CN111593200A - Method for recovering valuable metals in waste lithium ion batteries - Google Patents

Method for recovering valuable metals in waste lithium ion batteries Download PDF

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Publication number
CN111593200A
CN111593200A CN202010362131.XA CN202010362131A CN111593200A CN 111593200 A CN111593200 A CN 111593200A CN 202010362131 A CN202010362131 A CN 202010362131A CN 111593200 A CN111593200 A CN 111593200A
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lithium
reaction
carbon dioxide
waste
valuable metals
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赵君梅
李波
刘会洲
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention provides a method for recovering valuable metals in waste lithium ion batteries, which comprises the following steps: s1, placing the mixed solution of the anode material waste and water into a reaction container; s2, introducing carbon dioxide gas into the reaction container to enable the positive electrode material waste to react with the carbon dioxide; s3, obtaining a leaching solution containing lithium after the reaction is finished; wherein the solute of the leach solution comprises a carbonate of lithium. The method has simple operation steps, the equipment belongs to conventional equipment, carbon dioxide is a main consumable in the operation process, other acids and bases are not used, the operation cost is low, no waste water is generated, and the purity of the obtained lithium salt product is high. During leaching, metal ions other than lithium are not substantially leached; in the process of preparing lithium salt from the leaching solution, the lithium salt product can be obtained only by heating without an additional precipitator, so that the problems of salt control and wastewater treatment can be effectively solved.

Description

Method for recovering valuable metals in waste lithium ion batteries
Technical Field
The invention relates to a lithium ion battery recovery technology, in particular to a method for recovering valuable metals in waste lithium ion batteries.
Background
Because fossil energy has great pollution to the environment, secondary batteries, especially lithium ion batteries, as clean energy are receiving more and more attention, and the application range of lithium ion batteries is wider and wider. However, the resource of lithium element is limited, and as the usage amount of lithium ion batteries is increased, there is a growing concern about sustainable supply of lithium resource. The life of lithium ion batteries is generally 3-5 years, and in view of the large-scale use of lithium ion batteries, more and more lithium ion batteries are in the end-of-life period at present. If the waste lithium ion battery can not be effectively treated, huge pressure is brought to the environment. Therefore, it is a great national demand to recover valuable metals from waste lithium ion batteries, especially valuable metal elements such as lithium from the waste powder of the positive electrode of waste batteries, both for the purpose of environmental protection and for the purpose of ensuring sustainable supply of resources.
At present, in the process for recovering lithium from the ternary positive electrode waste powder of the lithium ion battery, most of the steps for recovering lithium are arranged after other valuable metals (such as Ni, Co and Mn, or Ni, Co and Al) are recovered, so that the lithium recovery is very unfavorable, because Na and NH are introduced into the mother solution containing lithium in the process of recovering other valuable metals4And the like, and the large accumulation of impurity elements is extremely disadvantageous to the recovery of lithium. In addition, lithium losses also occur in the individual process steps for recovering other valuable metals. For the lithium iron phosphate anode material, because the value of Li is higher than that of other metal elements, the preferential lithium extraction has more economic benefit.
Therefore, for the main stream anode ternary material and the lithium iron phosphate material of the lithium battery, if Li can be recovered from the anode waste powder by one step without causing the loss of other metal elements, the method has great significance. The method has the advantages of achieving high recovery rate and high purity for recovering lithium salt products from the lithium battery anode waste powder, and solving the problem of salt control in the lithium salt precipitation process, and has great challenges.
Disclosure of Invention
The embodiment of the invention provides a method for recovering valuable metals in waste lithium ion batteries, which aims to solve the technical problems in the prior art.
According to a first aspect, an embodiment of the present invention provides a method for recovering valuable metals from waste lithium ion batteries, where the method includes the following steps:
s1, placing the mixed solution of the anode material waste and water into a reaction container;
s2, introducing carbon dioxide gas into the reaction container to enable the anode material waste to react with the carbon dioxide;
s3, obtaining a leaching solution containing lithium after the reaction is finished;
wherein the solute of the leach solution comprises a carbonate of lithium.
