, a large number of nickel cobalt lithium manganate ion batteries are scrapped and have high social value when being recycled.
However, the domestic technical route for recycling the waste nickel cobalt manganese acid battery still has defects at present, and the mainstream way for treating the leachate of the waste nickel cobalt lithium manganate battery is as follows: 1) precipitating to remove copper, and then adjusting the proportion of three elements of nickel, cobalt and manganese, adding alkali for coprecipitation; 2) extracting to remove copper, then extracting nickel, cobalt and manganese, and then performing acid back extraction to obtain a salt solution only containing nickel or cobalt or manganese. For example, the chinese patent CN105206889A discloses a method for processing a positive electrode material of a waste nickel cobalt lithium manganate ternary battery, which uses an acid leaching method to recover valuable metals in the nickel cobalt lithium manganate waste battery, removes impurities by a precipitation method, and then adds alkali to coprecipitate nickel cobalt manganese to prepare a precursor.
The existing leaching process of the waste lithium ion battery has the defects of low acid utilization rate and Ni in the leaching solution2+、Co2+、Mn2+Relatively low concentration, etc.
Disclosure of Invention
In order to solve the technical problems of low acid utilization rate and valuable elements (such as Ni, Co and Mn) in the leachate in the prior art, the invention aims to provide a leaching method of a waste ternary LNCM lithium ion battery, which aims to improve the acid utilization rate and the concentration of the valuable elements in the leachate.
The second purpose of the invention is to provide a method for recovering valuable metals from waste ternary LNCM lithium ion batteries, and aims to provide a method for efficiently and cleanly recovering effective components of nickel cobalt lithium manganate waste batteries.
The recovery process of the waste nickel-cobalt-manganese ternary lithium ion battery has particularity, for example, the content of valuable elements is low, the high-efficiency recovery is difficult by adopting the existing reported method, and a large amount of acidic wastewater is generated in the recovery process to cause secondary pollution. In addition, Ni is contained in the leachate obtained by the traditional acid leaching method2+，Co2+，Mn2+The plasma concentration is low, generally 2-15 g/L, and cannot meet the industrial requirements of static electrolysis production, so the leachate is often subjected to evaporation concentration before static electrolysis, the production cost is increased due to operations such as element separation, and the like, and moreover, the problems of loss of valuable elements, quality change and the like are easily caused when the leachate with low concentration is subjected to concentration treatment.
In order to solve the technical defects, the invention innovatively provides a two-stage countercurrent leaching method of a waste ternary LNCM lithium ion battery, which comprises the following steps:
step (1): recycling electrode active materials from the waste ternary LNCM lithium ion battery;
step (2): two stage countercurrent leaching
The electrode active material is sequentially subjected to first-stage countercurrent leaching and second-stage countercurrent leaching in N batches; wherein the acidity of the leaching agent of the first-stage countercurrent leaching is 0.1-0.5 mol/L; the leaching agent of the second-stage countercurrent leaching contains an organic reducing agent, and the acidity is 0.5-3 mol/L;
will NiTaking a second-stage countercurrent leaching solution obtained by performing first-stage countercurrent leaching and second-stage countercurrent leaching on the batch of electrode active materials as the Nthi+1 batch of electrode active material leaching agent by one-stage countercurrent leaching; i is an integer of 1, 2, 3.. N-1;
and collecting a section of countercurrent leaching liquid of each batch of electrode active materials, namely the total leaching liquid of the waste lithium ion battery.
In order to further improve the recovery effect of valuable components of the waste nickel-cobalt-manganese ternary lithium ion battery, the invention applies the countercurrent leaching technology to the field of waste battery recovery for the first time; the concept of the countercurrent leaching method is innovatively provided, and the control of parameters, particularly acidity, among the steps can be cooperated, so that the concentration of valuable metal ions in the leaching solution can be obviously improved, the leaching solution after impurity removal is not required to be concentrated, the effective utilization rate of the leaching acid can be effectively improved, a large amount of acidic wastewater generated in the recovery process is reduced, and no secondary pollution is caused
Preferably, N is1The first-section countercurrent leaching agent of the batch of electrode active materials is acid liquor a; the leaching agent for the first-stage countercurrent leaching of the other batches of electrode active materials is leachate of the second-stage countercurrent leaching which is recycled.
