CN108539309B - Method for recycling waste nickel cobalt lithium manganate positive electrode material - Google Patents
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Abstract
The invention discloses a method for recycling a waste nickel cobalt lithium manganate positive electrode material. Disassembling the waste nickel cobalt lithium manganate battery, crushing the positive plate, sieving the crushed material, and then putting the sieved crushed material into a reduction furnace for hydrogen reduction; washing the obtained reducing material with hot pure water to obtain washing liquid and washing slag, introducing carbon dioxide into the washing liquid to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, calcining the aluminum hydroxide to obtain superfine aluminum oxide, and performing pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate; adding hydrazine hydrate solution into washing slag, then adding sodium hydroxide, stirring, reacting and filtering to obtain second filtrate and second filter residue, putting the second filter residue into a vacuum drying oven for vacuum drying, and screening and magnetically separating the dried material to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain nickel-cobalt-manganese ternary mixed solution. The invention has low cost, high recovery rate and high added value of products, and can realize separation and recovery of all components.
Description
Technical Field
The invention relates to a method for recycling a waste nickel cobalt lithium manganate positive electrode material, and belongs to the technical field of waste treatment of lithium battery materials.
Background
With the development of new energy automobiles, a large number of waste lithium batteries can be generated, and the scale of the recovery market for growth promotion is very large. The recycling value of the waste lithium battery is mainly the ternary materials, cobalt, lithium, nickel and other metals. It is estimated that by 2020, the relevant market space can reach the billion level. In recent years, particularly in 2017, the price of cobalt, lithium and other related metals has obviously increased, and the processing and utilization of waste lithium batteries are becoming more and more valuable.
The lithium nickel cobalt manganese oxide battery has the highest energy density, and along with the improvement of the technology, the safety of the lithium nickel cobalt manganese oxide battery is greatly improved, and the lithium nickel cobalt manganese oxide battery is applied to various tools, chargers and even electric automobiles.
Aiming at the recovery of the nickel cobalt lithium manganate cathode material, the recovery value is relatively high due to the fact that the nickel cobalt lithium manganate cathode material contains noble metals such as cobalt and nickel, but the conventional recovery process is high in recovery cost, long in process flow and low in profit, and a large amount of waste water can be generated.
Disclosure of Invention
In view of the above, the invention provides a method for recovering a waste nickel cobalt lithium manganate positive electrode material, which has the advantages of short flow, simple process, low cost, high recovery rate, high purity of the finally obtained product and high added value of the product, and can realize separation and recovery of all components.
The invention solves the technical problems by the following technical means:
a method for recycling waste nickel cobalt lithium manganate cathode materials comprises the following steps:
(1) preprocessing, namely disassembling the waste nickel-cobalt lithium manganate battery, crushing the positive plate in a liquid nitrogen freezing crusher, then sieving, sieving with a 100-mesh and 200-mesh sieve, returning oversize products to continue freezing and crushing, and reserving undersize products for later use;
(2) placing the undersize obtained in the step (1) into a reducing furnace, introducing hydrogen for reduction, wherein the retention time of the undersize in the reducing furnace is 8-12 hours, the loading thickness of the undersize in a sagger is 3-5cm, the flow speed of the hydrogen in the reducing furnace is 3-5m/s, the hydrogen content in the atmosphere in the reducing furnace is more than 99.5 percent, the reducing temperature is 400-450 ℃, cooling to the temperature of less than 40 ℃ in a cooling section in the reducing furnace, and taking out the undersize to obtain a reducing material;
(3) and (3) placing the reducing material obtained in the step (2) into a storage box filled with nitrogen for storage, and then adding hot pure water for washing, wherein the solid-to-liquid ratio is 1: 10-15, obtaining washing liquid and washing slag through three-stage countercurrent washing, introducing carbon dioxide into the washing liquid, then filtering to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, carrying out 3-stage countercurrent washing on the aluminum hydroxide precipitate, and then calcining to obtain superfine aluminum oxide, and carrying out pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate;
(4) adding hydrazine hydrate solution into the washing slag obtained in the step (3), adding sodium hydroxide to adjust the pH value of the solution to 13-14, pouring the solution into a stirring and grinding tank, heating to 75-85 ℃, stirring and reacting for 1-2 hours, pouring out the materials, filtering to obtain a second filtrate and a second filter residue, adding the second filter residue into the hydrazine hydrate solution to perform 3-stage countercurrent washing, then putting the second filter residue into a vacuum drying box to perform vacuum drying, and performing screening and magnetic separation on the dried materials, and then mixing the dried materials with outsourced cobalt powder, nickel powder and manganese powder to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain nickel-cobalt-manganese ternary mixed solution.
