CN111082043A - Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material - Google Patents
Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material Download PDFInfo
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Abstract
The invention discloses a recycling method of a waste nickel cobalt lithium manganate ternary battery positive electrode material, which comprises the following steps: 1) acid leaching, namely adding powder containing elements such as a ternary positive electrode material, negative electrode powder, copper-aluminum powder, iron and the like into dilute acid, and simultaneously adding a reducing agent for stirring and leaching to obtain leachate containing nickel, cobalt, manganese, aluminum, lithium, copper and iron; 2) removing copper, namely adding iron powder into the leaching solution, reacting at a certain temperature, and filtering to obtain a copper-removed solution; 3) removing iron and aluminum, adding a phosphoric acid compound into the copper-removed solution, synchronously adding dilute alkali to adjust the pH value to 2.5-3.5, and removing iron and aluminum; 4) p204 extraction and impurity removal; 5) preparing a nickel-cobalt-manganese ternary precursor; 6) adding saturated sodium carbonate solution into the lithium-containing liquid, evaporating and concentrating to obtain lithium carbonate powder. The invention has the advantages that: the recovery rate of nickel, cobalt, manganese and lithium is more than 95%, and the obtained nickel, cobalt, manganese and ternary precursor and lithium carbonate have high purity, can be directly used for preparing ternary battery materials, and really realizes resource recycling.
Description
Technical Field
The invention relates to the technical field of battery recycling, in particular to a recycling method of a waste nickel cobalt lithium manganate ternary battery positive electrode material.
Background
With the rapid growth of the electric automobile industry, according to the forecast of the research center of automobile technology in China, the annual accumulated scrappage of electric automobile power electric cars in China will reach the scale of 32.3 million tons by 2020. The prediction shows that: the scale of 50 million yuan can be achieved in 2018, the scale of 136 million yuan can be achieved in 2020, and the scale of 311 million yuan can be achieved in 2023.
The power battery does not contain heavy metal elements such as mercury, cadmium and lead with high toxicity, but also can cause environmental pollution, for example, the pH value of the environment can be increased by the heavy metal in the battery anode material, and toxic gas can be generated due to improper treatment. In addition, the power battery contains various metals and electrolytes, which are harmful to human health. The power battery contains a large amount of recyclable valuable metals, such as Co, Ni, Mn, Cu, Li, Al, Fe and the like. Part of metal resources belong to elements which are relatively lacked in the nature, the price is relatively expensive, and if the power battery cannot be recycled in a limited way, precious metals are inevitably lost.
The recovery of the power battery not only has economic value, but also has environmental protection significance. At present, two methods for recycling waste ternary batteries mainly comprise a high-temperature solid phase repair method and a wet element extraction method. The high-temperature solid phase repairing method is to separate nickel cobalt lithium manganate from other impurity elements by methods of sorting, chemical impurity removal and the like, the obtained nickel cobalt lithium manganate is subjected to lithium supplement and high-temperature calcination to obtain the nickel cobalt lithium manganate ternary battery anode material with restored performance, for example, the patent number US 8616475B1, the invention adopts wet crushing to disassemble waste lithium ion batteries, and metallic aluminum, copper, plastics and the like are separated by processes of screening, flotation and the like to obtain the anode material, and then the anode material is subjected to lithium supplement and calcination at 800 ℃ to obtain the recyclable anode material. The anode material obtained by the method has high impurity content and poor electrochemical performance;
the wet element extraction method is to carry out acid leaching, chemical impurity removal, deep impurity removal by extraction or nickel, cobalt and manganese separation on the nickel cobalt lithium manganate ternary powder to obtain sulfate, and add sodium carbonate into a lithium-containing solution to carry out evaporation concentration to obtain lithium carbonate. For example, patent number WO2017/091562AI, the invention is to leach and dissolve and recover valuable metals such as nickel, cobalt, manganese, aluminum and the like from the obtained positive electrode material in a waste lithium ion battery. And (3) coprecipitating to obtain the required precursor of the cathode material by adjusting the molar ratio in the solution. The method is that a positive electrode material obtained after grading treatment of a scrapped power battery material is placed in a sulfuric acid system, valuable metals in the positive electrode material are presoaked-pressure leached by taking pure oxygen as an oxidant, and a solution containing the valuable metals is prepared by adopting a P204 extraction impurity removal or P507 extraction purification mode; patent No. CN105789726A, the method comprises the following steps: (1) physically disassembling the fully discharged waste lithium ion battery, and taking out the positive plate; (2) and (4) putting the separated positive plate into an ultrasonic cleaning machine for ultrasonic cleaning, so that the positive active substance falls off from the upper surface of the current collector aluminum foil. Drying the aluminum foil and directly recovering; (3) dissolving the positive active substance obtained in the step 2 in acid, and adding sodium hydroxide to remove aluminum; (4) and (3) measuring the concentration of metal ions in the leaching solution after aluminum removal, adding soluble nickel salt, cobalt salt and manganese salt to adjust the molar ratio, adding a sodium carbonate precipitator to precipitate three metal elements of nickel, cobalt and manganese simultaneously, filtering and drying to obtain the nickel-cobalt-manganese ternary material precursor.