In the leaching method, the electrode active materials are preferably divided into N batches, and each batch of electrode active materials sequentially passes through the first-stage countercurrent leaching step and the second-stage leaching step; the conditions for one-stage leaching of each batch were the same, the main difference being that the first batch of electrode active material (N)1Batches) in the first-stage leaching process, the acid liquor a with the acidity is added as a starting leaching agent, and the leaching agents in the first-stage leaching of the electrode active materials in the other batches are all leaching liquids in the second-stage leaching of the electrode active materials in the previous batch. The condition control range of each batch of the two-stage leaching process is the same, and the two-stage leaching process is realized by adding a high-acid solution containing an organic reducing agentThe leaching agent, the leachate from the second leaching of the last batch of electrode active material is not circulated, and can be combined into the leachate from the first leaching of other batches to form the total leachate.
The acid solution a is, for example, 0.1 to 0.5mol/L sulfuric acid.
In the invention, the acidity of each leaching step is further reasonably controlled by the two-stage countercurrent leaching process, so that the utilization rate of acid in the leaching process can be further improved, and the organic metal content in the leaching solution can be further improved.
The acidity referred to herein refers to the molar concentration of the acid.
Preferably, the acidity of the second countercurrent leaching process is 2 to 4 times the acidity of the first countercurrent leaching process.
Preferably, the acidity of the leaching agent in the first-stage countercurrent leaching process is 0.3-0.5 mol/L.
Preferably, the acidity of the leaching agent in the two-stage countercurrent leaching process is 1-3 mol/L; further preferably 2 to 3 mol/L.
The first-stage countercurrent leaching agent of the first batch of electrode active materials is a sulfuric acid solution with the concentration of 0.3-0.5 mol/L, and the first-stage countercurrent leaching agent of other batches is the second-stage leaching liquid of the previous batch. By controlling the parameters described in the present invention, it is surprisingly possible to maintain batches of secondary leach liquor within the acidity range of the primary leach. In the actual production process, if the second-stage leachate is not in the acidity range of the first-stage leaching, the second-stage leachate can be regulated and controlled by the existing means so as to meet the acidity requirement of the first-stage leaching.
In the invention, the organic reducing agent is at least one of starch, waste tea, wheat straw or wood chips.
Preferably, the concentration of the organic reducing agent in the leaching agent is 1-10 g/L.
Research finds that in addition to reasonably controlling the leaching acidity of different leaching steps, further controlling the temperature of each leaching step contributes to further improving the leaching effect, and in addition, contributes to further improving the acid utilization rate and the concentration of valuable metals in the leaching solution.
Preferably, the temperature of the second countercurrent leaching process is not lower than the temperature of the first countercurrent leaching process.
Preferably, the temperature of the one-stage countercurrent leaching process is 25-55 ℃.
Preferably, the temperature of the two-stage countercurrent leaching process is 55-95 ℃.
The inventor researches and discovers that in addition to controlling the acidity and the temperature in the leaching process, parameters such as solid-liquid ratio, reaction time (leaching time) and organic matter addition amount in the leaching process are further regulated and controlled, and valuable metals in the leaching process can be further efficiently recovered.
Preferably, the period of the countercurrent leaching is 10-30min, the solid-liquid ratio is controlled to be 30-100g/L, and the rotating speed is 100-600 r/min.
Preferably, the leaching time of the two-stage countercurrent leaching is 30-180min, the solid-liquid ratio is controlled at 200g/L of 100-.
Preferably, in step (1): and the electrode active material is obtained by short-circuit discharging, disassembling, binder stripping, crushing and screening the waste ternary LNCM lithium ion battery.
In the invention, the operations of short-circuit discharging the waste batteries, disassembling the discharged waste batteries, crushing the electric core part obtained after disassembly, stripping the binder, separating to obtain the electrode active component and the like can adopt the operations known in the field.
Preferably, the waste ternary LNCM lithium ions are short-circuited in a sodium chloride solution. The solute concentration of the sodium chloride solution is 5-20%. Short-circuit discharge to the end voltage below 1V.
Preferably, the cell components are obtained through disassembly, then the cell components are crushed, the crushed materials are heated to 400-600 ℃ at the speed of 2-10 ℃/min in the air atmosphere, the temperature is kept, roasting is carried out, and the adhesive is stripped.
Preferably, in the adhesive stripping process, lime water with the concentration not lower than 50mg/L is adopted to absorb waste gas released in the stripping process, so that calcium fluoride is obtained; and separating the stripped product to obtain Al and Cu foils and an electrode active material.
