CN115852152B - Method for cooperatively treating battery black powder and nickel cobalt hydroxide - Google Patents
Method for cooperatively treating battery black powder and nickel cobalt hydroxide Download PDFInfo
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- CN115852152B CN115852152B CN202310173475.XA CN202310173475A CN115852152B CN 115852152 B CN115852152 B CN 115852152B CN 202310173475 A CN202310173475 A CN 202310173475A CN 115852152 B CN115852152 B CN 115852152B
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Abstract
The application provides a method for cooperatively treating battery black powder and nickel cobalt hydroxide, and relates to the technical field of battery recovery treatment. The method for cooperatively treating the battery black powder and the nickel cobalt hydroxide specifically comprises the following steps: roasting the battery black powder and a reducing agent to obtain calcine; grinding and leaching the calcine to obtain ore pulp; adding nickel cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag; and carrying out acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and nickel-cobalt-manganese-rich leaching liquid. According to the method, lithium in the battery black powder can be extracted preferentially, and then elements such as nickel, cobalt and manganese in the battery black powder and nickel, cobalt and hydroxide are extracted in an enrichment mode, so that enrichment and recovery of valuable metals are achieved.
Description
Technical Field
The application relates to the technical field of battery recycling, in particular to a method for cooperatively treating battery black powder and nickel cobalt hydroxide.
Background
Along with the increase of the popularization strength of the new energy automobiles, the new energy automobiles keep 784 tens of thousands of vehicles by the end of 2021, and are in a high-speed growth situation, so that the contradictory relation between supply and demand of resources such as nickel/cobalt/lithium is further aggravated, and resource replenishment is urgently required. Based on the consideration of related policy, production cost and other factors, more and more enterprises choose to supplement nickel/cobalt/lithium from intermediate products, namely nickel cobalt hydroxide and secondary resource waste lithium batteries.
At present, in the method for realizing the recovery of substances such as nickel, cobalt and the like in an intermediate product, namely nickel cobalt hydroxide, some selection is madeFirstly, performing concentrated sulfuric acid curing on nickel-cobalt hydroxide, and then reducing and leaching the curing leaching solution to prepare nickel-cobalt sulfate solution, thereby realizing nickel-cobalt recovery; some methods sequentially perform the steps of sulfuric acid-sodium sulfite reduction leaching, neutralization impurity removal, extraction separation of nickel and cobalt and the like, so that high-purity recovery of nickel and cobalt is realized. Aiming at the recovery method of valuable metals in waste batteries, some waste lithium batteries and carbonaceous reducing agents are subjected to carbothermic reduction roasting at a certain temperature, so that lithium exists in the form of lithium carbonate, and then direct water leaching or CO is adopted 2 Leaching water to realize preferential extraction of lithium; some waste lithium batteries are roasted with ammonium sulfate, potassium hydrogen sulfate or sodium bisulfate at a certain temperature, and then the roasted product is soaked in water to realize the separation of lithium and nickel/cobalt/manganese.
However, the intermediate product, namely nickel cobalt hydroxide and the waste lithium battery are cooperatively treated, so that the recovery method of nickel/cobalt/lithium and other resources is less, and if the nickel/cobalt/lithium resources are combined, the method can be optimized to a certain extent in the aspects of equipment investment, process cost and the like. Therefore, a method for cooperatively treating nickel cobalt hydroxide and waste lithium batteries is urgently needed to realize the enrichment and recovery of valuable metals.
Disclosure of Invention
The purpose of the application is to provide a method for cooperatively processing battery black powder and nickel cobalt hydroxide, lithium in the battery black powder can be preferentially extracted by the method for cooperatively processing, and then elements such as nickel, cobalt, manganese and the like in the battery black powder and the nickel cobalt hydroxide are enriched and extracted, so that enrichment and recovery of valuable metals are realized.
In order to achieve the above object, the technical scheme of the present application is as follows:
the application provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
roasting the battery black powder and a reducing agent to obtain calcine;
grinding and leaching the calcine to obtain ore pulp;
adding nickel cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag;
and carrying out acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and nickel-cobalt-manganese-rich leaching liquid.
