CN114480854A - Method for extracting valuable metals from waste lithium ion battery materials - Google Patents
Method for extracting valuable metals from waste lithium ion battery materials Download PDFInfo
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- CN114480854A CN114480854A CN202210148869.5A CN202210148869A CN114480854A CN 114480854 A CN114480854 A CN 114480854A CN 202210148869 A CN202210148869 A CN 202210148869A CN 114480854 A CN114480854 A CN 114480854A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
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- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The application provides a method for extracting valuable metals from waste lithium ion battery materials, and relates to the field of solid waste recovery. The method for extracting valuable metals from waste lithium ion battery materials comprises the following steps: mixing raw materials including waste lithium ion battery materials and elemental sulfur to obtain a mixed material, and roasting the mixed material in an oxygen-enriched environment to obtain a roasted material; crushing the roasted material, performing first leaching by using water, and performing first solid-liquid separation to obtain a lithium-containing solution and filter residue; and mixing the filter residue, water and acid for secondary leaching, and then carrying out secondary solid-liquid separation to obtain a valuable metal solution. The method for extracting the valuable metals from the waste lithium ion battery materials is simple to operate, small in influence on the environment and low in cost.
Description
Technical Field
The application relates to the field of solid waste recovery, in particular to a method for extracting valuable metals from waste lithium ion battery materials.
Background
Under the promotion of energy and environmental crisis, along with the rapid development and popularization of new energy automobiles, the demand of large-scale lithium ion batteries is brought, if the waste batteries are discarded, not only can serious pollution be brought to the environment, but also resource waste is caused, and therefore, the method has very important significance in harmless treatment of the waste lithium batteries and recycling of resources in the waste lithium batteries.
At present, the main approaches for recycling and treating the waste lithium ion batteries are a pyrometallurgical method and a hydrometallurgical method, and because the pyrometallurgical method has some key problems in domestic application, the hydrometallurgical method becomes a mainstream method for treating the waste lithium ion batteries in China and is widely researched. The wet process mainly comprises the following steps: in the treatment process, lithium is simultaneously leached into the solution along with nickel, cobalt, manganese and the like, and after the nickel, the cobalt and the manganese are extracted by methods of extraction, chemical precipitation and the like, the lithium remains in the residual solution, and at the moment, the concentration of lithium ions in the solution is low, the content of sodium ions in the solution is high, and the difficulty in recovering the lithium from the solution is high.
In the existing reduction roasting-water leaching method, lithium in a roasted product exists in the form of lithium carbonate, then the lithium carbonate is dissolved in water in a water leaching mode, other elements such as nickel, cobalt and manganese enter slag in the form of insoluble substances, and preferential separation and extraction of lithium are realized.
The existing method for treating the anode material of the waste lithium ion battery by adopting a sulfur reduction mode inevitably converts nickel, cobalt and manganese in the material of the waste lithium ion battery into corresponding sulfides during roasting, and the sulfides are difficult to be directly leached, so that great difficulty is brought to the subsequent acid leaching recovery of nickel-cobalt-manganese sulfide slag, and toxic hydrogen sulfide gas is easily released in the acid leaching process.
The research and development of a recovery method which is simple in operation, small in environmental impact and low in cost becomes a problem to be solved urgently.
Disclosure of Invention
The present application aims to provide a method for extracting valuable metals from waste lithium ion battery materials, so as to solve the above problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a method for extracting valuable metals from waste lithium ion battery materials comprises the following steps:
mixing raw materials including waste lithium ion battery materials and elemental sulfur to obtain a mixed material, and roasting the mixed material in an oxygen-enriched environment to obtain a roasted material;
crushing the roasted material, performing first leaching by using water, and performing first solid-liquid separation to obtain a lithium-containing solution and filter residue;
and mixing the filter residue, water and acid for secondary leaching, and then carrying out secondary solid-liquid separation to obtain a valuable metal solution.
Preferably, the amount of the elemental sulfur is 0.05-2 times of the mass of the waste lithium ion battery material.
Preferably, the amount of the elemental sulfur is 0.1-0.5 times of the mass of the waste lithium ion battery material.