And (3) adopting corundum, mullite or stainless steel sagger in the step (2).
The temperature of the hot pure water is 75-90 ℃ in the process of washing the reducing material with the hot pure water in the step (3), when carbon dioxide is introduced to precipitate aluminum, a pH meter is inserted into a washing liquid, the process of introducing the carbon dioxide is started, the pH value is gradually reduced, aluminum hydroxide and lithium carbonate precipitate are obtained in the process, then the carbon dioxide is continuously introduced, the pH value of the washing liquid is gradually increased, then the introduction of the carbon dioxide is stopped until the pH meter is not changed, then the filtration is carried out, washing water obtained after 3-stage countercurrent washing of the aluminum hydroxide precipitate is mixed with a lithium bicarbonate solution, the mass ratio of the aluminum hydroxide precipitate to the washing water in the washing process is 1:4, the temperature of the washing water is 35-45 ℃, the calcination temperature of the washed aluminum hydroxide precipitate is 750-850 ℃, the calcination time is 2-4 hours, the temperature of the lithium bicarbonate solution in the high-temperature decomposition process is 95-99 ℃, stirring speed is 150-200r/min, decomposition time is 2.5 hours, the decomposed filtrate is returned to wash the reducing material, and the obtained lithium carbonate is dried, sieved and packaged to obtain battery-grade lithium carbonate.
In the step (4), the concentration of the hydrazine hydrate solution is 0.5mol/L, the mass ratio of the washing slag to the hydrazine hydrate solution is 1:3, the stirring of a stirring mill is 30r/min, the added grinding ball is made of zirconia, the diameter of the grinding ball is 0.2-1cm, carbon dioxide gas is introduced to ensure that aluminum precipitate is aluminum hydroxide, the aluminum hydroxide is washed and then mixed with the aluminum hydroxide precipitate in the step (3) for calcination, the concentration of the hydrazine hydrate solution adopted for washing the second filter residue is 0.06mol/L, the drying temperature of the vacuum drying process of the second filter residue is 60-70 ℃, and the vacuum degree is-0.09-0.08 MPa.
And (4) returning the nickel-cobalt-manganese ternary mixed solution in the step (4) to prepare the nickel-cobalt lithium manganate positive electrode material.
This patent is through freezing breakage, the aluminium foil breakage that will load nickel cobalt lithium manganate cathode material is tiny granule, then sieve, through hydrogen reduction under high temperature, aluminum powder also can carry out the replacement reaction with the nickel cobalt manganese among the nickel cobalt lithium manganate simultaneously, reduce nickel cobalt manganese to the simple substance, and lithium exists with the oxide form, then through the washing, the production obtains lithium hydroxide solution, thereby quick separating lithium and cobalt nickel manganese, and the washing process, thereby there is partial aluminium and lithium hydroxide reaction and get into in the lithium solution, then through letting in carbon dioxide gas, get off the aluminium sediment, turn into lithium hydroxide lithium carbonate simultaneously, then continue to let in carbon dioxide, lithium carbonate then turns into hydrogen carbonate lithium and dissolves the aquatic again, the separation of aluminium and lithium has been realized.
The obtained nickel, cobalt and manganese can be completely dissolved by the reaction in the mixed solution of hydrazine hydrate and sodium hydroxide, the oxidation of the nickel, cobalt and manganese is avoided, and the nickel, cobalt and manganese ternary metal powder is obtained after magnetic separation or the sulfuric acid solution is added to obtain the nickel, cobalt and manganese ternary solution.
The method realizes the separation of lithium and nickel, cobalt and manganese by utilizing hydrogen reduction, has short process flow, high recovery rate of lithium, high recovery rate of nickel, cobalt and manganese, low cost and less generated wastewater compared with a method of separating nickel, cobalt and manganese by completely entering nickel, manganese and cobalt into a solution by adopting acid dissolution, and can simply obtain battery-grade lithium carbonate, and the obtained nickel, cobalt and manganese can also be returned to be used as a nickel, cobalt and manganese lithium manganate positive electrode material. Meanwhile, the aluminum in the aluminum oxide can be recovered to obtain the ultrafine aluminum oxide.