In some embodiments of the present application, the battery black powder includes at least one of a waste lithium ion battery positive electrode powder and a waste lithium ion battery positive and negative electrode mixed powder.
In some embodiments of the present application, the reducing agent comprises at least one of carbon powder, hydrogen, metal salts.
In some embodiments of the present application, the firing is at a temperature of 300 ℃ to 800 ℃ for a time of 1h to 6h.
In some embodiments of the present application, the calcine has a particle size of greater than or equal to 200 mesh after grinding.
In some embodiments of the present application, at least one of the following conditions is also satisfied:
a. the water leaching treatment process also comprises carbon dioxide introduction;
b. the liquid-solid ratio of water in the water leaching treatment to the calcine is 2mL/g-10mL/g;
c. the temperature of the water leaching treatment is 10-100 ℃ and the time is 0.5-3 h.
In some embodiments of the present application, the pH of the slurry after the nickel cobalt hydroxide is added to the slurry is 10 to 12;
the reaction temperature is 10-100 ℃ and the reaction time is 1-3 h.
In some embodiments of the present application, the sulfuric acid is concentrated sulfuric acid, and the amount of the sulfuric acid is 1 to 1.5 times of the theoretical amount;
before the acid leaching treatment is carried out, the method further comprises the following steps: mixing the nickel-cobalt-manganese rich slag with water, and then adding the sulfuric acid; the liquid-solid ratio of the water to the nickel-cobalt-manganese rich slag is 3mL/g-10 mL/g.
In some embodiments of the present application, the acid leaching treatment is performed at a temperature of 40 ℃ to 90 ℃ for a time of 2 hours to 6 hours.
In some embodiments of the present application, the firing is performed in an atmosphere of a shielding gas including at least one of argon, nitrogen.
The beneficial effects of this application:
in the method, after the battery black powder is reduced by a reducing agent, nickel/cobalt exists in a metal form, and lithium exists in a lithium salt form which is easy to dissolve in water. After the ore pulp is prepared by water leaching, nickel cobalt hydroxide has a certain alkalinity and can be used as a neutralizing agent for impurity removal, nickel/cobalt/manganese plasma in the ore pulp exists in solid slag after solid-liquid separation in a hydroxide form which is difficult to dissolve in water, so that a purified lithium-rich solution is obtained, wherein the nickel/cobalt/manganese/aluminum/copper plasma can be reduced to below 10ppm, and the requirement of preparing an aqueous solution by using battery-grade lithium carbonate can be met only by removing impurities aiming at part of ions in the follow-up process. In the acid leaching process, metals such as nickel/cobalt and the like obtained from the calcine can be used as a reducing agent of high-valence cobalt, so that the high-valence cobalt in the nickel cobalt hydroxide is subjected to oxidation-reduction reaction under the action of sulfuric acid, and the high-efficiency leaching of nickel/cobalt/manganese can be realized without adding other reducing agents, and the leaching rate can reach more than 99%. Compared with the method for independently treating the waste batteries and the method for independently treating the nickel cobalt hydroxide, the method has the advantages of being high in cost and beneficial to industrial popularization and application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope of the present invention.
Fig. 1 is an XRD phase analysis diagram of calcine obtained by roasting battery black powder and reducing agent carbon powder at different temperatures.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The application provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
s1, roasting battery black powder and a reducing agent to obtain calcine;
s2, grinding and leaching the calcine to obtain ore pulp;
s3, adding nickel-cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag;
s4, carrying out acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and nickel-cobalt-manganese-rich leaching liquid.
In some optional embodiments of the present application, the battery black powder in S1 includes at least one of a waste lithium ion battery positive electrode powder and a waste lithium ion battery positive and negative electrode mixed powder.
It can be understood that the battery black powder can be purchased directly, or can be obtained by discharging, disassembling, crushing and separating the waste lithium ion battery, and the disassembled battery black powder is mainly an active positive electrode material and also contains carbon materials of a plurality of negative electrodes. The waste lithium ion battery can be a unitary lithium ion battery containing any one of nickel, cobalt and manganese or any two binary lithium ion batteries, and can also be a ternary lithium ion battery containing nickel, cobalt and manganese or nickel, cobalt and aluminum.
