CN113200574A - Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery - Google Patents
Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery Download PDFInfo
- Publication number
- CN113200574A CN113200574A CN202110331503.7A CN202110331503A CN113200574A CN 113200574 A CN113200574 A CN 113200574A CN 202110331503 A CN202110331503 A CN 202110331503A CN 113200574 A CN113200574 A CN 113200574A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- manganese
- waste
- rich manganese
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing 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
- H01M10/05—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
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for regenerating a lithium-rich manganese-based positive electrode from mixed waste lithium batteries, which comprises the following steps of: 1) waste LiNixCoyMnzO2And LiCoO2Mixing waste pole piece raw materials, directly crushing, and leaching by alkaline reduction ammonia to obtain leaching solution rich in Li, Ni and Co and leaching slag containing a large amount of Mn elements; 2) leaching slag and waste LiMn2O4Mixing the powders, and performing acid leaching to obtain a leaching solution rich in Li and Mn; 3) mixing the leachate obtained in steps 1 and 2 and adding a proper metalSalt, fixing the molar ratio of lithium, nickel, cobalt and manganese elements; 4) and preparing a lithium-rich manganese-based precursor from the mixed solution in a hydrothermal mode, and calcining in a muffle furnace to obtain the lithium-rich manganese-based anode material. The method for recycling the lithium-rich manganese-based positive electrode material based on mixing of multiple waste lithium batteries has the advantages of high applicability, relatively low energy consumption, high added value of recycled products and strong process controllability.
Description
Technical Field
The invention relates to a method for recycling waste lithium batteries, in particular to a method for recycling metal elements in mixed type waste lithium battery anode materials and recycling valuable metal elements, and belongs to the technical field of solid waste resource utilization.
Background
The proportion of petrochemical energy in the energy production structure of China is relatively high, so that the pollution to the environment is more and more serious day by day. The lithium ion battery as a high-energy green battery has the obvious advantages of long cycle life and good safety due to high voltage and high capacity, is widely applied to portable equipment, electric automobiles, space technology, national defense industry and the like, and plays a great economic benefit. The industrial scale of lithium batteries in China is increased year by year, the lithium battery yield in 2019 is 157.22 billion yuan, and the industrial scale reaches 2058 billion yuan.
However, the service life of lithium batteries is generally 3-6 years, and the large number of lithium batteries put into use means that waste lithium batteries are accumulated continuously. The lithium battery anode material which is commercially used at present is LiCoO2、LiNixCoyMnzO2、LiMn2O4Which contains a large amount of valuable metal elements. The valuable metals are important components of the anode material of the lithium battery, occupy the price of the battery with a large share, and control the market trend of the lithium battery. The decommissioned lithium ion battery can bring various hazards to the environment and the society due to improper treatment or idling, and also can cause the waste of valuable metal resources in the lithium ion battery. Therefore, valuable metals are recycled and utilized, and the method has positive significance for relieving the problem of lack of strategic metal resources in China, promoting the recyclable strategic development of non-ferrous metal resources and the like. Therefore, it is necessary to effectively recycle the waste lithium ion battery by using an appropriate method.
At present, the method for recycling the waste lithium ion batteries comprises the direct regeneration of single-element chemical products (Li)2CO3，CoSO4，NiSO4Etc.) and regenerated into electrode material. Regenerating a single chemical product process streamThe process is long, and the added value of the regenerated commodity is low, so that the recovery economic benefit is low. The regeneration of electrode materials is a hot point in research at present, and the steps of regenerating electrode materials generally are as follows: firstly, leaching by a wet method, extracting valuable metals in the leaching solution by methods of coprecipitation, sol-gel, spray drying and the like, and finally sintering to obtain the regeneration material. Acid leaching is widely applied due to the advantages of high metal recovery rate, low energy consumption and the like, but the pH of an acid leaching system is extremely low, and a large amount of alkali liquor is needed for neutralizing a leaching solution, so that the waste cost of the alkali liquor is increased. The alkaline leaching is suitable for efficiently and selectively separating and recovering valuable metals due to selectivity on the valuable metals, but does not have selectivity on manganese metals, so that the valuable metals are precipitated in slag. The recovery and regeneration of the waste lithium ion battery into the commercial electrode material is the main direction of the existing recovery and regeneration method, and the purpose of short-flow high-efficiency recovery is realized. However, as the social requirement for energy storage of lithium batteries is increasing, the method cannot meet the future requirements for higher working voltage and higher capacity of lithium batteries. The lithium-rich manganese-based cathode material has the specific energy exceeding 900Wh kg-1Has a wide operating voltage window of 2.0 to 4.8V and is relatively low in price, and thus is considered as one of the most promising positive electrode materials for next-generation lithium batteries. On the other hand, the lithium ion batteries are various in variety, so that the waste lithium battery recovery method has universality and can be really applied to large-scale production.