The invention has the beneficial effects that: the method has the advantages of short flow, simple process, low cost, high recovery rate, high purity of the finally obtained product, high added value of the product and realization of recycling of materials, and can realize separation and recovery of all components.
Detailed Description
The invention will be described in detail with reference to specific embodiments, and the method for recycling the waste nickel cobalt lithium manganate positive electrode material of the embodiment comprises the following steps:
(1) preprocessing, namely disassembling the waste nickel-cobalt lithium manganate battery, crushing the positive plate in a liquid nitrogen freezing crusher, then sieving, sieving with a 100-mesh and 200-mesh sieve, returning oversize products to continue freezing and crushing, and reserving undersize products for later use;
(2) placing the undersize obtained in the step (1) into a reducing furnace, introducing hydrogen for reduction, wherein the retention time of the undersize in the reducing furnace is 8-12 hours, the loading thickness of the undersize in a sagger is 3-5cm, the flow speed of the hydrogen in the reducing furnace is 3-5m/s, the hydrogen content in the atmosphere in the reducing furnace is more than 99.5 percent, the reducing temperature is 400-450 ℃, cooling to the temperature of less than 40 ℃ in a cooling section in the reducing furnace, and taking out the undersize to obtain a reducing material;
(3) and (3) placing the reducing material obtained in the step (2) into a storage box filled with nitrogen for storage, and then adding hot pure water for washing, wherein the solid-to-liquid ratio is 1: 10-15, obtaining washing liquid and washing slag through three-stage countercurrent washing, introducing carbon dioxide into the washing liquid, then filtering to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, carrying out 3-stage countercurrent washing on the aluminum hydroxide precipitate, and then calcining to obtain superfine aluminum oxide, and carrying out pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate;
(4) adding hydrazine hydrate solution into the washing slag obtained in the step (3), adding sodium hydroxide to adjust the pH value of the solution to 13-14, pouring the solution into a stirring and grinding tank, heating to 75-85 ℃, stirring and reacting for 1-2 hours, pouring out the materials, filtering to obtain a second filtrate and a second filter residue, adding the second filter residue into the hydrazine hydrate solution to perform 3-stage countercurrent washing, then putting the second filter residue into a vacuum drying box to perform vacuum drying, and performing screening and magnetic separation on the dried materials, and then mixing the dried materials with outsourced cobalt powder, nickel powder and manganese powder to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain nickel-cobalt-manganese ternary mixed solution.
And (3) adopting corundum, mullite or stainless steel sagger in the step (2).
The temperature of the hot pure water is 75-90 ℃ in the process of washing the reducing material with the hot pure water in the step (3), when carbon dioxide is introduced to precipitate aluminum, a pH meter is inserted into a washing liquid, the process of introducing the carbon dioxide is started, the pH value is gradually reduced, aluminum hydroxide and lithium carbonate precipitate are obtained in the process, then the carbon dioxide is continuously introduced, the pH value of the washing liquid is gradually increased, then the introduction of the carbon dioxide is stopped until the pH meter is not changed, then the filtration is carried out, washing water obtained after 3-stage countercurrent washing of the aluminum hydroxide precipitate is mixed with a lithium bicarbonate solution, the mass ratio of the aluminum hydroxide precipitate to the washing water in the washing process is 1:4, the temperature of the washing water is 35-45 ℃, the calcination temperature of the washed aluminum hydroxide precipitate is 750-850 ℃, the calcination time is 2-4 hours, the temperature of the lithium bicarbonate solution in the high-temperature decomposition process is 95-99 ℃, stirring speed is 150-200r/min, decomposition time is 2.5 hours, the decomposed filtrate is returned to wash the reducing material, and the obtained lithium carbonate is dried, sieved and packaged to obtain battery-grade lithium carbonate.
In the step (4), the concentration of the hydrazine hydrate solution is 0.5mol/L, the mass ratio of the washing slag to the hydrazine hydrate solution is 1:3, the stirring of a stirring mill is 30r/min, the added grinding ball is made of zirconia, the diameter of the grinding ball is 0.2-1cm, carbon dioxide gas is introduced to ensure that aluminum precipitate is aluminum hydroxide, the aluminum hydroxide is washed and then mixed with the aluminum hydroxide precipitate in the step (3) for calcination, the concentration of the hydrazine hydrate solution adopted for washing the second filter residue is 0.06mol/L, the drying temperature of the vacuum drying process of the second filter residue is 60-70 ℃, and the vacuum degree is-0.09-0.08 MPa.