Preferably, the reaction vessel comprises a reaction kettle;
preferably, the reaction vessel comprises a high pressure reaction vessel.
Preferably, the positive electrode material includes a ternary positive electrode material, lithium cobaltate and/or lithium manganate, and the method specifically includes the following steps:
s1, mixing the mixed solution of the anode material waste and water according to a certain solid-to-liquid ratio and placing the mixture into a reaction container;
s2, introducing carbon dioxide gas into the reaction vessel, controlling the pressure at 0.5-5Mpa, controlling the reaction temperature at 100-220 ℃ and the reaction time at 1-30 h;
s3, after the reaction is finished, cooling the reaction kettle, releasing pressure, and filtering reactants to obtain leachate containing lithium;
preferably, the solid-to-liquid ratio is 20g/L-300 g/L;
preferably, stirring is carried out simultaneously with the reaction in step S2, and the stirring speed is 50-1000 rpm;
preferably, the main components of the filter residue obtained by filtering the reactant comprise Ni, Co, Mn, Al and/or Cu elements;
preferably, the filter residue is subjected to acid leaching, and then hydrometallurgical separation is adopted, so that valuable metals of Ni, Co, Mn, Al and/or Cu are recovered;
preferably, the hydrometallurgical separation comprises precipitation separation or extraction separation.
Preferably, the method further comprises the steps of:
s4, heating the lithium-containing leaching solution at 50-100 ℃ under normal pressure or vacuum environment or heating at 50-100 ℃ by adopting a rotary evaporation heating mode, and drying at 70-90 ℃ to obtain the lithium carbonate.
Preferably, the positive electrode material includes a lithium iron phosphate positive electrode material, and the method specifically includes the following steps:
s1, mixing the mixed solution of the anode material waste and water according to a certain solid-to-liquid ratio and placing the mixture into a reaction container;
s2, adding 2-10% of hydrogen peroxide in volume percentage relative to the mixed solution into the reaction container, and then starting to introduce carbon dioxide gas with the flow of 0.2-10L/min, controlling the reaction temperature at 0-60 ℃ and the reaction time at 1-30 h;
s3, after the reaction is finished, filtering the reactant to obtain leachate containing lithium;
preferably, the solid-to-liquid ratio is 25g/L-300 g/L;
preferably, in step S2, stirring is carried out simultaneously with the reaction, and the stirring speed is 100-2000 rpm;
preferably, the reaction vessel comprises an atmospheric pressure reaction vessel;
preferably, the main component of the filter residue obtained by filtering the reactant comprises iron phosphate;
preferably, the filter residue is further recycled by adopting an acid leaching impurity removal or direct regeneration mode.
Preferably, the method further comprises the steps of:
s4, heating the lithium-containing leaching solution at 50-100 ℃ under normal pressure or vacuum environment or heating at 50-100 ℃ by adopting a rotary evaporation heating mode, and drying at 70-90 ℃ to obtain the lithium carbonate.
Preferably, after step S3, the other valuable metal ions in the residue other than lithium or the residue itself is recycled;
preferably, recovery of other valuable metals than lithium is not performed before step S3;
preferably, the other valuable metals include elements of Ni, Co, Mn, Al, Cu and/or Fe.
Preferably, the carbon dioxide gas in step S2 is derived from flue gas from coal combustion or industrial grade CO2。
Preferably, the method further includes the following steps before step S1:
and S0, pretreating the disassembled lithium ion battery anode material, and milling to obtain anode material waste.
Preferably, the obtained leaching solution is heated to obtain a lithium carbonate product, the product purity is more than 99%, and the recovery rate of lithium is more than 95%.
The invention is realized by adding carbon dioxide (CO)2) The selective extraction of Li is realized under certain conditions by introducing the aqueous solution of the anode waste powder, and the extraction of Li is prior to the extraction of other valuable metals, so that the loss of Li caused in the process of extracting other valuable metals in the prior art is avoided. Heating the obtained leaching solution to obtain a lithium carbonate product, wherein the purity of the product is more than 99 percent, and the recovery rate of Li is more than 95 percent.
