CN111041230A - Method for recovering metal from waste lithium ion battery - Google Patents

Method for recovering metal from waste lithium ion battery Download PDF

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Publication number
CN111041230A
CN111041230A CN201910758182.1A CN201910758182A CN111041230A CN 111041230 A CN111041230 A CN 111041230A CN 201910758182 A CN201910758182 A CN 201910758182A CN 111041230 A CN111041230 A CN 111041230A
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lithium
ion battery
lithium ion
metal salt
salt
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CN111041230B (en
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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
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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
    • 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
    • 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 metal from waste lithium ion batteries, which comprises the following steps: mixing the recovered lithium ion battery positive electrode material with a metal salt and reacting the lithium ion battery positive electrode material with the metal salt; and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide. The method is based on the ion exchange principle, and realizes the stripping of lithium ions from the anode material through the selective exchange between metal ions and lithium ions, thereby obtaining a single lithium solution and metal oxide. The method has the advantages that the extraction rate of lithium can reach 93-100%, other metal ions are not lost, the process is green, efficient and simple, the flow is short, the energy consumption is low, and the industrialization is easy.

Description

Method for recovering metal from waste lithium ion battery
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a method for recovering metals from waste lithium batteries.
Background
With the increasingly prominent problems of environmental pollution and energy crisis, clean energy such as lithium ion batteries and the like are receiving more and more attention. However, after a period of use, the capacity of the lithium ion battery is reduced, and a new energy vehicle and the like using the lithium ion battery as power also need to be upgraded, and the number of the waste lithium ion batteries is increasing. However, if the valuable metals are not recovered and recycled, but the lithium ion batteries are directly discarded as waste, not only environmental pollution is caused, but also rare resources such as metallic lithium, cobalt and the like are wasted, so that the recovery and recycling of the valuable metals in the waste lithium ion batteries, particularly in the positive electrode materials, has become a research hotspot in recent years.
The existing methods for recovering the anode materials of the waste lithium ion batteries are various, and mainly comprise wet acid leaching, pyrogenic calcination and mechanical methods, or a combination of several methods. However, the wet acid leaching process has long flow, large acid and alkali consumption, strong corrosion resistance of equipment and difficult environmental problem reaching the standard; pyrometallurgical processes are energy intensive, equipment demanding and costly, and difficult to recover all metals, especially lithium. Moreover, the above methods have the phenomenon of incomplete extraction or failure to obtain pure products, which causes difficulty in recycling the substances recovered subsequently.
Disclosure of Invention
The embodiment of the invention provides a method for recovering metals from waste lithium ion batteries, which aims to solve various problems of various recovery methods in the prior art.
According to a first aspect, embodiments of the present invention provide a method for recovering metals from used lithium ion batteries, the method including the following steps:
mixing the recovered lithium ion battery positive electrode material with a metal salt and reacting the lithium ion battery positive electrode material with the metal salt;
and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide.
Optionally, the method includes the following steps:
and mixing the lithium ion battery anode material and the metal salt, carrying out hydrothermal reaction at 50-240 ℃ for 1-48 hours, and filtering the suspension obtained by the reaction to obtain a lithium solution and a metal oxide.
Optionally, the method includes the following steps:
mixing the lithium ion battery anode material and the metal salt, adding ultrapure water, uniformly mixing, and adding into a polytetrafluoroethylene lining;
putting the polytetrafluoroethylene lining into a stainless steel reaction kettle for hydrothermal reaction at the hydrothermal temperature of 50-240 ℃ for 1-48 hours;
carrying out solid-liquid separation on the suspension obtained by the reaction to respectively obtain filtrate and filter residue;
wherein the filtrate is a lithium solution.
Optionally, the filtrate is free of metal ions other than lithium.
Optionally, the method includes the following steps:
and mixing the recovered lithium ion battery anode material with the metal salt, stirring and heating the obtained mixture at normal pressure, and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide.
Optionally, the method includes the following steps:
mixing the recovered lithium ion battery anode material with the metal salt, adding ultrapure water, uniformly mixing, and putting into a flask;
sealing the flask, heating the flask in oil bath at normal pressure, and stirring;
carrying out solid-liquid separation on the obtained mixture to respectively obtain filtrate and filter residue;
wherein the filtrate is a lithium solution.