Disclosure of Invention
Aiming at the defects of the existing valuable metal recovery method of the waste lithium battery, the invention aims to provide a method for regenerating a lithium-rich manganese-based positive electrode from a mixed waste lithium battery.
The method adopts alkaline reduction ammonia leaching to carry out leaching on waste LiNixCoyMnzO2And LiCoO2Leaching the pole piece to obtain leaching solution rich in Li, Ni and Co and leaching slag containing a large amount of Mn elements, and leaching the leaching slag and LiMn2O4And mixing, namely leaching by using inorganic acid to obtain an acidic leaching solution rich in lithium and manganese, mixing the alkaline leaching solution and the acidic leaching solution, and directly obtaining the lithium-rich manganese-based positive electrode material with excellent electrochemical performance by using a hydrothermal method. The method recovers the process pairThe waste battery has low requirement on the type, can be commonly used, combines the advantages of acid leaching and alkali leaching, does not waste acid-base solution in the recovery process, and simultaneously the electrochemical performance of the prepared lithium-rich manganese-based anode material is superior to that of the lithium ion battery anode material commercially applied at present, thereby realizing the regeneration of high value-added products and increasing the recovery economic benefit.
The purpose of the experiment is realized by the following technical scheme:
a method for regenerating a lithium-rich manganese-based positive electrode from mixed waste lithium batteries comprises the following steps:
(1) waste LiNixCoyMnzO2And LiCoO2Directly crushing the mixed pole piece raw materials, and performing alkaline leaching to obtain a leaching solution rich in Li, Ni and Co and leaching residues containing a large amount of Mn elements;
(2) leaching slag containing a large amount of Mn element in the step (1) and directly crushed waste LiMn2O4Mixing the pole piece materials, dissolving the mixed powder by using inorganic acid to obtain leachate rich in lithium and manganese, and removing impurities of aluminum and iron in the leachate;
(3) mixing the leachate obtained in the step (1) and the leachate obtained after impurity removal in the step (2), adding corresponding metal salt for regulation according to the molar ratio of lithium, nickel, cobalt and manganese in the mixed solution, and hydrothermally synthesizing a lithium-rich manganese-based ternary cathode material precursor in an inert atmosphere;
(4) and (4) calcining the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (3) in a muffle furnace to obtain the lithium-rich manganese-based positive electrode material.
Preferably, in the step (1), the waste LiNixCoyMnzO2And LiCoO2The mixed pole piece is crushed by a crusher, and the particle size is 45-200 meshes.
Preferably, in the step (1), the alkaline leaching agent is composed of ammonia, a reducing agent and a pH buffering agent, wherein the reducing agent is one or more of sodium sulfite, hydrogen peroxide and hydrazine hydrate, and the pH buffering agent is one or more of ammonium carbonate, ammonium bicarbonate and ammonium sulfate.
Preferably, in the step (1), the concentration of ammonia is 1-5M, the concentration of the reducing agent is 0.5-3M, and the concentration of the pH buffering agent is 0-3M.
Preferably, in the step (1), the solid-to-liquid ratio of the waste powder to the leachate is 5-30 g/L.
Preferably, in the step (1), the reaction temperature is 50-90 ℃.
Preferably, in the step (1), the reaction time is 0.5-12 h.
Preferably, in the step (2), the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
Preferably, in the step (2), the concentration of the inorganic acid is 0.5-5M.
Preferably, in the step (2), the solid-to-liquid ratio of the leaching powder to the inorganic acid leaching solution is 5-30 g/L.
Preferably, in the step (2), the reaction temperature is 50-90 ℃.
Preferably, in the step (2), the reaction time is 0.5-12 h.
Preferably, in the step (2), impurities of aluminum and iron in the leachate are removed, and an impurity removing agent is composed of sodium sulfate and sodium carbonate.