The technology for recovering Li has simple operation steps, the equipment belongs to conventional equipment, and carbon dioxide (CO) is used in the operation process2) The method is a main consumable, does not use other acid or alkali, does not produce waste water, has low operation cost, and obtains a lithium salt product with high purity. During leaching, metal ions other than lithium are not substantially leached; in the process of preparing lithium salt from the leaching solution, the lithium salt product can be obtained only by heating without additional precipitator, so that the problem of salt control can be effectively solvedAnd wastewater treatment problems. The technology has high application value.
Another value of this technology is that the flue gas or industrial grade CO of coal combustion can be fully utilized2Carbon dioxide (CO) in flue gas2) The content of (A) is up to more than 90%. Flue gas or technical grade CO for burning coal2The method is combined with the waste powder of the positive electrode of the lithium ion battery to prepare the high-value lithium carbonate product, and is the best idea of waste utilization.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
FIG. 1 is a schematic flow diagram of the recovery process of the present invention.
Fig. 2 shows the XRD pattern of lithium carbonate extracted as in example one of the present invention.
Fig. 3 shows an XRD pattern of lithium carbonate extracted in example two of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The recovery method of the present invention will be described in detail below with reference to FIG. 1. As shown in fig. 1, the present invention provides a method for recovering valuable metals from waste lithium ion batteries, which comprises the following steps:
and S1, placing the mixed solution of the cathode material waste and water into a reaction container.
In this step, the reaction vessel comprises a reaction kettle; in a particular embodiment, the reaction vessel comprises a high pressure reaction vessel.
In a specific embodiment, the solid-to-liquid ratio is 20g/L to 300 g/L. The anode material comprises a ternary anode material, lithium cobaltate and/or lithium manganate or comprises a lithium iron phosphate anode material.
And S2, introducing carbon dioxide gas into the reaction container to enable the cathode material waste to react with the carbon dioxide.
In the step, the reaction time is controlled to be 1-30 h. The process parameters such as reaction temperature and the like are different according to different anode materials. When the anode material comprises a ternary anode material and lithium cobaltate and/or lithium manganate, the pressure in the reaction container is controlled to be 0.5-5Mpa, and the reaction temperature is controlled to be 100-220 ℃; stirring is carried out at the same time of the reaction, and the stirring speed is 50-1000 rpm. When the anode material comprises a lithium iron phosphate anode material, adding 2-10% of hydrogen peroxide relative to the volume percentage of the mixed solution into a reaction container, and then starting to introduce carbon dioxide gas with the flow rate of 0.2-10L/min, wherein the reaction temperature is controlled at 0-60 ℃; stirring can be carried out simultaneously with the reaction, and the stirring speed is 100-2000 rpm.
In this step, the carbon dioxide gas may be derived from coal-fired flue gas or industrial grade CO2. CO in flue gas2The content of (A) is up to more than 90%. Flue gas or technical grade CO for burning coal2The method is combined with the waste lithium battery positive electrode powder to prepare a high-value lithium carbonate product, and is the best idea of waste utilization.
S3, obtaining a leaching solution containing lithium after the reaction is finished;
wherein the solute of the leach solution comprises a carbonate of lithium.
In a specific embodiment, after step S3, the valuable metal ions in the residue other than lithium or the residue itself is recycled; that is, before step S3, no recovery of other valuable metals than lithium is performed, wherein the other valuable metals include elements of Ni, Co, Mn, Al, Cu, and/or Fe.
In a specific embodiment, the following steps are further included after step S3:
s4, heating the lithium-containing leaching solution at 50-100 ℃ under normal pressure or vacuum environment or heating at 50-100 ℃ by adopting a rotary evaporation heating mode, and drying at 70-90 ℃ to obtain the lithium carbonate. The product purity of the obtained lithium carbonate product is more than 99 percent, and the recovery rate of lithium is more than 95 percent.
In a specific embodiment, before step S1, the method further includes the following steps:
and S0, pretreating the disassembled lithium ion battery anode material, and milling to obtain anode material waste.
