CN113314778A - Recycling method of retired lithium ion battery positive electrode material - Google Patents

Recycling method of retired lithium ion battery positive electrode material Download PDF

Info

Publication number
CN113314778A
CN113314778A CN202110592746.6A CN202110592746A CN113314778A CN 113314778 A CN113314778 A CN 113314778A CN 202110592746 A CN202110592746 A CN 202110592746A CN 113314778 A CN113314778 A CN 113314778A
Authority
CN
China
Prior art keywords
lithium
ion battery
lithium ion
retired
anode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110592746.6A
Other languages
Chinese (zh)
Inventor
夏永高
高洁
申屠华剑
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN202110592746.6A priority Critical patent/CN113314778A/en
Publication of CN113314778A publication Critical patent/CN113314778A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides a recycling method of a retired lithium ion battery anode material. Compared with the prior art, the invention introduces CO2The lithium ion battery can be recycled as a leaching agent and a precipitating agent, no extra precipitating agent is required to be added, the consumption of acid-base reagents can be reduced, and no anion and cation impurities are introduced, so that the purity of a lithium product is improved; in addition, the invention extracts lithium element first, can realize one-step separation of lithium element and iron phosphorus element, and achieves the purpose of selectively extracting lithium; meanwhile, only leaching and thermal decomposition processes are needed, the process is short, the process is simple, the leaching process can be carried out in a weak alkaline environment without harsh conditions such as microwave heating and the like, the corrosion is less, the requirement on the material of production equipment is low, and the method is suitable for being carried out in a weak alkaline environmentAnd the cost is low for large-scale production.