The roasted material can be separated by the existing method to obtain Al and Cu foils and electrode active materials.
For example, the calcined material is subjected to operations such as sieving or magnetic separation, and the electrode active material is obtained by separation.
Preferably, the electrode active material includes a positive electrode active material.
Preferably, the electrode active material further comprises a negative electrode active material.
Compared with the prior method which is only suitable for a single anode active material or a single cathode active material, the method can still efficiently recover valuable elements and has wider application prospect.
The invention also discloses a method for recovering valuable metals of the waste ternary LNCM lithium ion battery, which comprises the following steps:
step (a): obtaining the total leachate of the waste lithium ion battery by adopting the two-stage countercurrent leaching method;
step (b): removing Fe from the total leaching solution at a pH of 3-53+、Al3+(ii) a To obtain Li+、Ni2+、Co2+、Mn2+Removing impurities and filtering;
step (c): regulating the pH value of the impurity-removed filtrate to 10-11; the solid obtained by solid-liquid separation is NiCoMn (OH)2And (3) precursor.
According to the invention, by adopting the innovative leaching method, the utilization rate can be effectively improved, the concentration of nickel, cobalt and manganese in the leaching solution is ensured, and the subsequent recycling is facilitated.
Preferably, in the step (c), Li in the impurity-removed filtrate is regulated in advance+：(Ni2++Co2++Mn2+) 1.05-1.1: 1, then regulating and controlling the pH value, and precipitating to obtain the NiCoMn (OH)2And (3) precursor.
Preferably, the method further comprises the step (d): adjusting the pH value of the liquid obtained by the solid-liquid separation in the step (c) to 13-14, and performing solid-liquid separation to obtain Li2CO3. The carbonate can be added in the form of an aqueous solution dissolved with carbonateFor example, addition of saturated Na2CO3Saturated (NH)4)2CO3Saturated K2CO3One or more of the solutions.
The preferred recovery method of the invention comprises the following steps:
step (a): carrying out short-circuit discharge, disassembly, binder stripping, crushing and screening on the waste ternary LNCM lithium ion battery to obtain an electrode active material;
leaching valuable metals from the electrode active material by adopting a two-stage countercurrent method, wherein one stage adopts low-acid and reducing-agent-free leaching to improve the utilization rate of acid, the second stage adopts high-temperature and high-acid leaching and adds organic matters as reducing agents to improve the leaching rate of the metals, then the solution obtained after the second stage leaching returns to the first stage to be used as the leaching solution of the first stage, and the leaching solutions of the first stage are combined to obtain the leaching solution to be purified (total leaching solution, also called countercurrent leaching solution) with the pH of 1-2;
step (b): regulating pH of the leachate to be purified to 3-5, and precipitating Fe in the leachate3+、Al3+(ii) a Then solid-liquid separation is carried out to obtain Li+、Ni2+、Co2+、Mn2+Removing impurities and filtering;
step (c): adjusting the concentration of metal ions in the impurity-removed filtrate to be Li+：(Ni2++Co2++Mn2+) 1.05-1.1: 1, then regulating the pH of the impurity-removed filtrate to about 10, and filtering to obtain NiCoMn (OH)2A precursor;
step (d): precipitating and filtering to obtain Li by continuously adjusting the pH of the filtrate to about 132CO3
According to the method, a two-stage countercurrent leaching method is innovatively adopted, the effective utilization rate of the leaching acid is efficiently improved, and the ion concentration in the leaching solution is greatly improved; the pH of the solution after countercurrent leaching is 1-2, so that the precipitation can be reduced and Fe can be removed3+、Al3+And the alkali consumption of the precursor is subsequently recovered, so that the recovery cost is further reduced. In addition, the method can also simultaneously treat the anode active material and the cathode active material without respectively recovering, has simple process and good process repeatability, is different from the prior method which is mostly only suitable for laboratories, and has the advantages of simple process, high repeatability, simple operation, low cost and low costIs not suitable for industrial scale-up production.
Preferably, in the impurity-removed filtrate, Li+、Ni2+、Co2+、Mn2+The ion concentration of (A) is not lower than 5 g/L; the method can effectively improve the concentration of valuable metal ions in the leaching solution. Compared with the existing method, the method for recycling the waste lithium ion batteries has more obvious advantages.
More preferably, in the impurity-removed filtrate, Li+、Ni2+、Co2+、Mn2+The ion concentration of (A) is 5 to 30 g/L.