Example one
In this embodiment, the positive electrode material of the waste lithium ion battery includes a ternary positive electrode material, lithium cobaltate and/or lithium manganate, and the method for recovering valuable metals from the waste lithium ion battery specifically includes the following steps:
s1, mixing the mixed solution of the anode material waste and water according to a certain solid-liquid ratio, and placing the mixed solution into a reaction container, wherein the solid-liquid ratio is 20g/L-300 g/L;
in a specific embodiment, the lithium battery ternary cathode waste powder may have a composition as shown in table 1 below:
TABLE 1
Figure BDA0002475351050000061
S2, introducing carbon dioxide gas into the reaction vessel, controlling the pressure at 0.5-5Mpa, controlling the reaction temperature at 100-220 ℃ and the reaction time at 1-30 h; stirring is carried out during the reaction in the step S2, and the stirring speed is 50-1000 rpm;
wherein, the reaction vessel comprises a high-pressure reaction kettle.
S3, after the reaction is finished, cooling the reaction kettle, releasing pressure, and filtering reactants to obtain leachate containing lithium;
the main components of filter residue obtained by filtering the reactant comprise Ni, Co, Mn and Al elements;
acid leaching the filter residue, and then separating by adopting hydrometallurgy to realize the recovery of valuable metals Ni, Co, Mn and/or Al; the hydrometallurgical separation comprises precipitation separation or extraction separation. It should be understood that the NCM ternary positive electrode material includes Ni, Co and Mn elements, and the main components of the filter residue obtained by filtering the reactant include Ni, Co and Mn elements; the NCA ternary positive electrode material comprises Ni, Co and Al elements, and the main components of filter residue obtained by filtering reactants comprise the Ni, Co and Al elements. The mixed positive electrode material of NCM and NCA simultaneously comprises Ni, Co, Mn and Al elements, and the filter residue also comprises the elements. The Al may also originate from the current collector Al foil of the lithium battery.
The XRD pattern of the lithium carbonate prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the lithium carbonate recovered completely matches the PDF standard card.
The resultant lithium carbonate was subjected to an Inductively Coupled Plasma (ICP) test to analyze its composition, resulting in the results shown in table 2 below:
TABLE 2
Figure BDA0002475351050000062
Figure BDA0002475351050000071
In the present embodiment, the recovery of the valuable metals other than lithium is performed after step S3, that is, the recovery of the valuable metals other than lithium is not performed before step S3.
Example two
In this embodiment, the positive electrode material of the waste lithium ion battery includes a lithium iron phosphate positive electrode material, and the method for recovering valuable metals from the waste lithium ion battery specifically includes the following steps:
s1, mixing the mixed solution of the anode material waste and water according to a certain solid-liquid ratio, and placing the mixed solution into a reaction container, wherein the solid-liquid ratio is 25g/L-300 g/L;
in a specific embodiment, the lithium iron phosphate cathode waste powder may have a composition as shown in table 3 below:
TABLE 3
Figure BDA0002475351050000072
S2, adding 2-10% of hydrogen peroxide in volume percentage relative to the mixed solution into the reaction container, and then starting to introduce carbon dioxide gas with the flow of 0.2-10L/min, controlling the reaction temperature at 0-60 ℃ and the reaction time at 1-30 h;
wherein the reaction vessel comprises a normal pressure reaction kettle. Because the normal pressure reaction kettle is adopted in the process, a high pressure reaction kettle is not needed, the process difficulty can be further reduced, and the preparation cost can be reduced.
S3, after the reaction is finished, filtering the reactant to obtain leachate containing lithium;
the main component of filter residue obtained by filtering the reactant comprises ferric phosphate; and carrying out acid leaching impurity removal or direct regeneration on the filter residue for further recycling.
The XRD pattern of the lithium carbonate prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the lithium carbonate recovered completely matches the PDF standard card.
The resultant lithium carbonate was subjected to an Inductively Coupled Plasma (ICP) test to analyze its composition, resulting in the results shown in table 4 below:
TABLE 4
Figure BDA0002475351050000073
In this embodiment, after step S3, the valuable metal ions in the residue other than lithium or the residue itself is recycled, that is, the valuable metals other than lithium are not recycled before step S3.