Preferably, the roasting temperature is 200-1200 ℃, and the roasting time is 30-600 min;
preferably, the roasting temperature is 500-1000 ℃ and the roasting time is 60-120 min.
Preferably, the oxygen-enriched environment comprises oxygen-enriched air or oxygen.
Preferably, the temperature of the first leaching is 20-90 ℃, the time is 15-240 min, and the liquid-solid ratio is 2ml:1g-15ml:1 g;
preferably, the temperature of the first leaching is 50-80 ℃, the time is 30-120 min, and the liquid-solid ratio is 2ml:1g-8ml:1 g.
Preferably, the acid comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid;
preferably, the acid is sulfuric acid.
Preferably, the temperature of the second leaching is 20-90 ℃ and the time is 15-240 min;
preferably, the temperature of the second leaching is 50-80 ℃ and the time is 30-120 min.
Preferably, the active material in the waste lithium ion battery material comprises one or more of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium manganese oxide.
Compared with the prior art, the beneficial effect of this application includes:
the method for extracting valuable metals from waste lithium ion battery materials comprises the steps of mixing raw materials including the waste lithium ion battery materials and elemental sulfur to obtain a mixed material, and roasting the mixed material in an oxygen-enriched environment to obtain a roasted material; crushing the roasted material, performing first leaching by using water, and performing first solid-liquid separation to obtain a lithium-containing solution and filter residue. In the roasting process, due to the existence of elemental sulfur, lithium oxide and sulfur oxide in the battery material are combined and converted into water-soluble lithium sulfate, meanwhile, part of molten sulfur is combined with valuable metals such as nickel, cobalt, manganese and the like and converted into corresponding sulfides, but the sulfides of nickel, cobalt and manganese are oxidized again in an oxygen-rich environment, so that under the process condition, the nickel, cobalt and manganese elements exist in filter residue in an oxide form finally, the water-soluble lithium sulfate and the nickel, cobalt and manganese oxide in solid slag can be separated simply and effectively, and then the filter residue is treated in an acid leaching mode, so that the high-efficiency recovery of lithium and the recovery and utilization of the valuable metals such as nickel, cobalt and manganese are realized.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
Fig. 1 is a schematic flow chart of a method for extracting valuable metals from waste lithium ion battery materials according to an embodiment.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: 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 unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A method for extracting valuable metals from waste lithium ion battery materials comprises the following steps:
mixing raw materials including waste lithium ion battery materials and elemental sulfur to obtain a mixed material, and roasting the mixed material in an oxygen-enriched environment to obtain a roasted material;
and crushing the roasted material, performing first leaching by using water, and performing first solid-liquid separation to obtain a lithium-containing solution and filter residue.
In an alternative embodiment, the amount of elemental sulfur is 0.05 to 2 times the mass of the waste lithium ion battery material.
In an alternative embodiment, the amount of the elemental sulfur is 0.1 to 0.5 times the mass of the waste lithium ion battery material.
Optionally, the amount of the elemental sulfur may be 0.05 times, 0.1 times, 0.5 times, 1.0 times, 1.5 times, 2 times, or any value between 0.05 and 2 times of the mass of the waste lithium ion battery material.
In an alternative embodiment, the temperature of the roasting is 200-1200 ℃ and the time is 30-600 min;
in order to effectively destroy the structure of the anode material and completely oxidize and remove sulfur, in an optional embodiment, the roasting temperature is 500-1000 ℃ and the roasting time is 60-120 min.
Optionally, the roasting temperature may be any value between 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or 200 ℃ to 1200 ℃, and the time may be any value between 30min, 60min, 120min, 180min, 240min, 300min, 360min, 420min, 480min, 540min, 600min or 30min to 600 min.
In an alternative embodiment, the oxygen-enriched environment comprises oxygen-enriched air or oxygen.
In an alternative embodiment, the temperature of the first leaching is 20-90 ℃, the time is 15-240 min, and the liquid-solid ratio is 2ml:1g-15ml:1 g;
in an alternative embodiment, the first leaching is carried out at a temperature of 50 ℃ to 80 ℃ for 30min to 120min, and the liquid-solid ratio is 2ml:1g to 8ml:1 g.