And (4) returning the nickel-cobalt-manganese ternary mixed solution in the step (4) to prepare the nickel-cobalt lithium manganate positive electrode material.
Example 1
A method for recycling waste nickel cobalt lithium manganate cathode materials comprises the following steps:
(1) preprocessing, namely disassembling the waste nickel-cobalt lithium manganate battery, crushing the positive plate in a liquid nitrogen freezing crusher, sieving with a 150-mesh sieve, returning the oversize to continue freezing and crushing, and keeping the undersize for later use;
(2) placing the undersize product obtained in the step (1) into a reducing furnace, introducing hydrogen for reduction, wherein the retention time of the undersize product in the reducing furnace is 10 hours, the charging thickness of the undersize product in a sagger is 4.5cm, the flow speed of the hydrogen in the reducing furnace is 4m/s, the hydrogen content in the atmosphere in the reducing furnace is more than 99.5 percent, the reducing temperature is 425 ℃, then cooling the undersize product in a cooling section of the reducing furnace to the temperature of less than 40 ℃, and discharging the product out of the reducing furnace to obtain a reduced material;
(3) and (3) placing the reducing material obtained in the step (2) into a storage box filled with nitrogen for storage, and then adding hot pure water for washing, wherein the solid-to-liquid ratio is 1: 12, performing three-stage countercurrent washing to obtain washing liquid and washing slag, introducing carbon dioxide into the washing liquid, filtering to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, performing 3-stage countercurrent washing on the aluminum hydroxide precipitate, calcining to obtain superfine aluminum oxide, and performing pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate;
(4) adding a hydrazine hydrate solution into the washing slag obtained in the step (3), adding sodium hydroxide to adjust the pH value of the solution to 13.5, pouring the solution into a stirring and grinding tank, heating to the temperature of 79 ℃, stirring and reacting for 1.8 hours, pouring the material out, filtering to obtain a second filtrate and a second filter residue, adding the second filter residue into the hydrazine hydrate solution to perform 3-stage countercurrent washing, then putting the second filter residue into a vacuum drying oven to perform vacuum drying, and performing screening and magnetic separation on the dried material, and then mixing and blending the dried material with purchased cobalt powder, nickel powder and manganese powder to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain a nickel-cobalt-manganese ternary mixed solution.
And (3) adopting a corundum sagger as the sagger in the step (2).
The temperature of the hot pure water is 79 ℃ in the process of washing the reducing material with the hot pure water in the step (3), when carbon dioxide is introduced to precipitate aluminum, a pH meter is inserted into a washing liquid, the process of introducing the carbon dioxide is started, the pH value is gradually reduced, aluminum hydroxide and lithium carbonate precipitate are obtained in the process, then the carbon dioxide is continuously introduced, the pH value of the washing liquid is gradually increased, then the introduction of the carbon dioxide is stopped until the pH meter is not changed, then the filtration is carried out, washing water obtained after 3-stage countercurrent washing of the aluminum hydroxide precipitate is mixed with a lithium bicarbonate solution, the mass ratio of the aluminum hydroxide precipitate to the washing water in the washing process is 1:4, the temperature of the washing water is 39 ℃, the calcination temperature of the washed aluminum hydroxide precipitate is 790 ℃, the calcination time is 3 hours, the temperature of the lithium bicarbonate solution in the high-temperature decomposition is 98 ℃, the stirring speed is 180r/min, the decomposition time is 2.5 hours, the decomposed filtrate is returned to wash the reducing material, and the obtained lithium carbonate is dried, sieved and packaged to obtain the battery-grade lithium carbonate.
In the step (4), the concentration of the hydrazine hydrate solution is 0.5mol/L, the mass ratio of the washing slag to the hydrazine hydrate solution is 1:3, the stirring of a stirring mill is 30r/min, the added grinding ball is made of zirconia, the diameter of the grinding ball is 0.2-1cm, carbon dioxide gas is introduced to ensure that aluminum precipitate is aluminum hydroxide, the aluminum hydroxide is washed and then mixed with the aluminum hydroxide precipitate in the step (3) for calcination, the concentration of the hydrazine hydrate solution adopted for washing the second filter residue is 0.06mol/L, the drying temperature of the vacuum drying process of the second filter residue is 66 ℃, and the vacuum degree is-0.085 Mpa.
And (4) returning the nickel-cobalt-manganese ternary mixed solution in the step (4) to prepare the nickel-cobalt lithium manganate positive electrode material.