Under the cooperative control of the two-stage countercurrent leaching process, the comprehensive recovery rate (more than 95%) of metal and the effective utilization efficiency (more than 95%) of acid can be effectively improved, and Ni remained in the solution2+，Co2+，Mn2+Ion concentration of 0.1g/L or less, Li+The residual concentration is 0.05g/L or less.
The method of the invention can efficiently recover the impurity-removed filtrate in the concentration range which is difficult to be effectively recovered in the prior art.
The invention discloses a more preferable recovery method, which mainly comprises the following steps:
step (a) splitting a nickel cobalt lithium manganate battery: discharging the waste nickel cobalt lithium manganate battery by using brine (5-20% of sodium chloride solution) (the discharge termination voltage is lower than 1V), and crushing and screening by using mechanical force (the particle size is smaller than 0.1mm) to obtain crushed materials;
active substance separation: and (b) roasting the crushed materials obtained in the step (a) for 1-5h at 400-600 ℃ in an air atmosphere (the temperature rise rate is 2-10 ℃/min). Absorbing the waste gas generated by roasting with lime water (the concentration is not less than 50mg/L) to obtain calcium fluoride, leaching the roasted material by using sulfuric acid and organic matter system in two-stage countercurrent mode, filtering and separating to obtain carbon residue and Li-containing material+、Ni2+、Co2+、Mn2+、Fe3+、Al3+A low acid leach solution of plasma;
recovering iron and aluminum from the leaching solution in the step (b): adding a proper amount of alkali liquor into the leachate obtained in the step (a) to adjust the pH of the solution to 3-5, wherein Fe is3+、Al3+Respectively with Fe (OH)3And Al (OH)3Precipitating in the form of (1), filtering to obtain Li-containing solution+、Ni2+、Co2+、Mn2+The first filtrate (filtrate from impurity removal);
step (c) recovery of lithium nickel cobalt manganese: continuously adding ammonia water or ammonium hydroxide into the first filtrate obtained in the step (b) to adjust the pH value to 10, and filtering to obtain a nickel-cobalt-manganese precursor;
finally, adding saturated carbonate solution into the filtered solution of the prepared precursor to precipitate and recover Li2CO3。
Valuable metals and other materials are separated one by using simple chemistry, so that high-quality products are efficiently recovered, valuable elements of all parts of the waste nickel cobalt lithium manganate battery are comprehensively recovered at low cost, the process is simple, and the recovery rate is high.
The invention has the beneficial effects that:
1) the comprehensive method of two-stage countercurrent leaching and chemical composite precipitation is adopted in the process of leaching valuable metals from the waste lithium ion battery, so that the problem of secondary pollution possibly caused by a large amount of acidic wastewater generated in the acid leaching process is solved; secondly, the use of expensive extracting agents when valuable metals such as Cu, Ni and Co are separately recovered is avoided, and the recovery cost can be greatly reduced;
2) the method is suitable for forming a closed-loop process, does not produce secondary pollution, has environmental protection and economic benefits, has simple process and low production cost, and is suitable for large-scale industrial production.
Drawings
FIGS. 1 and 2 are schematic process flow diagrams of the present invention.
Detailed Description
The following are exemplary embodiments of the invention, but it should be understood that the invention is not limited to these embodiments.