Optionally, the filtrate is free of metal ions other than lithium.
Optionally, the method includes the following steps:
and mixing the recovered lithium ion battery anode material with the metal salt, carrying out high-energy ball milling on the obtained mixture, adding water into the obtained mixture after the reaction is finished, and further carrying out solid-liquid separation to obtain a lithium salt solution and a metal oxide.
Optionally, water is added or not added during the high energy ball milling process.
Optionally, the method includes the following steps:
mixing the recovered lithium ion battery anode material with the metal salt, adding the mixture into a stainless steel ball milling tank for high-energy ball milling, adding water, and performing solid-liquid separation to obtain filter residue and filtrate;
wherein the filtrate is a lithium solution.
Optionally, the filtrate is free of metal ions other than lithium.
Optionally, the metal salt comprises one or more of a sulfate, a hydrochloride, or a nitrate; the cation of the metal salt comprises one or more of magnesium ion, calcium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, or aluminum ion.
Optionally, the lithium ion battery includes one or more of lithium manganate type, lithium cobaltate type, and lithium nickel cobalt manganese oxide ternary type.
Optionally, the lithium ion battery comprises a lithium manganate type lithium ion battery, and the metal salt is preferably a manganese salt.
Optionally, the lithium ion battery comprises a lithium cobalt oxide type lithium ion battery, and the metal salt is preferably a cobalt salt.
Optionally, the lithium ion battery includes a nickel cobalt lithium manganate ternary type lithium ion battery, and the metal salt is preferably a mixed salt of nickel, cobalt and manganese, a cobalt salt or a manganese salt.
Optionally, the ratio of the number of moles of lithium in the lithium ion battery positive electrode material to the total number of moles of the metal salt is 2: 0.95 to 2: 1.05.
optionally, the ratio of the number of moles of lithium in the lithium ion battery positive electrode material to the total number of moles of the metal salt is preferably 2: 1.
optionally, the mass percentage of the metal ions (calculated according to the metal ions) in the solution formed by the metal salt is 1% to 60%.
Optionally, the method further comprises the following steps:
and adding sodium carbonate into the lithium salt solution to obtain the lithium carbonate with the purity of more than 99%.
Optionally, no acid or base is added to react with the recycled lithium ion battery positive electrode material during the entire recycling process.
Optionally, the stirring and heating temperature is 50-90 ℃, the stirring and heating time is 10-60 hours, and the stirring rotation speed is 300-1500 rpm.
Optionally, the weight ratio of the mixture to the grinding balls is 1: 0.01-1, the rotation speed of ball milling is 100-1800 rpm, and the ball milling time is 0.5-48 h.
The invention provides a method for recycling valuable metals in a waste lithium ion battery anode material, which is based on an ion exchange principle and realizes the stripping of lithium ions from the anode material through the selective exchange between the metal ions and the lithium ions, thereby obtaining a single lithium solution and a single metal oxide. The method can be universally used for one or more of the anode materials in lithium manganate type, lithium cobaltate type and nickel cobalt lithium manganate ternary type lithium batteries, wherein the lithium is selectively extracted and the corresponding valuable metals are recycled. The extraction rate of lithium can reach 93-100%. No other metal ions are lost. The process is green, efficient and simple, the flow is short, the energy consumption is low, and the industrialization is easy.
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 shows XRD patterns of products (lithium cobaltate raw material, hydrothermal product, cobaltosic oxide standard card from top to bottom) obtained in each step of hydrothermal method of waste lithium cobaltate positive electrode material of the present invention.
Fig. 2 shows XRD patterns of products (hydrothermal product, manganite standard card, lithium manganate raw material, lithium manganate standard card from top to bottom) obtained in each step of the normal pressure heating and stirring method of waste lithium manganate positive electrode material 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 embodiment of the invention provides a method for recovering metals from waste lithium ion batteries, which comprises the following steps: mixing the recovered lithium ion battery positive electrode material with a metal salt and reacting the lithium ion battery positive electrode material with the metal salt; and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide.