The method directly removes the iron and the aluminum by chemical precipitation, and because the aluminum hydroxide and the ferric hydroxide are both flocculent colloids, the precipitation is extremely difficult to filter, and the industrial production is difficult to realize; meanwhile, the surface activity of the flocculent colloid is high, so that the loss of valuable metals such as nickel-cobalt-manganese-lithium is more than 10%, and the recovery value of the waste nickel-cobalt-lithium manganate ternary battery is reduced.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a method for recycling a waste nickel cobalt lithium manganate ternary battery positive electrode material, which has the advantages of simple process, no generation of flocculent iron and aluminum hydroxide, solving the problem of difficult filtration in industrial scale-up production and greatly improving the recovery rate of valuable metal elements.
1. In order to solve the technical problems, the technical scheme provided by the invention is as follows: a recycling method of a waste nickel cobalt lithium manganate ternary battery positive electrode material mainly comprises the following steps:
(1) acid leaching: leaching the positive powder by using an acid and reducing agent system and filtering to obtain a leaching solution;
(2) copper removal: adding iron powder into the leaching solution, reacting at a certain temperature, and filtering to obtain copper-removed solution;
(3) removing iron and aluminum: adding a phosphoric acid compound into the copper-removed solution, and synchronously adding an alkali solution to adjust the pH value to 2.5-3.5 so as to remove iron and aluminum in a phosphate form;
(4) deeply removing impurities by extraction, and removing metal impurities in the solution by using an extraction method to obtain a purified solution;
(5) adding different salt solutions into the purified solution to adjust the ratio, and adding ammonia water and alkali liquor by a coprecipitation method to obtain ternary positive electrode precursor precipitate with not less than one molar ratio;
(6) and filtering, washing and drying the ternary precursor precipitate to obtain a ternary positive electrode precursor material, wherein the filtrate is a lithium-containing solution, and adding sodium carbonate to precipitate lithium to obtain lithium carbonate.
Preferably, the acid in the step 1 refers to one or a mixture of more of sulfuric acid, hydrochloric acid and nitric acid, and the concentration is 0.1-1 mol/L; the reducing agent is one or two of hydrogen peroxide, sodium sulfite solution and ascorbic acid; solid-liquid ratio 1: 3 to 5, the leaching temperature is 40 to 80 ℃, the leaching time is 1 to 3 hours, and the stirring speed is 200-.
Preferably, the adding amount of the iron powder in the step 2 is 0.8-1 time of the copper content in the solution, the reaction temperature is 30-80 ℃, and the stirring is carried out for 10-60 min.
Preferably, the phosphorus compound in step 3 is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, trisodium phosphate and sodium dihydrogen phosphate.
Preferably, the alkali solution in step 3 is one or a mixture of sodium hydroxide, ammonia water, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate.