Preferably, in the step (2), the mass concentration of sodium sulfate is 3-5 g/L, the mass concentration of sodium carbonate is 80-200 g/L, the pH of the solution is 4.0-5.0, the reaction temperature is 60-80 ℃, and the reaction time is 0.5-2 h.
Preferably, in the step (3), the corresponding metal lithium nickel cobalt manganese salt is any one of sulfate, chloride, nitrate and acetate.
Preferably, in the step (3), the inert atmosphere is any one of argon and nitrogen, and the aeration time is 2-64 h.
Preferably, in the step (3), the hydrothermal synthesis temperature is 100-300 ℃.
Preferably, in the step (3), the reaction time is 2-64 h.
Preferably, in the step (4), the muffle furnace calcination temperature is 700-1000 ℃, and the calcination temperature is 6-12 h.
The invention has the beneficial effects that
(1) The method adopts alkaline reduction ammonia leaching to remove the waste LiCoO2、LiNixCoyMnzO2Pole pieceLeaching to obtain Li, Ni and Co-rich leachate and leaching residue containing a large amount of Mn elements, and mixing the leaching residue with LiMn2O4And mixing, namely leaching by using inorganic acid to obtain an acidic leaching solution rich in lithium and manganese, mixing the alkaline leaching solution and the acidic leaching solution, and directly obtaining the lithium-rich manganese-based positive electrode material with excellent electrochemical performance by using a hydrothermal method. The complex process of multi-metal separation is avoided, the process flow is shortened, the operation is simple, and the purposes of closed-loop green recovery and solid waste recycling are realized.
(2) The method disclosed by the invention comprehensively utilizes the advantages of alkaline leaching and acidic leaching according to different types of waste lithium batteries, does not generate a large amount of acid-base waste liquid and a large amount of waste residues in the recovery process, is simple, simple in using equipment, high in controllability, low in requirement on the waste lithium batteries, high in universality and has a commercial application prospect.
(3) The lithium-rich material regenerated by the method has excellent electrochemical performance, is consistent with the electrochemical performance of the lithium-rich material prepared by a pure chemical reagent, and increases the economic benefit of waste lithium battery recovery.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of a lithium-rich manganese-based positive electrode material prepared in example 1 of the invention;
FIG. 2 is a SEM image of the morphology of the lithium-rich manganese-based positive electrode material prepared in example 1 of the present invention;
fig. 3 is a data diagram of the electrochemical cycle of the lithium-rich manganese-based cathode material prepared in example 1 of the present invention applied to a lithium ion battery.
Detailed Description
The invention is further illustrated by the following specific examples and figures.
Example 1
The embodiment comprises the following steps:
(1) 5g of waste LiNixCoyMnzO2And 5g LiCoO2The mixed pole piece raw materials are directly crushed by a crusher and sieved by a 200-mesh screen to form uniformly dispersed mixed powder. Adding 5g of the mixed powder into a 1000mL three-neck flask, ensuring the solid-to-liquid ratio to be 10g/L, weighing 112mL of ammonia water, 59.295g of ammonium bicarbonate and 189.06g of sulfurous acidSodium, the reaction temperature is 80 ℃, the reaction time is 5 hours, leaching solution rich in Li, Ni and Co and leaching slag containing a large amount of Mn elements are obtained, and the leaching slag is placed in a blast drying oven and dried for 12 hours at 120 ℃;
(2) 3g of leaching residue containing a large amount of Mn element and 3g of waste LiMn obtained by directly crushing and sieving through a 200-mesh screen2O4Ball milling and mixing the pole pieces to obtain a mixture. Putting 5g of the mixture into a 1000mL three-neck flask, ensuring the solid-to-liquid ratio to be 10g/L, weighing 54.35mL of concentrated sulfuric acid, reacting at 80 ℃ for 2 hours to obtain an acid leaching solution; adding 1.05g of sodium sulfate and 24g of sodium carbonate into 300ml of pickle liquor, controlling the pH to be 4.5, reacting at the temperature of 70 ℃, reacting for 2 hours, and then separating filtrate and filter residue;
(3) mixing the alkaline leaching solution and the acid filtrate, measuring the concentration of lithium, nickel, cobalt and manganese in the solution by adopting ICP (inductively coupled plasma), adding 9.114g of manganese acetate and 0.08g of cobalt acetate into 200ml of mixed leaching solution to fix the molar concentration of the lithium, nickel, cobalt and manganese in the solution to 1.2:0.13:0.13: 0.54. Placing the mixed solution in a hydrothermal reaction kettle, and continuously introducing nitrogen during the reaction period of 18h at 210 ℃ to obtain a lithium-rich manganese-based precursor;
(4) and calcining the precursor in a muffle furnace at 800 ℃ for 10h to obtain the lithium-rich manganese-based material.