The method can be implemented by three methods, specifically comprising: A. hydrothermal method; B. normal pressure heating and stirring method; C. high energy ball milling method. The following are detailed below:
A. hydrothermal method:
the embodiment of the invention provides a method for recovering metals from waste lithium ion batteries, which comprises the hydrothermal method, and the method comprises the following steps:
and mixing the lithium ion battery anode material and the metal salt, carrying out hydrothermal reaction at 50-240 ℃ for 1-48 hours, and filtering the suspension obtained by the reaction to obtain a lithium solution and a metal oxide.
In a specific embodiment, the method comprises the steps of:
mixing the lithium ion battery anode material and the metal salt, adding ultrapure water, uniformly mixing, and adding into a polytetrafluoroethylene lining;
and (3) putting the polytetrafluoroethylene lining into a stainless steel reaction kettle for hydrothermal reaction at the hydrothermal temperature of 50-240 ℃ for 1-48 hours.
Carrying out solid-liquid separation on the suspension obtained by the reaction to respectively obtain filtrate and filter residue;
wherein the filtrate is a lithium solution.
The filtrate is free of metal ions other than lithium.
B. Normal pressure heating and stirring method:
the embodiment of the invention provides a method for recovering metals from waste lithium ion batteries, which comprises the normal-pressure heating and stirring method, and comprises the following steps:
and mixing the recovered lithium ion battery anode material with the metal salt, stirring and heating the obtained mixture at normal pressure, and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide.
In a specific embodiment, the method comprises the steps of:
mixing the recovered lithium ion battery anode material with the metal salt, adding ultrapure water, uniformly mixing, and putting into a flask;
sealing the flask, heating the flask in oil bath at normal pressure, and stirring;
carrying out solid-liquid separation on the obtained mixture to respectively obtain filtrate and filter residue;
wherein the filtrate is a lithium solution.
The filtrate is free of metal ions other than lithium.
The stirring and heating temperature is 50-90 ℃, the stirring and heating time is 10-60 h, and the stirring rotating speed is 300-1500 rpm.
C. High-energy ball milling method:
the embodiment of the invention provides a method for recovering metals from waste lithium ion batteries, which comprises the following steps:
and mixing the recovered lithium ion battery anode material with the metal salt, carrying out high-energy ball milling on the obtained mixture, adding water into the obtained mixture after the reaction is finished, and further carrying out solid-liquid separation to obtain a lithium salt solution and a metal oxide.
Water may or may not be added during the high energy ball milling process.
In a specific embodiment, the method comprises the steps of:
mixing the recovered lithium ion battery anode material with the metal salt, adding the mixture into a stainless steel ball milling tank for ball milling, adding water, and performing solid-liquid separation to obtain filter residue and filtrate;
wherein the filtrate is a lithium solution.
The filtrate is free of metal ions other than lithium.
In the ball milling process, the weight ratio of the mixture to the grinding balls is 1: 0.01-1, the rotation speed of ball milling is 100-1800 rpm, and the ball milling time is 0.5-48 h.
The method for recovering the metal from the waste lithium ion battery is implemented by adopting a hydrothermal method, a normal-pressure heating and stirring method or a high-energy ball milling method, wherein the metal salt comprises one or more of sulfate, hydrochloride or nitrate; the cation of the metal salt comprises one or more of magnesium ion, calcium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion, or aluminum ion. The lithium ion battery comprises one or more of lithium manganate type, lithium cobaltate type and nickel cobalt lithium manganate ternary type. In a particular embodiment, the lithium ion battery comprises a lithium manganate type lithium ion battery, and the metal salt is preferably a manganese salt. In a particular embodiment, the lithium ion battery comprises a lithium ion battery of the lithium cobaltate type, the metal salt preferably being a cobalt salt. In a specific embodiment, the lithium ion battery comprises a nickel cobalt lithium manganate ternary type lithium ion battery, and the metal salt is preferably a mixed salt of nickel, cobalt and manganese, a cobalt salt or a manganese salt.
The ratio of the number of moles of lithium in the lithium ion battery positive electrode material to the total number of moles of the metal salt is 2: 0.95 to 2: 1.05. in a specific embodiment, the ratio of the number of moles of lithium in the lithium ion battery positive electrode material to the total number of moles of the metal salt is preferably 2: 1.
the mass percentage of metal ions (calculated according to the metal ions) in the solution formed by the metal salt is 1-60%.