Preferably, the extractant used in the step 4 is P204, and impurities except lithium, nickel and cobalt in the leachate are all introduced into the organic phase by adjusting extraction conditions to obtain a purified solution containing lithium, nickel and cobalt; the saponification rate of P204 is 60-75%, the pH value of the aqueous phase solution is controlled to be 2-3, the volume ratio of the organic phase to the aqueous phase is 0.2-1: 1, P204 volume fraction is 15-25%, and extraction stage number is 3 stages of countercurrent extraction; .
Preferably, one or more of nickel sulfate, cobalt sulfate or manganese sulfate is/are added in the step 5 to enable the nickel, cobalt and manganese in the purified solution to reach the required molar ratio of the precursor of the ternary cathode material, alkali liquor is/are added during co-precipitation in the step 5, the alkali liquor is/are a mixture of one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate, the concentration of the alkali liquor is 1-2mol/L, the concentration of ammonia water is 10-15%, the reaction pH is 10.5-12.5, the reaction temperature is 40-90 ℃, and the stirring speed is 800-1500 r/min.
The invention has the advantages that: 1. the iron and aluminum removing process has no generation of hydroxide of iron and aluminum, so that the filtering performance of iron and aluminum slag is greatly improved, and large-scale industrial production is easy to realize;
2. the production of high-adsorbability aluminum hydroxide and ferric hydroxide is avoided, and the recovery rate of valuable metals is greatly improved;
3. the nickel-cobalt separation process is omitted, the components of the purified liquid are adjusted according to the proportion and then directly precipitated to obtain the ternary positive precursor materials with different proportions, and the production cost is greatly reduced;
4. the obtained ternary precursor and lithium carbonate have high purity, can be directly used for preparing the ternary battery anode material, and really realizes the cyclic utilization of resources.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is the results of analysis of the components of each liquid phase in example 1 of the present invention.
FIG. 3 shows the analysis results of the ternary precursor obtained in example 1 of the present invention.
Fig. 4 is a table showing the analysis results of lithium carbonate obtained in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
taking 25g of ternary powder, adding the ternary powder into 80ml of 0.25mol/L dilute sulfuric acid solution, stirring at the speed of 200-800r/min, dropwise adding hydrogen peroxide, reacting for 2 hours, and filtering to obtain a leachate, wherein the analysis result of the leachate is shown in Table 1; adding 0.5g of iron powder into the leachate, stirring at 50 ℃ for reaction for 30min, and filtering to obtain a copper-removed solution; adding 6g of 85% phosphoric acid into the copper-removed solution, stirring, and slowly dropwise adding 6ml of industrial hydrogen peroxide, wherein the reaction temperature is 45 ℃ and the dropwise adding time is 60 min; adding 1mol/L sodium hydroxide at the temperature to adjust the PH to 3, reacting for 30min, filtering the iron-aluminum slag to obtain iron-removed aluminum liquid, wherein the content analysis result is shown in Table 1; adding 30ml of P204 with 65% saponification rate into the iron-removed aluminum liquid, controlling the water phase balance pH to be 2.8, and performing 3-stage countercurrent extraction to obtain a purified liquid, wherein the analysis result of the purified liquid is shown in Table 1; adding a proper amount of cobalt sulfate, nickel sulfate and manganese sulfate solution into the purified solution, and adjusting the element ratio of nickel, cobalt and manganese in the solution to be 5: 2: and 3, simultaneously adding 2mol/L sodium hydroxide solution and 10% by volume of ammonia water solution in a concurrent manner, maintaining the pH value of the solution at 11, stirring at the speed of 1000r/min, reacting at the temperature of 80 ℃, aging for 10 hours after the reaction is finished, filtering, washing with deionized water for multiple times, and drying to obtain the Ni0.5Co0.2Mn0.3(OH)2 precursor. The results of the ternary precursor analysis are shown in table 2; a saturated sodium carbonate solution was added to the filtrate after coprecipitation of the ternary precursor and evaporated at 90 degrees to obtain 3.9g of white lithium carbonate powder, and the analytical results of lithium carbonate are shown in table 3.