Optionally, the temperature of the first leaching may be any value between 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 20 ℃ to 90 ℃, the time may be any value between 15min, 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min or 15min to 240min, and the liquid-solid ratio may be 2ml:1g, 3ml:1g, 4 ml:1g, 5ml:1g, 6 ml:1g, 7 ml:1g, 8ml:1g, 9 ml:1g, 10 ml:1g, 11 ml:1g, 12 ml:1g, 13 ml:1g, 14 ml:1g, 15ml:1g or any value between 2ml:1g and 15ml:1 g.
In an alternative embodiment, the acid comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid;
in an alternative embodiment, the acid is sulfuric acid.
In an alternative embodiment, the temperature of the second leaching is 20 ℃ to 90 ℃ and the time is 15min to 240 min;
in an alternative embodiment, the second leach is at a temperature of 50 ℃ to 80 ℃ for a time of 30min to 120 min.
Optionally, the temperature of the second leaching may be any value between 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 20 ℃ to 90 ℃, and the time may be any value between 15min, 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min or 15min to 240 min.
In an alternative embodiment, the active material in the waste lithium ion battery material comprises one or more of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate and lithium manganese.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
As shown in fig. 1, the embodiment provides a method for extracting valuable metals from waste nickel cobalt lithium manganate battery materials, which includes the following steps:
(1) mixing the waste lithium ion battery material with elemental sulfur to obtain a mixed material; the mass of the elemental sulfur is 0.1 time of that of the waste lithium ion battery material.
(2) And (2) putting the mixed material in the step (1) into a roasting furnace/kiln, introducing oxygen into the furnace, and roasting at the roasting temperature of 1200 ℃ for 30 min.
(3) And crushing a roasted product.
(4) Adding water to the crushed product obtained in the step (3) for leaching, wherein the water leaching temperature is 20 ℃, the water leaching time is 240min, and the liquid-solid ratio is 3ml:1g of the total weight of the composition.
(5) And (4) filtering the leached slurry liquid in the step (4) to obtain filtrate and filter residue, wherein the filtrate is used for preparing a lithium compound product.
(6) After the filter residue in the step (5) is mixed with water for size mixing, sulfuric acid is added for leaching, and filtration is carried out to obtain lithium-containing nickel-cobalt-manganese filtrate for further recovering valuable metals therein; the acid leaching temperature is 60 ℃, and the acid leaching time is 120 min.
Example 2
The embodiment provides a method for extracting valuable metals from waste lithium manganate battery materials, which comprises the following steps:
(1) mixing the waste lithium ion battery material with elemental sulfur to obtain a mixed material; the mass of the elemental sulfur is 1.0 time of that of the waste lithium ion battery material.
(2) And (2) putting the mixed material in the step (1) into a roasting furnace/kiln, introducing oxygen-enriched air into the furnace, roasting at the roasting temperature of 200 ℃ for 600 min.
(3) And crushing a roasted product.
(4) Adding water to the crushed product obtained in the step (3) for leaching, wherein the water leaching temperature is 90 ℃, the water leaching time is 15min, and the liquid-solid ratio is 5ml:1g of the total weight of the composition.
(5) And (4) filtering the leached slurry liquid in the step (4) to obtain filtrate and filter residue, wherein the filtrate is used for preparing a lithium compound product.
(6) After the filter residue in the step (5) is mixed with water for size mixing, sulfuric acid is added for leaching, and filtration is carried out to obtain lithium-containing nickel-cobalt-manganese filtrate for further recovering valuable metals therein; the acid leaching temperature is 20 ℃, and the acid leaching time is 240 min.
Example 3
The embodiment provides a method for extracting valuable metals from waste lithium cobaltate battery materials, which comprises the following steps:
(1) mixing the waste lithium ion battery material with elemental sulfur to obtain a mixed material; the mass of the elemental sulfur is 0.5 time of that of the waste lithium ion battery material.