In a specific embodiment, the method further comprises the steps of: and adding sodium carbonate into the lithium salt solution to obtain the lithium carbonate with the purity of more than 99%.
In the method for recovering metal from the waste lithium ion battery, acid or alkali is not added to react with the recovered lithium ion battery anode material in the whole recovery process.
The invention provides a method for recycling valuable metals in a waste lithium ion battery anode material, which is based on an ion exchange principle and realizes the stripping of lithium ions from the anode material through the selective exchange between the metal ions and the lithium ions, thereby obtaining a single lithium solution and a single metal oxide. The method can be universally used for one or more of the anode materials in lithium manganate type, lithium cobaltate type and nickel cobalt lithium manganate ternary type lithium batteries, wherein the lithium is selectively extracted and the corresponding valuable metals are recycled. The extraction rate of lithium can reach 93-100%. No other metal ions are lost. The process is green, efficient and simple, the flow is short, the energy consumption is low, and the industrialization is easy.
Example one
The invention provides a method for recovering metal from waste lithium ion batteries, which comprises the following steps:
(1) the recovered lithium cobaltate positive electrode material was analyzed, and contained 71mg/g of lithium and 314.1mg/g of cobalt.
(2) Taking 1g of lithium cobaltate material, and mixing the materials according to the weight ratio of lithium: cobalt molar ratio 2: 1, 1.4g of cobalt sulfate heptahydrate was added, and then 10mL of ultrapure water was added to the mixture, followed by uniformly mixing the mixture and adding the mixture to a 50mL polytetrafluoroethylene liner.
(3) And (3) putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, carrying out hydrothermal reaction in an oven, and reacting the mixture for 12 hours at 160 ℃.
(4) And (4) taking out the materials after the reaction is finished, and carrying out solid-liquid separation to obtain filtrate and filter residue respectively.
(5) Drying the filter residue in an air drying oven at 80 ℃ for 5h, and then transferring the filter residue to a vacuum drying oven to dry at 120 ℃ for 12 h. The bottom XRD curve in fig. 1 shows that the residue is pure cobaltosic oxide.
(6) The filtrate was analyzed for lithium content of 17.93ppm and cobalt was not detectable. The leaching rate of lithium was calculated to be 100% and the loss rate of cobalt was calculated to be 0.
The method realizes the recycling of valuable metals in the lithium cobaltate cathode material.
Example two
The invention provides a method for recovering metal from waste lithium ion batteries, which comprises the following steps:
(1) analyzing the content of lithium in the recycled nickel cobalt lithium manganate positive electrode material as follows: 72.4mg/g, nickel content: 184.8mg/g, cobalt content: 192mg/g, manganese content: 180.8 mg/g.
(2) Taking 1g of nickel cobalt lithium manganate ternary material, and preparing lithium: manganese molar ratio 2: 0.8771g of manganese sulfate monohydrate was added to 1, and 10mL of ultrapure water was added to the mixture, followed by uniformly mixing the mixture and adding the mixture to a 25mL polytetrafluoroethylene liner.
(3) And (3) putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, carrying out hydrothermal reaction in an oven, and reacting the mixture for 24 hours at 200 ℃.
(4) And (4) taking out the materials after the reaction is finished, and carrying out solid-liquid separation to obtain filtrate and filter residue respectively.
(5) And drying the filter residue in a forced air drying oven at 80 ℃ for 5h, and then transferring the filter residue to a vacuum drying oven to dry the filter residue for 12h at 120 ℃. Finally, the oxide containing nickel, cobalt and manganese is obtained.
(6) The leaching rate of lithium is calculated by analyzing the content of lithium in the filtrate and is 100%, and nickel, cobalt and manganese elements in the filtrate cannot be detected. The leaching rate of lithium is calculated to be 100%, and the loss rate of nickel, cobalt and manganese is calculated to be 0.
The method realizes the recycling of valuable metals in the nickel cobalt lithium manganate (111) cathode material.
EXAMPLE III
The invention provides a method for recovering metal from waste lithium ion batteries, which comprises the following steps:
(1) analyzing black powder after the positive and negative electrodes in the lithium ion battery cell are mechanically broken, wherein the lithium content is as follows: 52.9mg/g, and contains Al, Cu, graphite, conductive carbon, nickel, cobalt, manganese, and the like.