Example 2:
taking 25g of ternary powder, adding the ternary powder into 120ml of 0.5mol/L dilute hydrochloric acid solution, stirring at the speed of 200-800r/min, adding 10ml of 1mol/L sodium sulfite solution, reacting for 2.5h, and filtering to obtain leachate; adding 1g of iron powder into the leachate, stirring at 60 ℃ for reaction for 20min, and filtering to obtain a copper-removed solution; adding 15ml of 30 wt% diammonium hydrogen phosphate solution into the solution after copper removal, stirring and slowly dripping 6ml of industrial hydrogen peroxide, wherein the reaction temperature is 50 ℃, and the dripping time is 90 min; adding 1mol/L sodium carbonate solution at the temperature to adjust the PH to 2.8, reacting for 60min, and filtering the iron-aluminum slag to obtain iron-removed aluminum liquid; adding 40ml of P204 with 70% saponification rate into the iron-removed aluminum liquid, controlling the water phase balance pH to be 2.5, and performing 3-stage countercurrent extraction to obtain a purified liquid; adding a proper amount of cobalt sulfate, nickel sulfate and manganese sulfate solution into the purified solution, and adjusting the element ratio of nickel, cobalt and manganese in the solution to be 6: 2: 2, simultaneously adding 2mol/L sodium hydroxide solution and 15% ammonia water solution by volume fraction in a parallel flow manner, maintaining the pH value of the solution at 10.5, stirring at the speed of 800r/min and the reaction temperature of 70 ℃, aging for 10h after the reaction is finished, filtering, washing with deionized water for multiple times, and drying to obtain a Ni0.6Co0.2Mn0.2(OH)2 precursor; a saturated sodium carbonate solution was added to the filtrate after coprecipitation of the ternary precursor and evaporated at 90 degrees to obtain 3.88g of white lithium carbonate powder.
Therefore, the recovery rate of the nickel, cobalt, manganese and lithium is more than 95%, and the obtained nickel, cobalt, manganese and lithium ternary precursor and lithium carbonate have high purity, can be directly used for preparing the ternary battery material, and really realizes the cyclic utilization of resources.
The present invention and its embodiments have been described above, and the description is not intended to be limiting, and the drawings are only one embodiment of the present invention, and the actual structure is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A recycling method of a waste nickel cobalt lithium manganate ternary battery positive electrode material is characterized by comprising the following steps: the method mainly comprises the following steps:
(1) acid leaching: leaching the positive powder by using an acid and reducing agent system and filtering to obtain a leaching solution;
(2) copper removal: adding iron powder into the leaching solution, reacting at a certain temperature, and filtering to obtain copper-removed solution;
(3) removing iron and aluminum: adding a phosphoric acid compound into the copper-removed solution, and synchronously adding an alkali solution to adjust the pH value to 2.5-3.5 so as to remove iron and aluminum in a phosphate form;
(4) deeply removing impurities by extraction, and removing metal impurities in the solution by using an extraction method to obtain a purified solution;
(5) adding different salt solutions into the purified solution to adjust the ratio, and adding ammonia water and alkali liquor by a coprecipitation method to obtain ternary positive electrode precursor precipitate with not less than one molar ratio;
(6) and filtering, washing and drying the ternary precursor precipitate to obtain a ternary positive electrode precursor material, wherein the filtrate is a lithium-containing solution, and adding sodium carbonate to precipitate lithium to obtain lithium carbonate.
2. The recycling method of the anode material of the waste nickel cobalt lithium manganate ternary battery according to claim 1, characterized in that: in the step 1, the acid refers to one or a mixture of more of sulfuric acid, hydrochloric acid and nitric acid, and the concentration is 0.1-1 mol/L; the reducing agent is one or two of hydrogen peroxide, sodium sulfite solution and ascorbic acid; solid-liquid ratio 1: 3 to 5, the leaching temperature is 40 to 80 ℃, the leaching time is 1 to 3 hours, and the stirring speed is 200-.
3. The recycling method of the anode material of the waste nickel cobalt lithium manganate ternary battery according to claim 1, characterized in that: in the step 2, the adding amount of the iron powder is 0.8-1 time of the copper content in the solution, the reaction temperature is 30-80 ℃, and the stirring is carried out for 10-60 min.