Example 1
The waste nickel cobalt lithium manganate battery is soaked in 5 percent sodium chloride solution until the discharge termination voltage is 1V, and crushed materials with the particle size of less than 0.1mm are obtained by integral crushing and screening through mechanical force and are sent to the roasting process. The crushed materials are roasted for 1h at 450 ℃ in the air to remove the binder, the roasting waste gas is absorbed by 50mg/L lime water solution, and the roasted materials are sent to be soakedAnd (3) taking out the working procedure, wherein the parameters of the second-stage countercurrent leaching are as follows: first-stage leaching: 0.1mol/LH2SO4The solid-liquid ratio is 30g/L, the leaching time is 10min, the leaching temperature is 25 ℃, and a first-stage leaching residue and a first-stage leaching liquid are obtained by filtration and separation. Then, the first-stage leaching slag is subjected to second-stage leaching, and the parameters of the second-stage leaching are as follows: 1mol/LH2SO4The solid-liquid ratio is 100g/L, the leaching time is 60min, the leaching temperature is 55 ℃, the addition amount of organic starch is 1g/L, two-stage leaching liquid and two-stage leaching slag are obtained by filtration, the acidity of the two-stage leaching liquid is adjusted to be 0.1mol/L, the two-stage leaching liquid is returned to the first stage for leaching the next electrode active material, and in this way, N is continuously addediTaking the second-stage countercurrent leaching solution obtained from the batch of the electrode active materials as the NthiThe leaching agent for the first-stage countercurrent leaching of the +1 batches of electrode active materials is subjected to countercurrent series leaching for multiple times, and then the first-stage leaching solution and the last-stage leaching solution of each batch are combined to obtain a total leaching solution;
adding appropriate amount of 1mol/L NaOH solution into the total leaching solution, adjusting pH to 3-5, and filtering to obtain Fe (OH)3And Al (OH)3. Then the filtrate (impurity-removed filtrate; wherein, Li+、Ni2+、Co2+、Mn2+The total ion concentration of more than 50g/L), continuously adding 1mol/L NaOH solution until the PH value is 10, filtering to obtain a nickel-cobalt-manganese precursor and a filtered precursor solution, and finally adding saturated Na into the filtered precursor solution2CO3Adjusting the pH of the solution to 12, and filtering to obtain Li2CO3。
The comprehensive recovery of aluminum and iron exceeds 95%, the comprehensive leaching rate of nickel, cobalt, manganese and lithium is more than 90%, the purity of the obtained precursor product and lithium carbonate exceeds 99%, and the effective utilization rate of acid in the whole process exceeds 90%.
Example 2
The waste nickel cobalt lithium manganate battery is soaked in 5 percent sodium chloride solution until the discharge termination voltage is 1V, and crushed materials with the particle size of less than 0.1mm are obtained by integral crushing and screening through mechanical force and are sent to the roasting process. The crushed aggregates are roasted for 1 hour at 450 ℃ in the air to remove the binder, the roasting waste gas is absorbed by 50mg/L lime water solution, the roasted materials are sent to a leaching procedure, and the parameters of the second-stage countercurrent leaching are as follows:first-stage leaching: 0.3mol/L H2SO4The solid-liquid ratio is 60g/L, the leaching time is 20min, the leaching temperature is 40 ℃, and a first-stage leaching residue and a first-stage leaching liquid are obtained by filtration and separation. Then, the first-stage leaching slag is subjected to second-stage leaching, and the parameters of the second-stage leaching are as follows: 2mol/LH2SO4The solid-liquid ratio is 150g/L, the leaching time is 120min, the leaching temperature is 70 ℃, the addition amount of organic starch is 5g/L, two-stage leaching liquid and two-stage leaching slag are obtained by filtration, the acidity of the two-stage leaching liquid is adjusted to be 0.3mol/L, the two-stage leaching liquid is returned to the first stage for leaching the next electrode active material, and in this way, N is continuously addediTaking the second-stage countercurrent leaching solution obtained from the batch of the electrode active materials as the NthiThe leaching agent for the first-stage countercurrent leaching of the +1 batches of electrode active materials is subjected to countercurrent series leaching for multiple times, and then the first-stage leaching solution and the last-stage leaching solution of each batch are combined to obtain a total leaching solution;
adding appropriate amount of 1mol/L NaOH solution into the total leaching solution, adjusting pH to 3-5, and filtering to obtain Fe (OH)3And Al (OH)3. Then the filtrate (impurity-removed filtrate; wherein, Li+、Ni2+、Co2+、Mn2+The total ion concentration of more than 50g/L), continuously adding 1mol/L NaOH solution until the PH value is 10, filtering to obtain a nickel-cobalt-manganese precursor and a filtered precursor solution, and finally adding saturated Na into the filtered precursor solution2CO3Adjusting the pH of the solution to 12, and filtering to obtain Li2CO3。
The comprehensive recovery of aluminum and iron exceeds 95%, the comprehensive leaching rate of nickel, cobalt, manganese and lithium is more than 93%, the purity of the obtained precursor product and lithium carbonate exceeds 99%, and the effective utilization rate of acid in the whole process exceeds 90%.