It should be noted that, the black powder of the battery in the present application S1 may be replaced by a positive powder of the battery, which is mainly derived from an unqualified product generated in the process of producing the positive material.
In some alternative embodiments of the present application, the reducing agent in S1 includes at least one of carbon powder, hydrogen, metal salts.
It is understood that if the black powder of the battery in S1 itself contains carbon powder or the like, the carbon powder contained in itself may be used as a reducing agent for reduction. If the battery black powder is subjected to carbothermal reduction roasting, the nickel/cobalt compound is reduced into nickel/cobalt metal, and lithium exists in the form of water-soluble lithium carbonate, and the specific reaction mechanism is as follows:
specifically, the inventor of the application carries out roasting treatment on the battery black powder and the reducing agent carbon powder at different temperatures, and other conditions are consistent except the temperature. Finally, XRD detection is carried out on calcines obtained at different temperatures, and the corresponding XRD patterns are shown in figure 1. As can be seen from the figure, the Ni/Co simple substance appears in the calcine at 550 ℃ and above.
If the battery black powder is reduced by hydrogen, nickel/cobalt exists in the calcine in the metal form, and lithium exists in the form of lithium hydroxide which is easy to dissolve in water, the specific reaction mechanism is as follows:
in the roasting process, metal sulfate (such as nickel/cobalt/manganese sulfate) can be used as a reducing agent, wherein metal can be replaced with lithium in the waste lithium battery, the rest of the metal exists in a metal oxide form, and part of the metal exists in a metal form after being reduced due to the fact that the raw material contains a small amount of negative electrode material C, so that direct water leaching can be adopted to realize preferential extraction of the lithium.
In some alternative embodiments of the present application, the firing temperature at which the firing is performed in S1 is 300 ℃ to 800 ℃, e.g., may be 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, or any value between 300 ℃ to 800 ℃, and the firing time is 1h to 6h, e.g., may be 1h, 2h, 3h, 4h, 5h, 6h, or any value between 1h to 6h.
In some alternative embodiments of the present application, the firing in S1 also needs to be performed under an atmosphere of a shielding gas including at least one of argon and nitrogen.
In some alternative embodiments of the present application, the calcine particle size after grinding in S2 is ≡200 mesh. It is understood that the lithium-containing compounds in the calcine are more soluble in water when stirred in water by leaching after grinding.
In some optional embodiments of the present application, the step of performing the water leaching treatment in S2 further includes introducing carbon dioxide.
It is to be noted that the solubility of the lithium carbonate formed after thermal reduction roasting using carbon is not very high, and thus the lithium carbonate is converted into lithium bicarbonate which is more soluble in water by passing carbon dioxide into an aqueous solution.
In some alternative embodiments of the present application, the liquid-to-solid ratio of water to calcine used in the water leaching treatment in S2 is between 2mL/g and 10mL/g, and may be, for example, between 2mL/g, 3mL/g, 4mL/g, 5mL/g, 6mL/g, 7mL/g, 8mL/g, 9mL/g, 10mL/g, or any value between 2mL/g and 10mL/g.
Further, the temperature of the water immersion treatment is 10 ℃ to 100 ℃, for example, 10 ℃, 20 ℃, 40 ℃, 70 ℃, 100 ℃ or any value between 10 ℃ to 100 ℃, and the time is 0.5h to 3h, for example, 0.5h, 1h, 1.5h, 2h, 2.5h, 3h or any value between 0.5h to 3h. After water immersion at room temperature, solid-liquid separation is not required.
In some alternative embodiments of the present application, after the nickel cobalt hydroxide is added to the pulp in S3, the pH of the pulp is 10-12.
It should be noted that the nickel cobalt hydroxide can be purchased directly, or prepared from laterite nickel ore as raw material by high-pressure acid leaching technology, or prepared from battery black powder.