4. The recycling method of the anode material of the waste nickel cobalt lithium manganate ternary battery according to claim 1, characterized in that: in the step 3, the phosphorus compound is one or a mixture of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, trisodium phosphate and sodium dihydrogen phosphate.
5. The recycling method of the anode material of the waste nickel cobalt lithium manganate ternary battery according to claim 1, characterized in that: and 3, the alkali solution is one or a mixture of sodium hydroxide, ammonia water, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate.
6. The recycling method of the anode material of the waste nickel cobalt lithium manganate ternary battery according to claim 1, characterized in that: the extractant used in the step 4 is P204, and impurities except lithium, nickel and cobalt in the leachate are all introduced into an organic phase by adjusting extraction conditions to obtain a purified solution containing lithium, nickel and cobalt; the saponification rate of P204 is 60-75%, the pH value of the aqueous phase solution is controlled to be 2-3, the volume ratio of the organic phase to the aqueous phase is 0.2-1: 1, P204 volume fraction is 15-25%, and the extraction stage number is 3 stages of countercurrent extraction.
7. The recycling method of the anode material of the waste nickel cobalt lithium manganate ternary battery according to claim 1, characterized in that: and 5, adding one or more of nickel sulfate, cobalt sulfate or manganese sulfate to enable the nickel, cobalt and manganese in the purified solution to reach the required molar ratio of the precursor of the ternary cathode material, adding alkali liquor which is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate when carrying out coprecipitation in the step 5, wherein the concentration of the alkali liquor is 1-2mol/L, the concentration of ammonia water is 10-15%, the reaction pH is 10.5-12.5, the reaction temperature is 40-90 ℃, and the stirring speed is 800-.
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Cited By (12)
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| CN111825110A (en) * | 2020-05-12 | 2020-10-27 | 宁夏百川新材料有限公司 | Recycling method of waste lithium ion battery anode material |
| CN111945002A (en) * | 2020-07-06 | 2020-11-17 | 广东邦普循环科技有限公司 | Method for removing copper from waste lithium batteries by recovery wet process |
| CN112126783A (en) * | 2020-08-25 | 2020-12-25 | 湖南邦普循环科技有限公司 | Recycling method of iron and aluminum in nickel-cobalt-manganese solution |
| CN112158894A (en) * | 2020-09-24 | 2021-01-01 | 广东邦普循环科技有限公司 | Method for recovering anode material of waste lithium battery |
| CN112342383A (en) * | 2020-09-17 | 2021-02-09 | 湖北金泉新材料有限公司 | Method for separating and recovering nickel, cobalt, manganese and lithium in ternary waste |
| CN112725621A (en) * | 2020-09-17 | 2021-04-30 | 湖北金泉新材料有限公司 | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method |
| CN113086996A (en) * | 2021-03-25 | 2021-07-09 | 宁夏百川新材料有限公司 | Recycling method of waste ternary fluorine-doped battery positive electrode material |
| CN114583316A (en) * | 2022-03-14 | 2022-06-03 | 广东邦普循环科技有限公司 | Lithium ion battery recycling and regenerating method and application thereof |
| CN114717419A (en) * | 2022-03-14 | 2022-07-08 | 中国矿业大学 | Method for separating and recovering nickel, cobalt, manganese and lithium from waste ternary lithium battery |
| CN115652109A (en) * | 2022-11-18 | 2023-01-31 | 广东邦普循环科技有限公司 | Treatment method of waste lithium battery leachate |
| CN116675265A (en) * | 2023-07-27 | 2023-09-01 | 宜宾光原锂电材料有限公司 | Nickel-copper-iron-manganese precursor, preparation method thereof, washing method thereof, positive electrode material and battery |
| CN116837216A (en) * | 2023-09-01 | 2023-10-03 | 北京怀柔北珂新能源科技有限公司 | Impurity removal method for recycling positive electrode powder of lithium ion battery |
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| WO2023173773A1 (en) * | 2022-03-14 | 2023-09-21 | 广东邦普循环科技有限公司 | Lithium ion battery recycling method and application thereof |
| CN115652109A (en) * | 2022-11-18 | 2023-01-31 | 广东邦普循环科技有限公司 | Treatment method of waste lithium battery leachate |
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