As shown in FIG. 1, the regenerated lithium-rich manganese-based material obtained in example 1 of the present invention has a smooth and uniformly dispersed surface and primary particles with a particle size of 100 to 200 μm.
As shown in FIG. 2, the regenerated lithium-rich manganese-based material obtained in example 1 of the present invention has good crystallinity and a distinct layered structure.
As shown in FIG. 3, the first-cycle discharge capacity of the regenerated lithium-rich manganese-based material obtained in example 1 of the present invention was 197.9 mAh/g.
The first-cycle discharge capacity of the lithium-rich manganese-based positive electrode material obtained in the example is 197.9mAh/g under the discharge rate of 0.2C, and the capacity retention rate is 78.32% after 80 cycles of circulation, which indicates that the lithium-rich manganese-based positive electrode material can be directly used as a lithium ion battery positive electrode material and has good electrochemical performance.
Example 2
The embodiment comprises the following steps:
(1) 10g of waste LiNixCoyMnzO2And 5g LiCoO2The mixed pole piece raw materials are directly crushed by a crusher and sieved by a 100-mesh screen to form uniformly dispersed mixed powder. Adding 10g of mixed powder into a 1000mL three-neck flask, ensuring that the solid-to-liquid ratio is 20g/L, weighing 67.26mL of ammonia water, 118.58g of ammonium bicarbonate and 189.06g of sodium sulfite, reacting at 80 ℃ for 8 hours to obtain leachate rich in Li, Ni and Co and leaching slag containing a large amount of Mn elements, placing the leaching slag in a forced air drying oven, and drying at 120 ℃ for 12 hours;
(2) 5g of leaching residue containing a large amount of Mn element and 3g of waste LiMn obtained by directly crushing and sieving through a 100-mesh screen2O4And ball milling and mixing the polar pieces to obtain a mixture. Placing 5g of the mixture into a 500mL three-neck flask, ensuring the solid-to-liquid ratio to be 20g/L, weighing 27.17mL of concentrated sulfuric acid, reacting at 80 ℃ for 3 hours to obtain an acid leaching solution; adding 1g of sodium sulfate and 25g of sodium carbonate into the pickle liquor, controlling the pH to be 4.1, the reaction temperature to be 75 ℃, reacting for 2 hours, and then separating the filtrate from the filter residue;
(3) mixing the alkaline leaching solution and the acid filtrate, measuring the concentration of lithium, nickel, cobalt and manganese in the solution by adopting ICP (inductively coupled plasma), adding 13.214g of manganese acetate and 0.59g of cobalt acetate into 200ml of mixed leaching solution to fix the molar concentration of the lithium, nickel, cobalt and manganese in the solution to 1.2:0.13:0.13: 0.54. Placing the mixed solution in a hydrothermal reaction kettle to react for 18h at 200 ℃, and continuously introducing nitrogen during the reaction period to obtain a lithium-rich manganese-based precursor;
(4) and calcining the precursor in a muffle furnace at 900 ℃ for 12h to obtain the lithium-rich manganese-based material.
The first-cycle discharge capacity of the lithium-rich manganese-based positive electrode material obtained in the example is 246.6mAh/g under the discharge rate of 0.2C, and the capacity retention rate is 78.6% after 100 cycles of circulation, which indicates that the lithium-rich manganese-based positive electrode material can be directly used as a lithium ion battery positive electrode material and has good electrochemical performance.