Nickel cobalt hydroxide (MHP), also known as cobalt nickel hydroxide, belongs to a nickel intermediate product, and can be used for preparing nickel sulfate, thereby preparing an electrode positive electrode material. The nickel cobalt hydroxide contains a large amount of alkaline substances, so that free metal ions in the ore pulp can be hydrolyzed and precipitated, nickel/cobalt/manganese plasma in the ore pulp is enriched in slag in the form of hydroxide which is difficult to dissolve in water, and effective separation of lithium and other metal impurities is realized. The amount of the nickel cobalt hydroxide added into the ore pulp is based on the optimal leaching rate of nickel/cobalt/manganese in the leaching solution after the acid leaching treatment of the nickel cobalt manganese slag.
In some alternative embodiments of the present application, the slurry is added to S3, and the reaction is performed at a temperature of 10 ℃ to 100 ℃, more preferably at room temperature, for a period of 1h to 3h, for example, 1h, 1.5h, 2h, 2.5h, 3h, or any value between 1h and 3h.
In some alternative embodiments of the present application, the sulfuric acid used in S4 is concentrated sulfuric acid, and the amount of the sulfuric acid is 1-1.5 times of the theoretical amount, so that leaching of each element in the nickel-cobalt-manganese-rich slag can be promoted. Further, the mass fraction of the concentrated sulfuric acid is 98%.
The obtained nickel-cobalt-manganese-rich slag contains simple-substance metals such as nickel/cobalt and the like, so that the metals can be used as a reducing agent, and high-valence cobalt in the nickel-cobalt-manganese-rich slag is subjected to oxidation-reduction reaction under the action of concentrated sulfuric acid, so that cobalt elements are fully and efficiently leached out, for example, co (OH) 3 can react with cobalt under a concentrated sulfuric acid system, and the method specifically comprises the following steps:
further, before the acid leaching treatment in S4, the method further includes: mixing the nickel-cobalt-manganese rich slag with water, and then mixing the mixed slag with sulfuric acid for acid leaching treatment. Wherein the liquid-solid ratio of water to nickel-cobalt-manganese-rich slag is 3mL/g-10mL/g, and can be any value between 3mL/g, 4mL/g, 5mL/g, 6mL/g, 7mL/g, 8mL/g, 9mL/g, 10mL/g or 3mL/g-10 mL/g.
In some alternative embodiments of the present application, the temperature of the acid leaching treatment in S4 is between 40 ℃ and 90 ℃, for example, may be between 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or any value between 40 ℃ and 90 ℃, for a time of between 2h and 6h, for example, may be between 2h, 3h, 4h, 5h, 6h or any value between 2h and 6h. After acid leaching treatment, leaching residues and nickel-cobalt-rich manganate leaching liquid can be obtained through solid-liquid separation.
Embodiments of the present invention will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate, crushing the positive plate, dissolving the positive plate in N-methyl pyrrolidone to remove a current collector, and then cleaning and drying to obtain the battery black powder containing positive electrode powder.
(2) Weighing 50g of battery black powder, introducing hydrogen to bake for 5 hours at 600 ℃ under the protection of argon, and cooling to obtain calcine.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of the calcine, adding 50mL of water, carrying out water leaching treatment at room temperature, and stirring for 2h to obtain ore pulp.
(4) Slowly adding nickel cobalt hydroxide into the ore pulp in the step (3), testing the pH value in the pulp, stopping adding when the pH value is between 10 and 11, stirring at room temperature, reacting for 2 hours, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag.
(5) Drying a small amount of nickel-cobalt-manganese-rich slag obtained in the step (4), analyzing the water content and the metal content of nickel, cobalt and manganese, and the like, obtaining the water content and the metal content of nickel, cobalt and manganese, and the like in all the nickel-cobalt-manganese-rich slag according to the result, and adding water to prepare the nickel-cobalt-manganese-rich slag into a liquid-solid ratio of 5mL:1g of ore pulp, adding 1.1 times of concentrated sulfuric acid (98%) with theoretical mass, stirring at 50 ℃, reacting for 6 hours, and performing solid-liquid separation to obtain leaching residues and nickel-cobalt-manganese-rich leaching liquid.