Description

Recycling method of retired lithium ion battery positive electrode material
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a recycling method of a retired lithium ion battery anode material.
Background
The lithium ion power battery is acknowledged to be capable of occupying a large application market in the field of new energy automobile batteries by virtue of good safety performance, good energy density (580Wh/kg), no memory effect, high theoretical specific capacity (170mAh/g) and good cycling stability. In recent years, lithium ion power batteries are applied to large-scale energy storage equipment and various electric vehicles on a large scale, but after the production of large-scale lithium ion power batteries in recent decades, a large batch of lithium ion power batteries will reach the retirement period due to the end of the service life of the lithium ion power batteries. Secondary recovery of precious metals in lithium ion power can also alleviate the problem of lithium resource shortage caused by the ever-increasing demand for electric vehicles. Therefore, it is necessary to develop a way for efficiently, economically and effectively recovering precious metals from the anode material of the retired lithium ion battery, so that the environmental problem caused by the power scrapping of lithium ions can be solved, and the problem of the exhaustion of lithium resources can be relieved.
A plurality of methods are provided for treating and recycling retired lithium ion batteries at home and abroad, and basically, the pretreatment is carried out firstly, and then valuable metals are recycled by a pyrometallurgical or hydrometallurgical method. The traditional method for the retired lithium ion battery adopts sulfuric acid to leach lithium iron phosphorus elements in the lithium ion battery anode material, the leaching rate can reach more than 97%, but not only a large amount of acidic reagents are consumed, but also the lithium iron phosphorus elements are not separated. In subsequent reports, it is proposed to add an oxidant such as hydrogen peroxide during sulfuric acid leaching, in order to separate lithium from iron phosphorus during leaching, and when the pH is greater than 2, the iron phosphate exists in a solid form, and the lithium enters into a solution to realize selective separation of lithium, while correspondingly reducing consumption of an acidic reagent. In addition, selective recovery of lithium iron phosphate is also reported to be achieved by using an acidic oxidant, for example, in the leaching process, lithium element enters a solution after a lithium iron phosphate positive electrode material reacts with sodium persulfate, while iron phosphorus element is precipitated in the form of iron phosphate, no acid is introduced in the process, and meanwhile, selective separation of the lithium iron phosphate is achieved. However, these methods do not completely solve the problem of large consumption of acid and alkali, and the recovery process is complicated. In addition, there are problems that inorganic salts in the waste liquid cannot be recovered efficiently, and introduction of an acidic reagent corrodes the experimental apparatus, and the requirement for the material of the equipment is high.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for recycling a lithium ion battery cathode material, which reduces the consumption of acid and alkali reagents, does not introduce anion and cation impurities, and has a short process, a simple process, and a high lithium recycling efficiency.
The invention provides a recycling method of an out-of-service lithium ion battery anode material, which comprises the following steps:
mixing the anode material of the retired lithium ion battery with hydrogen peroxide, and introducing carbon dioxide for reaction to obtain solid residues and a lithium-containing solution;
or ozone and carbon dioxide are introduced into the decommissioned lithium ion battery anode material in the aqueous solution to react to obtain solid residue and a lithium-containing solution; the water solution is water or hydrogen peroxide.
Preferably, the method further comprises the following steps:
and heating and decomposing the lithium-containing solution to obtain lithium carbonate.
Preferably, the temperature of the thermal decomposition is 40-90 ℃.
Preferably, the mass concentration of the hydrogen peroxide is 1-30%.
Preferably, the mass concentration of the hydrogen peroxide is 10-30%.
Preferably, the mass volume ratio of the retired lithium ion battery anode material to hydrogen peroxide is 1 g: 20-90 mL; the mass volume ratio of the retired lithium ion battery anode material to the aqueous solution is 1 g: 10-70 mL.
Preferably, the ozone is introduced at a rate of 0.1-3L/min; the carbon dioxide is introduced at a rate of 0.1-3L/min.
Preferably, the reaction temperature is 0-100 ℃; the reaction time is 1-5 h.
Preferably, the retired lithium ion battery positive electrode material is selected from one or more of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and lithium nickel manganate.
The invention provides a recycling method of an out-of-service lithium ion battery anode material, which comprises the following steps: mixing the anode material of the retired lithium ion battery with hydrogen peroxide, and introducing carbon dioxideReacting to obtain solid residue and lithium-containing solution; or ozone and carbon dioxide are introduced into the decommissioned lithium ion battery anode material in the aqueous solution to react to obtain solid residue and a lithium-containing solution; the water solution is water or hydrogen peroxide. Compared with the prior art, the invention introduces CO2The lithium ion battery can be recycled as a leaching agent and a precipitating agent, no extra precipitating agent is required to be added, the consumption of acid-base reagents can be reduced, and no anion and cation impurities are introduced, so that the purity of a lithium product is improved; in addition, the invention extracts lithium element first, can realize one-step separation of lithium element and iron phosphorus element, and achieves the purpose of selectively extracting lithium; meanwhile, only leaching and thermal decomposition processes are needed, the process is short, the process is simple, the leaching process does not need to be carried out under severe conditions such as microwave heating, the whole leaching process can be carried out in a weak alkaline environment, the corrosion is less, the requirement on the material of production equipment is low, and the method is suitable for large-scale production and has low cost.