Example 3
The waste nickel cobalt lithium manganate battery is soaked in 5 percent sodium chloride solution until the discharge termination voltage is 1V, and crushed materials with the particle size of less than 0.1mm are obtained by integral crushing and screening through mechanical force and are sent to the roasting process. The crushed aggregates are roasted for 1 hour at 450 ℃ in the air to remove the binder, the roasting waste gas is absorbed by 50mg/L lime water solution, the roasted materials are sent to a leaching procedure, and the parameters of the second-stage countercurrent leaching are as follows: first-stage leaching: 0.5mol/L H2SO4The solid-liquid ratio is 100g/L, the leaching time is 30min, the leaching temperature is 55 ℃, and a first-stage leaching residue and a first-stage leaching liquid are obtained by filtration and separation. Then, the first-stage leaching slag is subjected to second-stage leaching, and the parameters of the second-stage leaching are as follows: 3mol/LH2SO4The solid-liquid ratio is 200g/L, the leaching time is 180min, the leaching temperature is 80 ℃, the addition amount of organic starch is 10g/L, two-stage leaching liquid and two-stage leaching slag are obtained by filtration, the acidity of the two-stage leaching liquid is adjusted to be 0.5mol/L, the two-stage leaching liquid is returned to the first stage for leaching the next electrode active material, and in this way, N is continuously addediTaking the second-stage countercurrent leaching solution obtained from the batch of the electrode active materials as the NthiThe leaching agent for the first-stage countercurrent leaching of the +1 batches of electrode active materials is subjected to countercurrent series leaching for multiple times, and then the first-stage leaching solution and the last-stage leaching solution of each batch are combined to obtain a total leaching solution;
adding appropriate amount of 1mol/L NaOH solution into the obtained leachate, adjusting pH to 3-5, and filtering to obtain Fe (OH)3And Al (OH)3. Then the filtrate (impurity-removed filtrate; wherein, Li+、Ni2+、Co2+、Mn2+The total ion concentration of more than 50g/L), continuously adding 1mol/L NaOH solution until the PH value is 10, filtering to obtain a nickel-cobalt-manganese precursor and a filtered precursor solution, and finally adding saturated Na into the filtered precursor solution2CO3Adjusting the pH of the solution to 12, and filtering to obtain Li2CO3。
The comprehensive recovery of aluminum and iron exceeds 95%, the comprehensive leaching rate of nickel, cobalt, manganese and lithium is over 95%, the purity of the obtained precursor product and lithium carbonate exceeds 99%, and the effective utilization rate of acid in the whole process exceeds 95%.
Comparative example 1
The main difference compared with example 3 is that no Fe removal is carried out3+、Al3+The method comprises the following specific operations:
the waste nickel cobalt lithium manganate battery is soaked in 5 percent sodium chloride solution until the discharge termination voltage is 1V, and crushed materials with the particle size of less than 0.1mm are obtained by integral crushing and screening through mechanical force and are sent to the roasting process. The crushed aggregates are roasted for 1h at 450 ℃ in the air to remove the binder, and the roasting waste gas is absorbed by 50mg/L lime water solutionAnd (3) recovering, conveying the roasted material into a leaching process, wherein the parameters of the second-stage countercurrent leaching are as follows: first-stage leaching: 0.5mol/L H2SO4The solid-liquid ratio is 100g/L, the leaching time is 30min, the leaching temperature is 55 ℃, and a first-stage leaching residue and a first-stage leaching liquid are obtained by filtration and separation. Then, the first-stage leaching slag is subjected to second-stage leaching, and the parameters of the second-stage leaching are as follows: 3mol/LH2SO4The solid-liquid ratio is 200g/L, the leaching time is 180min, the leaching temperature is 80 ℃, the addition amount of organic starch is 10g/L, a second-stage leaching solution and a second-stage leaching residue are obtained by filtering, the acidity of the two-stage leaching solution is adjusted to be 0.5mol/L, the two-stage leaching solution is returned to the first stage for leaching the next electrode active material, and thus, the second-stage countercurrent leaching solution obtained from the Ni batch of electrode active materials is continuously used as the Nth countercurrent leaching solutioniThe leaching agent for the first-stage countercurrent leaching of the +1 batches of electrode active materials is subjected to countercurrent series leaching for multiple times, and then the first-stage leaching solution and the last-stage leaching solution of each batch are combined to obtain a total leaching solution;
adding a proper amount of 1mol/L NaOH solution into the total leachate to adjust the pH of the leachate to 10, filtering to obtain a nickel-cobalt-manganese precursor and a filtered precursor solution, and finally adding saturated Na into the filtered precursor solution2CO3Adjusting the pH of the solution to 12, and filtering to obtain Li2CO3。
The comprehensive leaching rate of nickel, cobalt, manganese and lithium is more than 95%, the purity of the obtained precursor product and lithium carbonate is lower than 90%, and the effective utilization rate of acid in the whole process is more than 95%.