The leaching rate of lithium in step (4) of this example was 98.15%, and nickel/cobalt/manganese was not substantially leached; acid leaching process of step (5): the leaching rates of nickel/cobalt/manganese are 98.23%, 98.65% and 96% respectively.
Example 2
The embodiment provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate and a negative plate, crushing, dissolving in N-methyl pyrrolidone to remove a current collector, and then cleaning and drying to obtain the battery black powder containing the positive and negative mixed powder.
(2) Weighing 50g of battery black powder and 10g of carbon powder, uniformly mixing, roasting for 3 hours at 800 ℃ in an argon atmosphere, and cooling to obtain calcine.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of the calcine, adding 30mL of water, carrying out water leaching treatment at room temperature, simultaneously introducing excessive carbon dioxide, and stirring for 2 hours to obtain ore pulp.
(4) Slowly adding nickel cobalt hydroxide into the ore pulp in the step (3), testing the pH value in the pulp, stopping adding when the pH value is between 10 and 11, stirring at room temperature, reacting for 2 hours, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag.
(5) Drying a small amount of nickel-cobalt-manganese-rich wet slag in the step (4), analyzing the water content, nickel-cobalt-manganese and other metal contents, obtaining the water content, nickel-cobalt-manganese and other metal contents in all the nickel-cobalt-manganese-rich slag according to the result, and adding water to prepare the nickel-cobalt-manganese-rich slag into a liquid-solid ratio of 5mL:1g of ore pulp, adding 1.1 times of concentrated sulfuric acid (98%) with theoretical mass, stirring at 50 ℃, reacting for 6 hours, and performing solid-liquid separation to obtain leaching residues and nickel-cobalt-manganese-rich leaching liquid.
The leaching rate of lithium in step (4) of this example was 80.12% and nickel/cobalt/manganese was essentially non-leaching; acid leaching process of step (5): the leaching rates of nickel/cobalt/manganese are 99.14%, 98.13% and 95.84% respectively.
Example 3
The embodiment provides a method for cooperatively processing battery black powder and nickel cobalt hydroxide, which comprises the following steps:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate and a negative plate, crushing, dissolving in N-methyl pyrrolidone to remove a current collector, and then cleaning and drying to obtain the battery black powder containing the positive and negative mixed powder.
(2) Weighing 50g of battery black powder and 60g of nickel sulfate hexahydrate, roasting for 5 hours at 800 ℃ under the protection of argon, and cooling to obtain calcine.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of the calcine, adding 50mL of water, carrying out water leaching treatment at room temperature, and stirring for 2h to obtain ore pulp.
(4) Slowly adding nickel cobalt hydroxide into the ore pulp in the step (3), testing the pH value in the pulp, stopping adding when the pH value is between 10 and 11, stirring at room temperature, reacting for 2 hours, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag.
(5) Drying a small amount of nickel-cobalt-manganese-rich wet slag in the step (4), analyzing the water content, nickel-cobalt-manganese and other metal contents, obtaining the water content, nickel-cobalt-manganese and other metal contents in all the nickel-cobalt-manganese-rich slag according to the result, and adding water to prepare the nickel-cobalt-manganese-rich slag into a liquid-solid ratio of 5mL:1g of ore pulp, adding 1.1 times of concentrated sulfuric acid (98%) with theoretical mass, stirring at 50 ℃, reacting for 6 hours, and performing solid-liquid separation to obtain leaching residues and nickel-cobalt-manganese-rich leaching liquid.
The leaching rate of lithium in step (4) of this example was 99.58% and nickel/cobalt/manganese was not substantially leached; acid leaching process of step (5): the leaching rates of nickel/cobalt/manganese are 99.35%, 99.24% and 98% respectively.
Comparative example 1
This comparative example provides a method of treating battery black powder comprising:
(1) Discharging the waste nickel-cobalt-manganese ternary battery, disassembling to obtain a positive plate, crushing the positive plate, dissolving the positive plate in N-methyl pyrrolidone to remove a current collector, and then cleaning and drying to obtain the battery black powder containing positive electrode powder.