The experimental result shows that the recovery processing method provided by the invention has higher leaching rate of lithium in the anode material of the retired lithium ion battery, and the leaching rate reaches more than 95%; the leaching rate of other components in the positive electrode material is low, such as the leaching rate of Fe is as low as 1 percent, and the leaching rate of P is as low as 3 percent.
Drawings
FIG. 1 is an XRD diffraction analysis pattern of the solid residue obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 invention provides a recycling method of an out-of-service lithium ion battery anode material, which comprises the following steps: mixing the anode material of the retired lithium ion battery with hydrogen peroxide, and introducing carbon dioxide for reaction to obtain solid residues and a lithium-containing solution; or ozone and carbon dioxide are introduced into the decommissioned lithium ion battery anode material in the aqueous solution to react to obtain solid residue and a lithium-containing solution; the water solution is water or hydrogen peroxide.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Mixing the anode material of the retired lithium ion battery with hydrogen peroxide, and introducing carbon dioxide for reaction; the material of the retired lithium ion battery positive electrode is preferably one or more of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and lithium nickel manganate; the retired lithium ion battery anode material is preferably crushed and then mixed with hydrogen peroxide; the mass concentration of the hydrogen peroxide is preferably 1-30%, more preferably 5-30%, still more preferably 10-25%, most preferably 10-20%; in the embodiment provided by the invention, the mass concentration of the hydrogen peroxide is specifically 12.5%, 18% or 18.6%; the mass volume ratio of the retired lithium ion battery anode material to hydrogen peroxide is preferably 1 g: 20-90 mL, more preferably 1 g: 30-90 mL, more preferably 1 g: 40-90 mL, more preferably 1 g: 50-90 mL, most preferably 1 g: 50-83 mL; in the embodiment provided by the invention, the mass-to-volume ratio of the retired lithium ion battery anode material to hydrogen peroxide is specifically 1 g: 50mL, 1 g: 83mL or 1 g: 66.7 mL; the carbon dioxide is preferably introduced at a rate of 0.1-3L/min, more preferably 0.1-2L/min, still more preferably 0.3-1.5L/min, still more preferably 0.5-1L/min, and most preferably 0.50L/min; the reaction is preferably carried out under stirring; the reaction temperature is preferably 0-100 ℃, more preferably 10-80 ℃, further preferably 20-40 ℃, and most preferably 20-30 ℃; the reaction time is preferably 1-5 h, more preferably 2-4 h, and further preferably 3-4 h.
After the reaction is finished, preferably carrying out solid-liquid separation to obtain solid residues and a lithium-containing solution; the solid-liquid separation method is a method well known to those skilled in the art, and in the present invention, suction filtration is preferable, and washing is preferable after suction filtration, so that a lithium-containing solution and a solid residue are obtained.
Or ozone is introduced into the decommissioned lithium ion battery anode material in the water solution to react with carbon dioxide; the material of the anode of the retired lithium ion battery is preferably one or more of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and lithium nickel manganate; preferably crushing the retired lithium ion battery positive electrode material and then mixing the crushed retired lithium ion battery positive electrode material with an aqueous solution; the aqueous solution is water or hydrogen peroxide; the mass concentration of the hydrogen peroxide is preferably 1-30%, more preferably 5-30%, still more preferably 10-25%, most preferably 10-20%; in the embodiment provided by the invention, the mass concentration of the hydrogen peroxide is specifically 12.5%, 18% or 18.6%; the mass volume ratio of the retired lithium ion battery positive electrode material to the aqueous solution is preferably 1 g: 10-70 mL, more preferably 1 g: 15-70 mL; in the embodiment provided by the invention, the mass-to-volume ratio of the retired lithium ion battery anode material to the aqueous solution is specifically 1 g: 16.7mL or 1 g: 66.7 mL; the ozone introducing speed is preferably 0.1-3L/min, more preferably 0.1-2L/min, still more preferably 0.3-1.5L/min, still more preferably 0.5-1L/min, and most preferably 0.50L/min; the carbon dioxide is preferably introduced at a rate of 0.1-3L/min, more preferably 0.1-2L/min, still more preferably 0.3-1.5L/min, still more preferably 0.5-1L/min, and most preferably 0.50L/min; the reaction is preferably carried out under stirring; the reaction temperature is preferably 0-100 ℃, more preferably 10-80 ℃, further preferably 20-40 ℃, and most preferably 20-30 ℃; the reaction time is preferably 1-5 h, more preferably 2-4 h, and further preferably 3-4 h; after the reaction is completed, it is preferable to obtain a solid residue and a lithium-containing solution by solid-liquid separation.
According to the invention, the anode material of the retired lithium ion battery and hydrogen peroxide and/or ozone are subjected to oxidation leaching under the condition of introducing carbon dioxide, so that lithium in the anode material can be separated from other elements. The obtained lithium-containing solution is processed by one step to obtain a lithium-containing product.
Heating and decomposing the lithium-containing solution to obtain lithium carbonate; the temperature of the heating decomposition is preferably 40-90 ℃, and more preferably 40-80 ℃; the heating is preferably stopped until the white precipitate is not increased. The lithium carbonate in the lithium-containing solution can be precipitated by thermal saturation through a heating decomposition method.
The invention introduces CO2As a leaching agent and a precipitating agent, the consumption of acid-base reagents can be reduced, and anion and cation impurities are not introduced, so that the purity of the lithium product is improved; in addition, the invention can realize the one-step separation of lithium element and iron phosphorus element, thereby achieving the purpose of selectively extracting lithium; meanwhile, only leaching and thermal decomposition processes are needed, the process is short, the process is simple, the process is not needed to be carried out under harsh conditions such as microwave heating, and the like, and the method is suitable for large-scale production and low in cost.