The finally obtained lithium carbonate meets the requirements of the industry standard YS/T582 and 2013. The obtained monitoring data of the nickel-cobalt-manganese ternary alloy powder are as follows:
| Ni+Co+Mn | Fe | Al | Zn | Li |
| 99.28％ | 34ppm | 38ppm | 8ppm | 29ppm |
| Na | Ca | Mg | S | O |
| 28ppm | 21ppm | 19ppm | 24ppm | 0.13％ |
the obtained monitoring data of the ultrafine alumina are as follows:
| principal content | Na | Co | Ni | Mn | Ca |
| 99.53％ | 25ppm | 2ppm | 2ppm | 5.1ppm | 5.9ppm |
| D50 | D100 | Primary particle diameter | BET | Sulfate radical | Tap density |
| 0.7 micron | 2.2 micron | 28nm | 112m2/g | 68ppm | 0.4g/mL |
Finally, the comprehensive recovery rate of lithium is 99.2%, the recovery rate of aluminum is 97.9%, and the recovery rates of nickel, cobalt and manganese are 99.3%, 99.5% and 99.3% respectively.
Example 2
A method for recycling waste nickel cobalt lithium manganate cathode materials comprises the following steps:
(1) preprocessing, namely disassembling the waste nickel-cobalt lithium manganate battery, crushing the positive plate in a liquid nitrogen freezing crusher, sieving with a 120-mesh sieve, returning the oversize to continue freezing and crushing, and keeping the undersize for later use;
(2) placing the undersize product obtained in the step (1) into a reducing furnace, introducing hydrogen for reduction, wherein the retention time of the undersize product in the reducing furnace is 11 hours, the charging thickness of the undersize product in a sagger is 4.2cm, the flow speed of the hydrogen in the reducing furnace is 4.5m/s, the hydrogen content in the atmosphere in the reducing furnace is more than 99.5 percent, the reducing temperature is 440 ℃, cooling the undersize product in a cooling section of the reducing furnace to the temperature of less than 40 ℃, and discharging the product to obtain a reducing material;
(3) and (3) placing the reducing material obtained in the step (2) into a storage box filled with nitrogen for storage, and then adding hot pure water for washing, wherein the solid-to-liquid ratio is 1: 13, performing three-stage countercurrent washing to obtain washing liquid and washing slag, introducing carbon dioxide into the washing liquid, filtering to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, performing 3-stage countercurrent washing on the aluminum hydroxide precipitate, calcining to obtain superfine aluminum oxide, and performing pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate;
(4) adding a hydrazine hydrate solution into the washing slag obtained in the step (3), adding sodium hydroxide to adjust the pH value of the solution to 13.8, pouring the solution into a stirring and grinding tank, heating to the temperature of 79 ℃, stirring and reacting for 1.5 hours, pouring the material out, filtering to obtain a second filtrate and a second filter residue, adding the second filter residue into the hydrazine hydrate solution to perform 3-stage countercurrent washing, then putting the second filter residue into a vacuum drying oven to perform vacuum drying, and performing screening and magnetic separation on the dried material, and then mixing and blending the dried material with purchased cobalt powder, nickel powder and manganese powder to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain a nickel-cobalt-manganese ternary mixed solution.
And (3) adopting a mullite sagger as the sagger in the step (2).
The temperature of the hot pure water is 79 ℃ in the process of washing the reducing material with the hot pure water in the step (3), when carbon dioxide is introduced to precipitate aluminum, a pH meter is inserted into a washing liquid, the process of introducing the carbon dioxide is started, the pH value is gradually reduced, aluminum hydroxide and lithium carbonate precipitate are obtained in the process, then the carbon dioxide is continuously introduced, the pH value of the washing liquid is gradually increased, then the introduction of the carbon dioxide is stopped until the pH meter is not changed, then the filtration is carried out, washing water obtained after 3-stage countercurrent washing of the aluminum hydroxide precipitate is mixed with a lithium bicarbonate solution, the mass ratio of the aluminum hydroxide precipitate to the washing water in the washing process is 1:4, the temperature of the washing water is 39 ℃, the calcination temperature of the washed aluminum hydroxide precipitate is 790 ℃, the calcination time is 3 hours, the temperature of the lithium bicarbonate solution in the high-temperature decomposition is 98 ℃, the stirring speed is 180r/min, the decomposition time is 2.5 hours, the decomposed filtrate is returned to wash the reducing material, and the obtained lithium carbonate is dried, sieved and packaged to obtain the battery-grade lithium carbonate.