(2) Weighing 50g of battery black powder and 60g of nickel sulfate hexahydrate, roasting for 5 hours at 800 ℃ under the protection of argon, and cooling to obtain calcine.
(3) Grinding the calcine obtained in the step (2) to 200 meshes, weighing 10g of the calcine, adding 30mL of water, carrying out water leaching treatment at room temperature, stirring for 2 hours, and carrying out solid-liquid separation to obtain a lithium-rich solution and solid slag.
(4) And (3) mixing the solid slag obtained in the step (3) with water in a liquid-solid ratio of 5mL:1g of the slurry is prepared, sulfuric acid (98%) is added, stirring is carried out at 50 ℃, solid-liquid separation is carried out after reaction is carried out for 6 hours, and leaching slag and nickel-cobalt-manganese-rich leaching liquid are obtained.
The water leaching process of the step (3) of the comparative example: the leaching rate of lithium is 99.15 percent, and the leaching rates of nickel/cobalt/manganese are 3.13 percent, 0.21 percent and 13.25 percent respectively; acid leaching process of step (4): the leaching rates of nickel/cobalt/manganese are 82.14%, 86.37% and 89.24% respectively.
Comparing the leaching rates of examples 1-3 and comparative example 1, it is evident that during the preferential leaching of lithium by water leaching, a significant portion of the nickel/manganese is not thoroughly separated as lithium enters the aqueous solution, and the leaching rate of nickel/cobalt/manganese is also lower in the resulting solid slag because there is no reducing agent such as elemental nickel/cobalt metal.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for cooperatively treating battery black powder and nickel cobalt hydroxide, comprising the steps of:
roasting the battery black powder and a reducing agent to obtain calcine;
grinding and leaching the calcine to obtain ore pulp;
adding nickel cobalt hydroxide into the ore pulp, reacting, and carrying out solid-liquid separation to obtain a lithium-rich solution and nickel-cobalt-manganese-rich slag;
and carrying out acid leaching treatment on the nickel-cobalt-manganese-rich slag and sulfuric acid to obtain leaching slag and nickel-cobalt-manganese-rich leaching liquid.
2. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the battery black powder comprises at least one of waste lithium ion battery positive electrode powder and waste lithium ion battery positive electrode and negative electrode mixed powder.
3. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the reducing agent comprises at least one of carbon powder, hydrogen gas, and metal salt.
4. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the roasting temperature is 300 ℃ to 800 ℃ and the time is 1h to 6h.
5. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the grain size of the calcine after grinding is more than or equal to 200 meshes.
6. The method of co-processing battery black powder and nickel cobalt hydroxide according to claim 1, further satisfying at least one of the following conditions:
a. the water leaching treatment process also comprises carbon dioxide introduction;
b. the liquid-solid ratio of water in the water leaching treatment to the calcine is 2mL/g-10mL/g;
c. the temperature of the water leaching treatment is 10-100 ℃ and the time is 0.5-3 h.
7. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the pH of the slurry after the nickel cobalt hydroxide is added to the slurry is 10 to 12;
the reaction temperature is 10-100 ℃ and the reaction time is 1-3 h.
8. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the sulfuric acid is concentrated sulfuric acid, and the amount of the sulfuric acid is 1 to 1.5 times of the theoretical amount;
before the acid leaching treatment is carried out, the method further comprises the following steps: mixing the nickel-cobalt-manganese rich slag with water, and then adding the sulfuric acid; the liquid-solid ratio of the water to the nickel-cobalt-manganese rich slag is 3mL/g-10 mL/g.
9. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to claim 1, wherein the acid leaching treatment is performed at a temperature of 40 ℃ to 90 ℃ for 2h to 6h.
10. The method for cooperatively treating battery black powder and nickel cobalt hydroxide according to any one of claims 1-9, wherein the firing is performed in an atmosphere of a shielding gas comprising at least one of argon and nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310173475.XA CN115852152B (en) | 2023-02-28 | 2023-02-28 | Method for cooperatively treating battery black powder and nickel cobalt hydroxide |
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