EXAMPLE III
Mixing the anode waste containing the lithium battery ternary material, lithium cobaltate and/or lithium manganate with water according to a certain solid-to-liquid ratio (20g/L-300g/L), putting the mixture into a reaction kettle, introducing carbon dioxide gas, and controlling the pressure to be 0.5-5 Mpa. The reaction temperature is controlled at 100 ℃ and 220 ℃, the stirring speed is 50-1000rpm, and the reaction time is 1-30 h. After the reaction is finished, cooling the reaction kettle, releasing pressure, filtering reactants to obtain leachate containing lithium, and performing normal pressure and vacuum treatmentHeating at 50-100 deg.C by rotary evaporation, and oven drying at 70-90 deg.C to obtain lithium carbonate (Li)2CO3) And (5) producing the product. The main components of the filter residue contain Ni, Co, Mn and/or Al and the like, and the recovery of valuable metals Ni, Co, Mn and/or Al can be realized by adopting acid leaching and then adopting hydrometallurgical separation (including means such as precipitation separation, extraction separation and the like).
Example four
Mixing waste containing lithium iron phosphate cathode material of lithium battery with water according to a certain solid-to-liquid ratio (25-300g/L), placing the mixture into a reaction kettle, adding hydrogen peroxide accounting for 2-10% of the volume percentage of the mixed solution, then introducing carbon dioxide gas with the flow rate of 0.2-10L/min for reaction, controlling the reaction temperature to be 0-60 ℃, stirring speed to be 100-2000rpm, and reaction time to be 1-30 h. After the reaction is finished, the reactant is filtered to obtain leachate containing lithium, the leachate is heated at 50-100 ℃ by heating modes such as normal pressure, vacuum, rotary evaporation and the like, and the leachate is dried at 70-90 ℃ to obtain lithium carbonate (Li)2CO3) And (5) producing the product. The main component of the filter residue is ferric phosphate, and the filter residue can be further utilized by adopting acid leaching or direct regeneration and other modes.
The invention converts carbon dioxide (CO)2) The selective extraction of Li is realized under certain conditions by introducing the aqueous solution of the anode waste powder, and the extraction of Li is prior to the extraction of other valuable metals, so that the loss of Li caused in the process of extracting other valuable metals in the prior art is avoided. Heating the obtained leaching solution to obtain a lithium carbonate product, wherein the purity of the product is more than 99 percent, and the recovery rate of Li is more than 95 percent.
The technology for recovering Li has simple operation steps, the equipment belongs to conventional equipment, and carbon dioxide (CO) is used in the operation process2) The method is a main consumable, does not use other acid or alkali, does not produce waste water, has low operation cost, and obtains a lithium salt product with high purity. During leaching, metal ions other than lithium are not substantially leached; in the process of preparing lithium salt from the leaching solution, the lithium salt product can be obtained only by heating without an additional precipitator, so that the problems of salt control and wastewater treatment can be effectively solved. The technology has high application value.
This technique is well knownAnother value of the technique is that the flue gas or industrial grade CO of coal combustion can be fully utilized2Carbon dioxide (CO) in flue gas2) The content of (A) is up to more than 90%. Flue gas or technical grade CO for burning coal2The method is combined with the waste powder of the positive electrode of the lithium ion battery to prepare the high-value lithium carbonate product, and is the best idea of waste utilization.
The foregoing embodiments are merely illustrative of the principles of this invention and its efficacy, rather than limiting it, and various modifications and variations can be made by those skilled in the art without departing from the spirit and scope of the invention, which is defined in the appended claims.

Claims (10)

1. A method for recovering valuable metals in waste lithium ion batteries is characterized by comprising the following steps:
s1, placing the mixed solution of the anode material waste and water into a reaction container;
s2, introducing carbon dioxide gas into the reaction container to enable the positive electrode material waste to react with the carbon dioxide;
s3, obtaining a leaching solution containing lithium after the reaction is finished;
wherein the solute of the leach solution comprises a carbonate of lithium.
2. The method of claim 1, wherein the reaction vessel comprises a reaction kettle;
preferably, the reaction vessel comprises a high pressure reaction vessel.