In the step (4), the concentration of the hydrazine hydrate solution is 0.5mol/L, the mass ratio of the washing slag to the hydrazine hydrate solution is 1:3, the stirring of a stirring mill is 30r/min, the added grinding ball is made of zirconia, the diameter of the grinding ball is 0.2-1cm, carbon dioxide gas is introduced to ensure that aluminum precipitate is aluminum hydroxide, the aluminum hydroxide is washed and then mixed with the aluminum hydroxide precipitate in the step (3) for calcination, the concentration of the hydrazine hydrate solution adopted for washing the second filter residue is 0.06mol/L, the drying temperature of the vacuum drying process of the second filter residue is 66 ℃, and the vacuum degree is-0.085 Mpa.
And (4) returning the nickel-cobalt-manganese ternary mixed solution in the step (4) to prepare the nickel-cobalt lithium manganate positive electrode material.
The finally obtained lithium carbonate meets the requirements of the industry standard YS/T582 and 2013. The obtained monitoring data of the nickel-cobalt-manganese ternary alloy powder are as follows:
the obtained monitoring data of the ultrafine alumina are as follows:
| principal content | Na | Co | Ni | Mn | Ca |
| 99.51％ | 25ppm | 2.1ppm | 1.8ppm | 5.1ppm | 5.8ppm |
| D50 | D100 | Primary particle diameter | BET | Sulfate radical | Tap density |
| 0.8 micron | 2.1 micron | 22nm | 123m2/g | 65ppm | 0.4g/mL |
Finally, the comprehensive recovery rate of lithium is 99.2%, the recovery rate of aluminum is 97.8%, and the recovery rates of nickel, cobalt and manganese are 99.3%, 99.5% and 99.2%, respectively.
Example 3
A method for recycling waste nickel cobalt lithium manganate cathode materials comprises the following steps:
(1) preprocessing, namely disassembling the waste nickel-cobalt lithium manganate battery, crushing the positive plate in a liquid nitrogen freezing crusher, sieving with a 170-mesh sieve, returning the oversize to continue freezing and crushing, and keeping the undersize for later use;
(2) placing the undersize product obtained in the step (1) into a reducing furnace, introducing hydrogen for reduction, wherein the retention time of the undersize product in the reducing furnace is 9.5 hours, the charging thickness of the undersize product in a sagger is 4.5cm, the flow speed of the hydrogen in the reducing furnace is 4.2m/s, the hydrogen content in the atmosphere in the reducing furnace is more than 99.5 percent, the reducing temperature is 440 ℃, cooling the undersize product in a cooling section in the reducing furnace to the temperature of less than 40 ℃, and discharging the undersize product to obtain a reduced material;
(3) and (3) placing the reducing material obtained in the step (2) into a storage box filled with nitrogen for storage, and then adding hot pure water for washing, wherein the solid-to-liquid ratio is 1: 11, performing three-stage countercurrent washing to obtain washing liquid and washing slag, introducing carbon dioxide into the washing liquid, filtering to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, performing 3-stage countercurrent washing on the aluminum hydroxide precipitate, calcining to obtain superfine aluminum oxide, and performing pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate;
(4) adding a hydrazine hydrate solution into the washing slag obtained in the step (3), adding sodium hydroxide to adjust the pH value of the solution to 13.8, pouring the solution into a stirring and grinding tank, heating to 82 ℃, stirring and reacting for 1.6 hours, pouring out the materials, filtering to obtain a second filtrate and a second filter residue, adding the second filter residue into the hydrazine hydrate solution to perform 3-stage countercurrent washing, then putting the second filter residue into a vacuum drying oven to perform vacuum drying, and performing screening and magnetic separation on the dried materials, and then mixing and blending the dried materials with purchased cobalt powder, nickel powder and manganese powder to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain a nickel-cobalt-manganese ternary mixed solution.
And (3) adopting a stainless steel sagger in the step (2).