(2) Taking 1g of black powder, and mixing the following raw materials according to the weight ratio of lithium: manganese molar ratio 2: 1, 0.64g of manganese sulfate monohydrate is added, 10mL of ultrapure water is added, and the mixture is uniformly mixed and then added into a 25mL polytetrafluoroethylene lining.
(3) And (3) putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, carrying out hydrothermal reaction in an oven, and reacting the mixture for 24 hours at 220 ℃.
(4) And (4) taking out the materials after the reaction is finished, and carrying out solid-liquid separation to obtain filtrate and filter residue respectively.
(5) And drying the filter residue in a forced air drying oven at 80 ℃ for 5h, and then transferring the filter residue to a vacuum drying oven to dry the filter residue for 12h at 120 ℃. Finally, the oxide containing nickel, cobalt, manganese, copper and aluminum is obtained, and the oxide contains graphite and carbon.
(6) The leaching rate of lithium is 93% by analyzing the content of lithium in the filtrate, nickel, cobalt and manganese elements in the filtrate can not be detected, and the loss rate of nickel, cobalt and manganese is 0.
The method realizes the recycling of valuable metals of the complex black powder.
Example four
The invention provides a method for recovering metal from waste lithium ion batteries, which comprises the following steps:
(1) the content of lithium in the recovered lithium manganate is analyzed to be 41.3mg/g, and the content of manganese is analyzed to be 169.8 mg/g.
(2) Taking 5g of lithium manganate material, and mixing the materials according to the weight ratio of lithium: the manganese molar ratio is 2: 1, 2.36g of manganese sulfate monohydrate was added, and 50ml of ultrapure water was added thereto and mixed well, followed by placing into a 250ml flask.
(3) After the flask was sealed, it was oil-bathed at 60 ℃ for 60 hours with stirring at 300 rpm.
(4) And after the reaction is finished, carrying out solid-liquid separation to obtain filtrate and filter residue respectively.
(5) The content of lithium in the analyzed filtrate was 42.84ppm, Mn could not be detected, and the leaching rate of lithium was calculated to be 98%, while the loss rate of Mn was calculated to be 0.
(6) And carrying out suction filtration on the mixture, drying the obtained filter residue for 5h at 80 ℃ in a forced air drying oven, and transferring the filter residue to a vacuum drying oven for drying for 12h at 120 ℃. As shown in fig. 2, XRD of the residue (product) confirmed that the main component was manganite mno (oh).
The method realizes the recycling of valuable metals in the lithium manganate cathode material.
EXAMPLE five
The invention provides a method for recovering metal from waste lithium ion batteries, which comprises the following steps:
(1) the content of lithium in the recovered lithium manganate is analyzed to be 41.3mg/g, and the content of manganese is analyzed to be 169.8 mg/g.
(2) Taking 5g of lithium manganate material, and mixing the materials according to the weight ratio of lithium: the manganese molar ratio is 2: 1 manganese sulfate monohydrate 2.36g was added, the mixture was charged to a stainless steel ball mill pot and two 5mm, two 3mm stainless steel grinding beads were added.
(3) And ball-milling the mixture at 500rpm for 48h, adding water, and performing solid-liquid separation to obtain filter residue and filtrate.
(4) The leaching rate of lithium in the filtrate is analyzed to be 95%, Mn cannot be detected, and the loss rate of Mn is calculated to be 0.
(5) And drying the filter residue after suction filtration in an air drying oven at 80 ℃ for 5h, and transferring to a vacuum drying oven for drying at 120 ℃ for 12 h. XRD analysis of the filter residue proves that the main component of the filter residue is manganite MnO (OH).
The method realizes the recycling of valuable metals in the lithium manganate cathode material.
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 (9)

1. A method for recovering metals from spent lithium ion batteries, the method comprising the steps of:
mixing the recovered lithium ion battery positive electrode material with a metal salt and reacting the lithium ion battery positive electrode material with the metal salt;
and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide.