3. The method according to any one of claims 1-2, wherein the positive electrode material comprises a ternary positive electrode material, lithium cobaltate and/or lithium manganate, the method comprising in particular the steps of:
s1, mixing the mixed solution of the anode material waste and water according to a certain solid-to-liquid ratio and placing the mixture into a reaction container;
s2, introducing carbon dioxide gas into the reaction vessel, controlling the pressure at 0.5-5Mpa, controlling the reaction temperature at 100-220 ℃ and the reaction time at 1-30 h;
s3, after the reaction is finished, cooling the reaction kettle, releasing pressure, and filtering reactants to obtain leachate containing lithium;
preferably, the solid-to-liquid ratio is 20g/L-300 g/L;
preferably, stirring is carried out simultaneously with the reaction in step S2, and the stirring speed is 50-1000 rpm;
preferably, the main components of the filter residue obtained by filtering the reactant comprise Ni, Co, Mn, Al and/or Cu elements;
preferably, the filter residue is subjected to acid leaching, and then hydrometallurgical separation is adopted, so that valuable metals of Ni, Co, Mn, Al and/or Cu are recovered;
preferably, the hydrometallurgical separation comprises precipitation separation or extraction separation.
4. The method according to claim 3, characterized in that the method further comprises the steps of:
s4, heating the lithium-containing leaching solution at 50-100 ℃ under normal pressure or vacuum environment or heating at 50-100 ℃ by adopting a rotary evaporation heating mode, and drying at 70-90 ℃ to obtain the lithium carbonate.
5. The method according to any one of claims 1 to 2, wherein the positive electrode material comprises a lithium iron phosphate positive electrode material, and the method specifically comprises the steps of:
s1, mixing the mixed solution of the anode material waste and water according to a certain solid-to-liquid ratio and placing the mixture into a reaction container;
s2, adding 2-10% of hydrogen peroxide in volume percentage relative to the mixed solution into the reaction container, and then starting to introduce carbon dioxide gas with the flow of 0.2-10L/min, controlling the reaction temperature at 0-60 ℃ and the reaction time at 1-30 h;
s3, after the reaction is finished, filtering the reactant to obtain leachate containing lithium;
preferably, the solid-to-liquid ratio is 25g/L-300 g/L;
preferably, in step S2, stirring is carried out simultaneously with the reaction, and the stirring speed is 100-2000 rpm;
preferably, the reaction vessel comprises an atmospheric pressure reaction vessel;
preferably, the main component of the filter residue obtained by filtering the reactant comprises iron phosphate;
preferably, the filter residue is further recycled by adopting an acid leaching impurity removal or direct regeneration mode.
6. The method of claim 5, further comprising the steps of:
s4, heating the lithium-containing leaching solution at 50-100 ℃ under normal pressure or vacuum environment or heating at 50-100 ℃ by adopting a rotary evaporation heating mode, and drying at 70-90 ℃ to obtain the lithium carbonate.
7. The method according to any one of claims 1 to 2, wherein after step S3, the other valuable metal ions in the residue other than lithium or the residue itself is recycled;
preferably, recovery of other valuable metals than lithium is not performed before step S3;
preferably, the other valuable metals include elements of Ni, Co, Mn, Al, Cu and/or Fe.
8. The method according to any one of claims 1 to 2, wherein the carbon dioxide gas in step S2 is derived from flue gas from coal combustion or industrial grade CO2。
9. The method according to any one of claims 1-2, further comprising, before step S1, the steps of:
and S0, pretreating the disassembled lithium ion battery anode material, and pulverizing to obtain the anode material waste.
10. The process according to any one of claims 1 to 2, wherein the leach solution is heated to produce a lithium carbonate product having a product purity of greater than 99% and a lithium recovery of greater than 95%.
CN202010362131.XA 2020-04-30 2020-04-30 Method for recovering valuable metals in waste lithium ion batteries Pending CN111593200A (en)

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CN114149016A (en) * 2021-12-15 2022-03-08 天齐锂业股份有限公司 Method for recovering lithium-copper composite belt
CN114875238A (en) * 2022-05-20 2022-08-09 北京化工大学 Method for recycling nickel, manganese, cobalt and lithium in waste lithium battery ternary cathode material

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Application publication date: 20200828