Comparative example 2
The comparative example discusses that the two-stage countercurrent leaching process (adopting one-step direct leaching process) is not adopted, and the specific operations are as follows:
the waste nickel cobalt lithium manganate battery is soaked in 5 percent sodium chloride solution until the discharge termination voltage is 1V, and crushed materials with the particle size of less than 0.1mm are obtained by integral crushing and screening through mechanical force and are sent to the roasting process. The crushed aggregates are roasted for 1 hour at 450 ℃ in the air to remove the binder, roasting waste gas is absorbed by 50mg/L lime water solution, the roasted materials are sent to a leaching process, and leaching parameters are as follows: 2mol/L H2SO47g/L organic starch with solid-liquid ratio of 50g/L, leaching time of 120min, leachingFiltering and separating at the temperature of 80 ℃ to obtain carbon residue and leachate. Then adding a proper amount of 1mol/L NaOH solution into the leaching solution to adjust the pH value to 3-5, and filtering to obtain Fe (OH)3And Al (OH)3. Then the filtrate (impurity-removed filtrate; wherein, Li+、Ni2+、Co2+、Mn2+The total ion concentration of not more than 25g/L), continuously adding 1mol/L NaOH solution until the PH value is 10, filtering to obtain a nickel-cobalt-manganese precursor and a filtered precursor solution, and finally adding saturated Na into the filtered precursor solution2CO3Adjusting the pH of the solution to 12, and filtering to obtain Li2CO3。
The comprehensive leaching rate of nickel, cobalt, manganese and lithium is more than 95%, the purity of the obtained precursor product and lithium carbonate is more than 99%, and the effective utilization rate of acid in the whole process is lower than 70%.
Comparative example 3
The comparative example discusses that the acidity of the two-stage countercurrent leaching process is not in the optimal range, and the operation is as follows:
the waste nickel cobalt lithium manganate battery is soaked in 5 percent sodium chloride solution until the discharge termination voltage is 1V, and crushed materials with the particle size of less than 0.1mm are obtained by integral crushing and screening through mechanical force and are sent to the roasting process. The crushed aggregates are roasted for 1 hour at 450 ℃ in the air to remove the binder, the roasting waste gas is absorbed by 50mg/L lime water solution, the roasted materials are sent to a leaching procedure, and the parameters of the second-stage countercurrent leaching are as follows: first-stage leaching: 1mol/L H2SO4The solid-liquid ratio is 100g/L, the leaching time is 30min, the leaching temperature is 55 ℃, and a first-stage leaching residue and a first-stage leaching liquid are obtained by filtration and separation. Then, the first-stage leaching slag is subjected to second-stage leaching, and the parameters of the second-stage leaching are as follows: 1mol/LH2SO4The solid-liquid ratio is 200g/L, the leaching time is 180min, the leaching temperature is 80 ℃, the addition amount of organic starch is 10g/L, two-stage leaching liquid and two-stage leaching slag are obtained by filtration, the acidity of the two-stage leaching liquid is adjusted to be 1mol/L, the two-stage leaching liquid returns to the first stage for leaching the next electrode active material, and thus, the two-stage countercurrent leaching liquid obtained by the Ni batch of electrode active materials is continuously used as the Nth electrode active materiali+1 batch of electrode active material leaching agent through one section of countercurrent leaching, multiple countercurrent serial leaching, merging eachObtaining a total leaching solution by using the first-stage leaching solution of the batch and the second-stage leaching solution of the last batch;
adding appropriate amount of 1mol/L NaOH solution into the obtained leachate, adjusting pH to 3-5, and filtering to obtain Fe (OH)3And Al (OH)3. Continuously adjusting the pH value of the purification solution to 10, filtering to obtain a nickel-cobalt-manganese precursor and a filtered precursor solution, and finally adding saturated Na into the filtered precursor solution2CO3Adjusting the pH of the solution to 13, and filtering to obtain Li2CO3。
The comprehensive leaching rate of nickel, cobalt, manganese and lithium is below 85%, the purity of the obtained precursor product and lithium carbonate is higher than 95%, and the effective utilization rate of acid in the whole process is below 50%.