In order to further explain the present invention, the following describes in detail a recycling method of a retired lithium ion battery positive electrode material provided by the present invention with reference to an embodiment.
The reagents used in the following examples are all commercially available.
Example 1
1g of retired lithium iron phosphate anode material is crushed and placed in a stirring device, deionized water is added to adjust the solid-to-liquid ratio to be 50g/L, 30mL of 30% hydrogen peroxide is slowly added, carbon dioxide is introduced (the introduction rate is 0.50L/min), stirring reaction is carried out for 4 hours, and the main components of retired lithium iron phosphate are shown in Table 1.
Table 1 main components of retired lithium iron phosphate used in the examples of the present invention
Composition (I) Li Fe P O Al
Content (wt%) 4.31 37.31 18.15 28.80 0.355
Carrying out suction filtration and washing on the reaction product to obtain lithium-containing filtrate and solid residue;
and heating the lithium-containing filtrate to 60 ℃ for heating decomposition to obtain lithium carbonate.
And carrying out ICP test on the lithium-containing filtrate, wherein the content of Li in the filtrate is 41.53mg, the content of Fe in the filtrate is 4.10mg, and the content of P in the filtrate is 5.33 mg.
Therefore, in the method provided by the invention, the leaching rate of Li is 96.4%; the leaching rate of Fe was 1% and that of P was 2.9%.
As a result of XRD diffraction analysis of the solid residue, see fig. 1, fig. 1 is a XRD diffraction analysis pattern of the solid residue obtained in example 1 of the present invention, and as can be seen from fig. 1, the obtained solid residue is iron phosphate.
Example 2
1g of retired lithium iron phosphate anode material is crushed and placed in a stirring device, deionized water is added to adjust the solid-to-liquid ratio to be 30g/L, 50mL of 20% hydrogen peroxide is slowly added, carbon dioxide is introduced (the introduction rate is 0.50L/min), stirring reaction is carried out for 3 hours, and the main components of retired lithium iron phosphate are shown in Table 1.
Carrying out suction filtration and washing on the reaction product to obtain lithium-containing filtrate and solid residue;
and heating the lithium-containing filtrate to 80 ℃ for heating decomposition to obtain lithium carbonate.
And carrying out ICP test on the lithium-containing filtrate, wherein the content of Li in the filtrate is 41.28mg, the content of Fe in the filtrate is 4.05mg, and the content of P in the filtrate is 5.41 mg.
Therefore, in the method provided by the invention, the leaching rate of Li is 95.03%; the leaching rate of Fe was 1% and that of P was 3%.
Example 3
1g of retired lithium iron phosphate anode material is crushed and placed in a stirring device, deionized water is added to adjust the solid-to-liquid ratio to be 60g/L, 50mL of 25% hydrogen peroxide is slowly added, carbon dioxide is introduced (the introduction rate is 0.50L/min), stirring reaction is carried out for 4 hours, and the main components of retired lithium iron phosphate are shown in Table 1.
Carrying out suction filtration and washing on the reaction product to obtain lithium-containing filtrate and solid residue;
and heating the lithium-containing filtrate to 40 ℃ for heating decomposition to obtain lithium carbonate.
And carrying out ICP test on the lithium-containing filtrate, wherein the content of Li in the filtrate is 42.08mg, the content of Fe in the filtrate is 3.98mg, and the content of P in the filtrate is 5.24 mg.
Therefore, in the method provided by the invention, the leaching rate of Li is 97.6%; the leaching rate of Fe was 1% and that of P was 2.9%.
Example 4
Crushing 1g of retired lithium iron phosphate anode material (the main components of which are shown in table 1), placing the crushed material in a stirring device, adding deionized water to adjust the solid-to-liquid ratio to be 60g/L, introducing carbon dioxide (the introduction rate is 0.50L/min) and ozone (the introduction rate is 0.50L/min), stirring and reacting for 4 hours, and performing suction filtration and washing on a reaction product to obtain lithium-containing filtrate and solid residues; and heating the lithium-containing filtrate to 40 ℃ for heating decomposition to obtain lithium carbonate. And performing ICP test on the lithium-containing filtrate, wherein the leaching rate of lithium is 98.63%.
Example 5
Crushing 1g of retired lithium iron phosphate anode material (the main components of which are shown in table 1), placing the crushed material in a stirring device, adding deionized water to adjust the solid-to-liquid ratio to be 60g/L, slowly adding 50mL of 25% hydrogen peroxide, introducing carbon dioxide (the introduction rate is 0.50L/min) and ozone, stirring and reacting for 4 hours, and performing suction filtration and washing on a reaction product to obtain lithium-containing filtrate and solid residues; and heating the lithium-containing filtrate to 40 ℃ for heating decomposition to obtain lithium carbonate. The lithium-containing filtrate is subjected to ICP test, and the leaching rate of lithium is 99.83%, the leaching rate of Fe is 0.3%, and the leaching rate of P is 1%.
Comparative example 1
The same as in example 3 except that an ICP test was performed on the obtained lithium-containing filtrate without introducing carbon dioxide gas, and the content of Li, Fe, and P in the filtrate was 15.77mg, 10.19mg, and 32.71mg, respectively; it can be seen that in comparative example 1, the leaching rate of Li was 36.6%; the leaching rate of Fe was 2.73%, and the leaching rate of P was 18.02%.
Comparative example 2
The same as example 3, except that instead of introducing carbon dioxide gas, air was introduced (introduction rate: 0.50L/min), and the obtained lithium-containing filtrate was subjected to ICP test, and the filtrate had a Li content of 16.59mg, a Fe content of 13.73mg, and a P content of 36.52 mg; it can be seen that in comparative example 1, the Li leaching rate was 38.49%; the leaching rate of Fe was 3.68% and that of P was 20.12%.