The temperature of the hot pure water is 79 ℃ in the process of washing the reducing material with the hot pure water in the step (3), when carbon dioxide is introduced to precipitate aluminum, a pH meter is inserted into a washing liquid, the process of introducing the carbon dioxide is started, the pH value is gradually reduced, aluminum hydroxide and lithium carbonate precipitate are obtained in the process, then the carbon dioxide is continuously introduced, the pH value of the washing liquid is gradually increased, then the introduction of the carbon dioxide is stopped until the pH meter is not changed, then the filtration is carried out, the washing water obtained after 3-stage countercurrent washing of the aluminum hydroxide precipitate and the lithium bicarbonate solution are mixed, the mass ratio of the aluminum hydroxide precipitate to the washing water in the washing process is 1:4, the temperature of the washing water is 42 ℃, the calcination temperature of the washed aluminum hydroxide precipitate is 820 ℃, the calcination time is 3.8 hours, the temperature of the lithium bicarbonate solution in the high-temperature decomposition is 98 ℃, and the stirring speed is 185r/, the decomposition time is 2.5 hours, the decomposed filtrate is returned to wash the reducing material, and the obtained lithium carbonate is dried, sieved and packaged to obtain the battery-grade lithium carbonate.
In the step (4), the concentration of the hydrazine hydrate solution is 0.5mol/L, the mass ratio of the washing slag to the hydrazine hydrate solution is 1:3, the stirring of a stirring mill is 30r/min, the added grinding ball is made of zirconia, the diameter of the grinding ball is 0.2-1cm, carbon dioxide gas is introduced to ensure that aluminum precipitate is aluminum hydroxide, the aluminum hydroxide is washed and then mixed with the aluminum hydroxide precipitate in the step (3) for calcination, the concentration of the hydrazine hydrate solution adopted for washing the second filter residue is 0.06mol/L, the drying temperature of the vacuum drying process of the second filter residue is 68 ℃, and the vacuum degree is-0.083 MPa.
And (4) returning the nickel-cobalt-manganese ternary mixed solution in the step (4) to prepare the nickel-cobalt lithium manganate positive electrode material.
The finally obtained lithium carbonate meets the requirements of the industry standard YS/T582 and 2013. The obtained monitoring data of the nickel-cobalt-manganese ternary alloy powder are as follows:
| Ni+Co+Mn | Fe | Al | Zn | Li |
| 99.31％ | 28ppm | 29ppm | 6ppm | 31ppm |
| Na | Ca | Mg | S | O |
| 29ppm | 21ppm | 18ppm | 28ppm | 0.11％ |
the obtained monitoring data of the ultrafine alumina are as follows:
| principal content | Na | Co | Ni | Mn | Ca |
| 99.48％ | 25ppm | 2.1ppm | 3.5ppm | 5.1ppm | 6.7ppm |
| D50 | D100 | Primary particle diameter | BET | Sulfate radical | Tap density |
| 0.7 micron | 2.0 micron | 21nm | 128m2/g | 61ppm | 0.4g/mL |
Finally, the comprehensive recovery rate of lithium is 99.3%, the recovery rate of aluminum is 97.9%, and the recovery rates of nickel, cobalt and manganese are 99.4%, 99.5% and 99.3% respectively.
The amount of the waste water generated in the embodiments 1, 2 and 3 of the invention is less than 15 tons per ton of waste nickel cobalt lithium manganate material, but the amount of the waste water generated in the conventional processes of preparing battery-grade lithium carbonate by using a sulfuric acid solution, precipitating and removing aluminum, extracting and separating nickel cobalt manganese and a carbonization method is more than 30 tons, the recovery rate of lithium is low and generally not more than 99%, and the process flow is long.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (3)
1. A method for recycling a waste nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps:
(1) preprocessing, namely disassembling the waste nickel-cobalt lithium manganate battery, crushing the positive plate in a liquid nitrogen freezing crusher, then sieving, sieving with a 100-mesh and 200-mesh sieve, returning oversize products to continue freezing and crushing, and reserving undersize products for later use;
(2) placing the undersize obtained in the step (1) into a reducing furnace, introducing hydrogen for reduction, wherein the retention time of the undersize in the reducing furnace is 8-12 hours, the loading thickness of the undersize in a sagger is 3-5cm, the flow speed of the hydrogen in the reducing furnace is 3-5m/s, the hydrogen content in the atmosphere in the reducing furnace is more than 99.5 percent, the reducing temperature is 400-450 ℃, cooling to the temperature of less than 40 ℃ in a cooling section in the reducing furnace, and taking out the undersize to obtain a reducing material;