2. Method according to claim 1, characterized in that it comprises the following steps:
mixing the lithium ion battery anode material and the metal salt, carrying out hydrothermal reaction at 50-240 ℃ for 1-48 hours, and filtering the suspension obtained by the reaction to obtain a lithium solution and a metal oxide;
preferably, the method comprises the steps of:
mixing the lithium ion battery anode material and the metal salt, adding ultrapure water, uniformly mixing, and adding into a polytetrafluoroethylene lining;
putting the polytetrafluoroethylene lining into a stainless steel reaction kettle for hydrothermal reaction at the hydrothermal temperature of 50-240 ℃ for 1-48 hours;
carrying out solid-liquid separation on the suspension obtained by the reaction to respectively obtain filtrate and filter residue;
wherein the filtrate is a lithium solution;
preferably, the filtrate is free of metal ions other than lithium.
3. Method according to claim 1, characterized in that it comprises the following steps:
mixing the recovered lithium ion battery anode material with the metal salt, stirring and heating the obtained mixture at normal pressure, and after the reaction is finished, carrying out solid-liquid separation on the obtained mixture to obtain a lithium salt solution and a metal oxide;
preferably, the method comprises the steps of:
mixing the recovered lithium ion battery anode material with the metal salt, adding ultrapure water, uniformly mixing, and putting into a flask;
sealing the flask, heating in oil bath under normal pressure, and stirring;
carrying out solid-liquid separation on the obtained mixture to respectively obtain filtrate and filter residue;
wherein the filtrate is a lithium solution;
preferably, the filtrate is free of metal ions other than lithium.
4. Method according to claim 1, characterized in that it comprises the following steps:
mixing the recovered lithium ion battery anode material with the metal salt, carrying out high-energy ball milling on the obtained mixture, adding water into the obtained mixture after the reaction is finished, and then carrying out solid-liquid separation to obtain a lithium salt solution and a metal oxide;
preferably, water is added or not added during the high energy ball milling process;
preferably, the method comprises the steps of:
mixing the recovered lithium ion battery anode material with the metal salt, adding the mixture into a stainless steel ball milling tank for high-energy ball milling, adding water, and performing solid-liquid separation to obtain filter residue and filtrate;
wherein the filtrate is a lithium solution;
preferably, the filtrate is free of metal ions other than lithium.
5. The method of any one of claims 1-4, wherein the metal salt comprises one or more of a sulfate, a hydrochloride, or a nitrate; the cation of the metal salt comprises one or more of magnesium ion, calcium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion or aluminum ion;
preferably, the lithium ion battery comprises one or more of lithium manganate type, lithium cobaltate type and lithium nickel cobalt manganese oxide ternary type;
preferably, the lithium ion battery comprises a lithium manganate type lithium ion battery, and the metal salt is preferably a manganese salt;
preferably, the lithium ion battery comprises a lithium cobalt oxide type lithium ion battery, and the metal salt is preferably a cobalt salt;
preferably, the lithium ion battery comprises a nickel cobalt lithium manganate ternary type lithium ion battery, and the metal salt is preferably a nickel cobalt manganese mixed salt, a cobalt salt or a manganese salt.
6. The method of any of claims 1-4, wherein the ratio of the number of moles of lithium in the lithium ion battery positive electrode material to the total number of moles of the metal salt is 2: 0.95 to 2: 1.05;
preferably, the ratio of the number of moles of lithium in the lithium ion battery positive electrode material to the total number of moles of the metal salt is preferably 2: 1;
preferably, the mass percentage of the metal ions (calculated according to the metal ions) in the solution formed by the metal salt is 1% -60%.
7. The method according to any of claims 1-4, characterized in that the method further comprises the steps of:
adding sodium carbonate into the lithium salt solution to obtain lithium carbonate with the purity of more than 99%;
preferably, no acid or base is added to react with the recovered lithium ion battery positive electrode material throughout the recovery process.
8. The method according to claim 3, wherein the stirring and heating temperature is 50 to 90 ℃, the stirring and heating time is 10 to 60 hours, and the stirring rotation speed is 300 to 1500 rpm.
9. The method of claim 4, wherein the weight ratio of the mixture to the milling balls is 1: 0.01-1, the rotation speed of ball milling is 100-1800 rpm, and the ball milling time is 0.5-48 h.
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