Claims (9)

1. A recycling method of a retired lithium ion battery anode material is characterized by comprising the following steps:
mixing the anode material of the retired lithium ion battery with hydrogen peroxide, and introducing carbon dioxide for reaction to obtain solid residues and a lithium-containing solution;
or ozone and carbon dioxide are introduced into the decommissioned lithium ion battery anode material in the aqueous solution to react to obtain solid residue and a lithium-containing solution; the water solution is water or hydrogen peroxide.
2. The recycling treatment method according to claim 1, further comprising:
and heating and decomposing the lithium-containing solution to obtain lithium carbonate.
3. The recovery processing method according to claim 2, wherein the temperature of the thermal decomposition is 40 ℃ to 90 ℃.
4. The recovery processing method according to claim 1, wherein the mass concentration of the hydrogen peroxide is 1-30%.
5. The recovery processing method according to claim 1, wherein the mass concentration of the hydrogen peroxide is 10-30%.
6. The recycling method of claim 1, wherein the mass-to-volume ratio of the retired lithium ion battery anode material to hydrogen peroxide is 1 g: 20-90 mL; the mass volume ratio of the retired lithium ion battery anode material to the aqueous solution is 1 g: 10-70 mL.
7. The recovery processing method according to claim 1, wherein the ozone is introduced at a rate of 0.1 to 3L/min; the carbon dioxide is introduced at a rate of 0.1-3L/min.
8. The recovery processing method according to claim 1, wherein the reaction temperature is 0 ℃ to 100 ℃; the reaction time is 1-5 h.
9. The recycling method according to claim 1, wherein the decommissioned lithium ion battery positive electrode material is selected from one or more of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and lithium nickelate manganate.
CN202110592746.6A 2021-05-28 2021-05-28 Recycling method of retired lithium ion battery positive electrode material Pending CN113314778A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110592746.6A CN113314778A (en) 2021-05-28 2021-05-28 Recycling method of retired lithium ion battery positive electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110592746.6A CN113314778A (en) 2021-05-28 2021-05-28 Recycling method of retired lithium ion battery positive electrode material

Publications (1)

Publication Number Publication Date
CN113314778A true CN113314778A (en) 2021-08-27

Family

ID=77375994

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110592746.6A Pending CN113314778A (en) 2021-05-28 2021-05-28 Recycling method of retired lithium ion battery positive electrode material

Country Status (1)