Claims (10)
1. A two-stage countercurrent leaching method for waste ternary LNCM lithium ion batteries is characterized by comprising the following steps:
step (1): recycling electrode active materials from the waste ternary LNCM lithium ion battery;
step (2): two stage countercurrent leaching
The electrode active material is sequentially subjected to first-stage countercurrent leaching and second-stage countercurrent leaching in N batches; wherein the acidity of the leaching agent of the first-stage countercurrent leaching is 0.1-0.5 mol/L; the leaching agent of the second-stage countercurrent leaching contains an organic reducing agent, and the acidity is 0.5-3 mol/L;
will NiTaking a second-stage countercurrent leaching solution obtained by performing first-stage countercurrent leaching and second-stage countercurrent leaching on the batch of electrode active materials as the Nthi+1 batch of electrode active material leaching agent by one-stage countercurrent leaching; i is an integer of 1, 2, 3.. N-1;
and collecting a section of countercurrent leaching liquid of each batch of electrode active materials, namely the total leaching liquid of the waste lithium ion battery.
2. The two-stage counter-current leaching process of claim 1, wherein N is1The first-section countercurrent leaching agent of the batch of electrode active materials is acid liquor a; the leaching agent for the first-stage countercurrent leaching of the other batches of electrode active materials is leachate of the second-stage countercurrent leaching which is recycled.
3. The two-stage counter-current leaching process according to claim 1, wherein the acidity of the two-stage counter-current leaching process is 2-4 times the acidity of the one-stage counter-current leaching process.
4. The two-stage counter-current leaching process according to claim 1, wherein the temperature of the two-stage counter-current leaching process is not lower than the temperature of the one-stage counter-current leaching process;
preferably, the temperature of the first stage of countercurrent leaching process is 25-55 ℃; the temperature of the two-stage countercurrent leaching process is 55-95 ℃.
5. The two-stage countercurrent leaching process of claim 1, wherein in step (3), the organic reducing agent is at least one of starch, waste tea, wheat straw or wood chips;
preferably, in the step (3), the concentration of the organic reducing agent in the leaching agent is 1-10 g/L.
6. The two-stage countercurrent leaching process according to any one of claims 1 to 5, characterized in that in step (1): the electrode active material is obtained by short-circuit discharging, disassembling, binder stripping, crushing and screening the waste ternary LNCM lithium ion battery;
preferably, the electrode active material includes a positive electrode active material;
preferably, the electrode active material further comprises a negative electrode active material.
7. The two-stage countercurrent leaching process of claim 6, wherein said spent ternary LNCM lithium ions are short-circuited in a sodium chloride solution having a solute concentration of 5-20%; short-circuit discharge is carried out until the termination voltage is lower than 1V;
preferably, disassembling after short-circuit discharge to obtain a battery cell component, crushing the battery cell component, heating the crushed material to 400-600 ℃ at a speed of 2-10 ℃/min in an air atmosphere, carrying out heat preservation roasting, and stripping the adhesive;
preferably, in the adhesive stripping process, lime water with the concentration not lower than 50mg/L is adopted to absorb waste gas released in the stripping process, so as to obtain calcium fluoride; and separating the stripped product to obtain Al and Cu foils and an electrode active material.
8. The two-stage counter-current leaching process according to any one of claims 1 to 7, wherein the total leach solution further comprises a second stage counter-current leach solution from which the last batch of electrode active material is not recycled.
9. A method for recovering valuable metals of waste ternary LNCM lithium ion batteries is characterized by comprising the following steps:
step (a): obtaining a total leachate of a waste lithium ion battery by adopting the two-stage countercurrent leaching method according to claims 1-8;
step (b): removing Fe from the total leaching solution at a pH of 3-53+、Al3+(ii) a To obtain Li+、Ni2+、Co2+、Mn2+Removing impurities and filtering;
step (c): regulating the pH value of the impurity-removed filtrate to 10-11; the solid obtained by solid-liquid separation is NiCoMn (OH)2And (3) precursor.
10. The recycling method according to claim 9,
in the step (c), Li in the impurity-removed filtrate is regulated and controlled in advance+：(Ni2++Co2++Mn2+) 1.05-1.1: 1, then regulating and controlling the pH value, and precipitating to obtain the NiCoMn (OH)2A precursor;
preferably, further comprising step (d): adjusting the pH value of the liquid obtained by the solid-liquid separation in the step (c) to 13-14, and performing solid-liquid separation to obtain Li2CO3。
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Application publication date: 20200623 |