(3) and (3) placing the reducing material obtained in the step (2) into a storage box filled with nitrogen for storage, and then adding hot pure water for washing, wherein the solid-to-liquid ratio is 1: 10-15, performing three-stage countercurrent washing to obtain washing liquid and washing slag, introducing carbon dioxide into the washing liquid, then filtering to obtain a lithium bicarbonate solution and an aluminum hydroxide precipitate, performing 3-stage countercurrent washing on the aluminum hydroxide precipitate, calcining to obtain superfine aluminum oxide, performing pyrolysis on the obtained lithium bicarbonate to obtain battery-grade lithium carbonate, wherein the temperature of hot pure water is 75-90 ℃ in the process of washing and reducing materials by the hot pure water, inserting a pH meter into the washing liquid when the carbon dioxide is introduced to precipitate aluminum, starting the process of introducing the carbon dioxide, gradually reducing the pH value to obtain aluminum hydroxide and lithium carbonate precipitate in the process, then continuously introducing the carbon dioxide, gradually increasing the pH value of the washing liquid, then stopping introducing the carbon dioxide until the pH meter is not changed, then filtering, mixing the washing water obtained after the aluminum hydroxide precipitate is subjected to 3-stage countercurrent washing with the lithium bicarbonate solution, the mass ratio of the aluminum hydroxide precipitate to the washing water in the washing process is 1:4, the temperature of the washing water is 35-45 ℃, the calcination temperature of the washed aluminum hydroxide precipitate is 750-850 ℃, the calcination time is 2-4 hours, the temperature of the lithium bicarbonate solution during pyrolysis is 95-99 ℃, the stirring speed is 150-200r/min, the decomposition time is 2.5 hours, the decomposed filtrate is returned to wash the reducing material, and the obtained lithium carbonate is dried, sieved and packaged to obtain battery-grade lithium carbonate;
(4) adding the washing slag obtained in the step (3) into a hydrazine hydrate solution, adding sodium hydroxide to adjust the pH value of the solution to 13-14, pouring the solution into a stirring mill tank, heating to 75-85 ℃, stirring for reaction for 1-2 hours, pouring out the materials, filtering to obtain a second filtrate and a second filter residue, adding the second filter residue into the hydrazine hydrate solution to perform 3-stage countercurrent washing, then putting the second filter residue into a vacuum drying box to perform vacuum drying, sieving and magnetically separating the dried materials, mixing the dried materials with purchased cobalt powder, nickel powder and manganese powder to obtain nickel-cobalt-manganese ternary alloy powder or directly adding acid to dissolve the nickel-cobalt-manganese ternary alloy powder to obtain a nickel-cobalt-manganese ternary mixed solution, wherein the concentration of the hydrazine hydrate solution is 0.5mol/L, the mass ratio of the washing slag to the hydrazine hydrate solution is 1:3, stirring of the stirring mill is 30r/min, and the added milling balls are made of zirconium oxide, and (3) introducing carbon dioxide gas to ensure that the aluminum precipitate is aluminum hydroxide, washing the aluminum hydroxide, mixing the washed aluminum hydroxide with the aluminum hydroxide precipitate obtained in the step (3) for calcination, wherein the concentration of a hydrazine hydrate solution used for washing the second filter residue is 0.06mol/L, the drying temperature of the vacuum drying process of the second filter residue is 60-70 ℃, and the vacuum degree is-0.09 MPa to-0.08 MPa.
2. The method for recycling the waste nickel cobalt lithium manganate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: and (3) adopting corundum, mullite or stainless steel sagger in the step (2).
3. The method for recycling the waste nickel cobalt lithium manganate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: and (4) returning the nickel-cobalt-manganese ternary mixed solution in the step (4) to prepare the nickel-cobalt lithium manganate positive electrode material.
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| CN109250802B (en) * | 2018-11-29 | 2021-07-16 | 黄河水利职业技术学院 | Electroplating wastewater comprehensive treatment process |
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| CN111786008B (en) * | 2020-07-10 | 2022-04-05 | 中国矿业大学 | Multi-process efficient and synergistic recycling method for retired lithium ion battery positive electrode material |
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| CN112680598A (en) * | 2020-12-15 | 2021-04-20 | 中南大学 | Method for low-cost clean treatment of waste lithium ion battery anode material |
| EP4359576A1 (en) | 2021-06-23 | 2024-05-01 | H.C. Starck Tungsten GmbH | Process for recycling battery materials by way of reductive, pyrometallurgical treatment |
| CN113690501B (en) * | 2021-07-23 | 2023-09-08 | 广东邦普循环科技有限公司 | Recycling process of acid-removed battery pole piece |
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