Country Link
CN (1) CN113314778A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116265386A (en) * 2021-12-16 2023-06-20 中国科学院宁波材料技术与工程研究所 Preparation method of phosphate positive electrode material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106340692A (en) * 2016-11-14 2017-01-18 中国科学院过程工程研究所 A kind of method that cleaning reclaims lithium in positive electrode
CN106910959A (en) * 2017-05-04 2017-06-30 北京科技大学 A kind of method of selective recovery lithium in waste material from LiFePO4
CN108808155A (en) * 2018-08-17 2018-11-13 湖南金凯循环科技有限公司 A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate
US20200071794A1 (en) * 2017-03-01 2020-03-05 The University Of Sydney Lithium extraction method
CN111129636A (en) * 2019-12-31 2020-05-08 深圳清华大学研究院 Regeneration method of waste lithium iron phosphate battery positive electrode material
CN111593200A (en) * 2020-04-30 2020-08-28 中国科学院过程工程研究所 Method for recovering valuable metals in waste lithium ion batteries
CN112441572A (en) * 2019-08-27 2021-03-05 比亚迪股份有限公司 Method for recovering waste lithium iron phosphate anode material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106340692A (en) * 2016-11-14 2017-01-18 中国科学院过程工程研究所 A kind of method that cleaning reclaims lithium in positive electrode
US20200071794A1 (en) * 2017-03-01 2020-03-05 The University Of Sydney Lithium extraction method
CN106910959A (en) * 2017-05-04 2017-06-30 北京科技大学 A kind of method of selective recovery lithium in waste material from LiFePO4
CN108808155A (en) * 2018-08-17 2018-11-13 湖南金凯循环科技有限公司 A method of by waste lithium ion cell anode material preparation battery-level lithium carbonate
CN112441572A (en) * 2019-08-27 2021-03-05 比亚迪股份有限公司 Method for recovering waste lithium iron phosphate anode material
CN111129636A (en) * 2019-12-31 2020-05-08 深圳清华大学研究院 Regeneration method of waste lithium iron phosphate battery positive electrode material
CN111593200A (en) * 2020-04-30 2020-08-28 中国科学院过程工程研究所 Method for recovering valuable metals in waste lithium ion batteries

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116265386A (en) * 2021-12-16 2023-06-20 中国科学院宁波材料技术与工程研究所 Preparation method of phosphate positive electrode material

Similar Documents

Publication Publication Date Title
CN112142077B (en) Method for preparing battery-grade lithium carbonate and iron phosphate by recycling lithium iron phosphate positive electrode waste
CN112331949B (en) Method for recovering phosphorus, iron and lithium from waste lithium iron phosphate batteries
CN112093785B (en) Method for efficiently recycling lithium in lithium iron phosphate cathode waste and preparing iron phosphate for battery
CN108550939B (en) A method of selective recovery lithium and lithium carbonate is prepared from waste lithium cell
CN113896211B (en) Treatment method for funding waste lithium iron phosphate battery
CN112410556B (en) Method for recovering waste lithium iron phosphate powder
CN110474123B (en) Comprehensive recovery method of waste lithium iron phosphate battery positive electrode material
CN109626350B (en) Method for preparing battery-grade iron phosphate from waste lithium iron phosphate battery positive plates
CN108178170A (en) It is a kind of that the method that lithium prepares battery-level lithium carbonate is recycled from lithium iron phosphate waste
CN109179359A (en) A method of extracting lithium and ferric phosphate from LiFePO4 waste material
CN111082043A (en) Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material
CN114349030B (en) Comprehensive wet recycling method for waste lithium iron phosphate positive plate
CN114655969B (en) Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste material
CN112723330B (en) Preparation method and application of iso-phospho-ferromanganese iron phosphate
CN111961839A (en) Method for synchronously leaching valuable metals from positive and negative electrode active materials of waste lithium ion batteries and removing impurities
CN111697282A (en) Method for extracting lithium from dilute solution recovered from waste battery positive electrode material
CN113122725A (en) Method for improving metal recovery rate and purity of waste lithium battery
CN113511664A (en) Method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste
CN112267023A (en) Two-stage defluorination method for fluorine-containing material
CN113314778A (en) Recycling method of retired lithium ion battery positive electrode material
CN113846219A (en) Method for extracting lithium from waste lithium batteries
CN115072688B (en) Method for recycling all components of waste lithium iron phosphate battery
CN115744864A (en) Method for efficiently recycling and reusing waste lithium iron phosphate battery positive electrode material
CN115947323A (en) Method for extracting lithium from waste lithium iron phosphate and preparing iron phosphate
CN101792862A (en) Method for recovering metal through purified flue gas of scrap nickel-hydrogen battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210827

RJ01 Rejection of invention patent application after publication