(2) And (2) putting the mixed material in the step (1) into a roasting furnace/kiln, introducing oxygen into the furnace for roasting, wherein the roasting temperature is 1000 ℃, and the roasting time is 120 min.
(3) And crushing a roasted product.
(4) Adding water to the crushed product obtained in the step (3) for leaching, wherein the water leaching temperature is 70 ℃, the water leaching time is 120min, and the liquid-solid ratio is 4 ml:1g of the total weight of the composition.
(5) And (4) filtering the leached slurry liquid in the step (4) to obtain filtrate and filter residue, wherein the filtrate is used for preparing a lithium compound product.
(6) After the filter residue in the step (5) is mixed with water for size mixing, sulfuric acid is added for leaching, and filtration is carried out to obtain lithium-containing nickel-cobalt-manganese filtrate for further recovering valuable metals therein; the acid leaching temperature is 80 ℃, and the acid leaching time is 120 min.
Comparative example 1 this comparative example provides a method for extracting valuable lithium metal from waste nickel cobalt lithium manganate battery materials, comprising the following steps:
(1) mixing the anode material of the waste lithium ion battery with coke to obtain a mixed material; the adding amount of the coke is 0.25 time of the mass of the waste lithium ion battery material.
(2) And (2) putting the mixed material in the step (1) into a roasting furnace/kiln, and roasting under the protection of nitrogen, wherein the roasting temperature is 750 ℃, and the roasting time is 120 min.
(3) And crushing a roasted product.
(4) And (4) adding water to the roasted product in the step (3) for leaching, wherein the water leaching temperature is 20 ℃, the water leaching time is 240min, and the liquid-solid ratio is 3ml:1 g.
(5) And (4) filtering the leached slurry in the step (4) to obtain filtrate and filter residue.
(6) After the filter residue in the step (5) is mixed with water for size mixing, sulfuric acid is added for leaching, and filtration is carried out to obtain lithium-containing nickel-cobalt-manganese filtrate for further recovering valuable metals therein; the acid leaching temperature is 60 ℃, and the acid leaching time is 120 min.
Comparative example 2
The comparative example provides a method for extracting valuable metal lithium from waste nickel cobalt lithium manganate battery materials, which comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with elemental sulfur to obtain a mixed material; the adding amount of the elemental sulfur is 0.1 time of the mass of the waste lithium ion battery material.
(2) And (2) putting the mixed material in the step (1) into a roasting furnace/kiln, and roasting the mixed material in an air atmosphere without introducing any gas, wherein the roasting temperature is 750 ℃, and the roasting time is 120 min.
(3) And crushing a roasted product.
(4) And (4) adding water to the roasted product in the step (3) for leaching, wherein the water leaching temperature is 20 ℃, the water leaching time is 240min, and the liquid-solid ratio is 3ml:1 g.
(5) And (4) filtering the leached slurry in the step (4) to obtain filtrate and filter residue.
(6) Mixing the filter residue obtained in the step (5) with water, adding sulfuric acid for leaching, and filtering to obtain lithium-containing nickel-cobalt-manganese filtrate for further recovering valuable metals in the filtrate; the acid leaching temperature is 60 ℃, and the acid leaching time is 120 min.
Comparative example 3
The comparative example provides a method for extracting valuable metals from waste nickel cobalt lithium manganate battery materials, which comprises the following steps:
(1) mixing the anode material of the waste lithium ion battery with elemental sulfur to obtain a mixed material; the adding amount of the elemental sulfur is 0.1 time of the mass of the waste lithium ion battery material.
(2) And (2) putting the mixed material in the step (1) into a roasting furnace/kiln, and roasting the mixed material in an air atmosphere without introducing any gas, wherein the roasting temperature is 1000 ℃ and the roasting time is 120 min.
(3) And crushing a roasted product.
(4) And (4) adding water to the roasted product in the step (3) for leaching, wherein the water leaching temperature is 20 ℃, the water leaching time is 240min, and the liquid-solid ratio is 3ml:1 g.
(5) And (4) filtering the leached slurry in the step (4) to obtain filtrate and filter residue.
(6) After the filter residue in the step (5) is mixed with water for size mixing, sulfuric acid is added for leaching, and filtration is carried out to obtain lithium-containing nickel-cobalt-manganese filtrate for further recovering valuable metals therein; the acid leaching temperature is 60 ℃, and the acid leaching time is 120 min.
The schemes provided in the examples and comparative examples, the leaching rates of lithium and other valuable metals finally obtained are shown in the following table 1:
TABLE 1 Leaching Rate data
As can be seen from the comparison of the leaching rate of lithium and the leaching rates of other valuable metals, comparative example 1 shows that when the waste lithium battery material is treated by the carbothermic reduction roasting-water leaching process, the leaching rate of lithium is very low during the leaching at a low liquid-solid ratio; comparative example 2 shows that roasting in an air atmosphere causes the leaching rate of other valuable metals to be greatly reduced compared with roasting in an oxygen-rich environment; comparative example 3 shows that the leaching rate of other valuable metals cannot be effectively increased even if the roasting temperature is increased by roasting in the air atmosphere.
The application proposes S + O2The method for extracting valuable metals by roasting the anode materials of the waste lithium ion batteries in the environment destroys the structure of the anode materials of the waste lithium ion batteries by utilizing the synergistic effect of elemental sulfur and oxygen in a high-temperature environment, so that lithium in the anode materials is converted into lithium sulfate, and nickel, cobalt and manganese are converted into corresponding oxides to avoid the generation of sulfides, and has the following advantages:
(1) lithium in the roasting slag exists in the form of lithium sulfate with good water solubility, nickel, cobalt and manganese exist in the form of oxides, and through water leaching, the efficient selective preferential extraction of lithium can be realized, and metals such as nickel, cobalt, manganese and the like are hardly leached.
(2) The nickel, cobalt and manganese in the water leaching slag exist in the form of easily leached oxides, sulfides which are difficult to leach do not exist, the nickel, cobalt and manganese elements in the water leaching slag can be leached through simple acid leaching, toxic hydrogen sulfide gas is not generated in the acid leaching process, and the high-efficiency recovery of nickel, cobalt and manganese is realized.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, 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 application 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 extracting valuable metals from waste lithium ion battery materials is characterized by comprising the following steps:
mixing raw materials including waste lithium ion battery materials and elemental sulfur to obtain a mixed material, and roasting the mixed material in an oxygen-enriched environment to obtain a roasted material;
crushing the roasted material, performing first leaching by using water, and performing first solid-liquid separation to obtain a lithium-containing solution and filter residue;
and mixing the filter residue, water and acid for secondary leaching, and then carrying out secondary solid-liquid separation to obtain a valuable metal solution.
2. The method of claim 1, wherein the amount of elemental sulfur is 0.05-2 times the mass of the used lithium ion battery material.
3. The method of claim 1, wherein the amount of elemental sulfur is 0.1-0.5 times the mass of the used lithium ion battery material.
4. The method according to claim 1, characterized in that the roasting temperature is 200-1200 ℃ and the roasting time is 30-600 min;
preferably, the roasting temperature is 500-1000 ℃ and the roasting time is 60-120 min.
5. The method of claim 1, wherein the oxygen-enriched environment comprises oxygen-enriched air or oxygen.
6. The method according to claim 1, wherein the temperature of the first leaching is 20-90 ℃, the time is 15-240 min, and the liquid-solid ratio is 2ml:1g-15ml:1 g;
preferably, the temperature of the first leaching is 50-80 ℃, the time is 30-120 min, and the liquid-solid ratio is 2ml:1g-8ml:1 g.
7. The method of claim 1, wherein the acid comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
8. The method of claim 7, wherein the acid is sulfuric acid.
9. The method according to claim 1, characterized in that the temperature of the second leaching is 20-90 ℃ and the time is 15-240 min;
preferably, the temperature of the second leaching is 50-80 ℃ and the time is 30-120 min.
10. The method according to any one of claims 1 to 9, wherein the active material in the spent lithium ion battery material comprises one or more of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese, lithium nickel cobalt aluminate, lithium manganese.
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