Example 3
The embodiment comprises the following steps:
(1) 5g of waste LiNixCoyMnzO2And 5g LiCoO2Mixing pole piece raw materials, pulverizing with pulverizer directly, and pulverizing with 200 deg.CSieving with mesh sieve to obtain uniformly dispersed mixed powder. Adding 5g of mixed powder into a 500mL three-neck flask, ensuring that the solid-to-liquid ratio is 20g/L, weighing 37.37mL of ammonia water, 39.53g of ammonium bicarbonate and 63.02g of sodium sulfite, reacting at 80 ℃ for 12h to obtain leachate rich in Li, Ni and Co and leaching slag containing a large amount of Mn elements, placing the leaching slag in a forced air drying oven, and drying at 120 ℃ for 12 h;
(2) 5g of leaching residue containing a large amount of Mn element and 5g of waste LiMn obtained by directly crushing and sieving through a 200-mesh screen2O4And ball milling and mixing the polar pieces to obtain a mixture. Putting 5g of the mixture into a 500mL three-neck flask, ensuring that the solid-to-liquid ratio is 25g/L, adding 16.30mL of concentrated sulfuric acid, reacting at 90 ℃ for 2 hours to obtain an acid leaching solution; adding 0.8g of sodium sulfate and 20g of sodium carbonate into the pickle liquor, controlling the pH to be 4.5, the reaction temperature to be 70 ℃, reacting for 2 hours, and then separating the filtrate from the filter residue;
(3) mixing the alkaline leaching solution and the acid filtrate, measuring the lithium nickel cobalt manganese concentration in the solution by adopting ICP (inductively coupled plasma), taking 200ml of mixed leaching solution, and adding 10.816g of manganese chloride and 0.39g of cobalt chloride to ensure that the molar concentration of the lithium nickel cobalt manganese in the solution is fixed to be 1.2:0.13:0.13: 0.54. Placing the mixed solution in a hydrothermal reaction kettle to react for 15 hours at 200 ℃, and continuously introducing argon gas during the reaction period to obtain a lithium-rich manganese-based precursor;
(4) and calcining the precursor in a muffle furnace at 1000 ℃ for 12h to obtain the lithium-rich manganese-based material.
The first-cycle discharge capacity of the lithium-rich manganese-based positive electrode material obtained in the example is 253.2mAh/g under the discharge rate of 0.2C, and the capacity retention rate is 76.4% after 100 cycles of circulation, which indicates that the lithium-rich manganese-based positive electrode material can be directly used as a lithium ion battery positive electrode material and has good electrochemical performance.
Example 4
The embodiment comprises the following steps:
(1) 5g of waste LiNixCoyMnzO2And 10g LiCoO2The mixed pole piece raw materials are directly crushed by a crusher and sieved by a 200-mesh screen to form uniformly dispersed mixed powder. Adding 10g of the mixed powder into a 500ml three-neck flask, ensuring the solid-to-liquid ratio to be 25g/L, and weighing 89 g of the mixed powder69mL of ammonia water, 47.436g of ammonium bicarbonate and 100.832g of sodium sulfite, the reaction temperature is 80 ℃, the reaction time is 7 hours, a leaching solution rich in Li, Ni and Co and leaching residues containing a large amount of Mn elements are obtained, and the leaching residues are placed in a forced air drying oven and dried for 12 hours at 120 ℃;
(2) 10g of leaching residue containing a large amount of Mn element and 5g of waste LiMn obtained by directly crushing and sieving through a 200-mesh screen2O4And ball milling and mixing the polar pieces to obtain a mixture. Putting 8g of the mixture into a 500mL three-neck flask, ensuring that the solid-to-liquid ratio is 20g/L, adding 86.96mL of concentrated sulfuric acid, reacting at 90 ℃ for 2 hours to obtain an acid leaching solution; adding 1.2g of sodium sulfate and 40g of sodium carbonate into the pickle liquor, controlling the pH to be 4.1, the reaction temperature to be 70 ℃, reacting for 2 hours, and then separating the filtrate from the filter residue;
(3) mixing the alkaline leaching solution and the acid filtrate, measuring the lithium nickel cobalt manganese concentration in the solution by adopting ICP (inductively coupled plasma), taking 300ml of mixed leaching solution, and adding 8.568g of manganese chloride and 0.24g of cobalt chloride to ensure that the molar concentration of the lithium nickel cobalt manganese in the solution is fixed to be 1.2:0.13:0.13: 0.54. Placing the mixed solution in a hydrothermal reaction kettle to react for 12 hours at the temperature of 250 ℃, and continuously introducing argon gas during the reaction period to obtain a lithium-rich manganese-based precursor;
(4) and calcining the precursor in a muffle furnace at 1000 ℃ for 8h to obtain the lithium-rich manganese-based material.
The first-cycle discharge capacity of the lithium-rich manganese-based positive electrode material obtained in the example is 265.3mAh/g under the discharge rate of 0.2C, and the capacity retention rate is 77.5% after 100 cycles of circulation, which indicates that the lithium-rich manganese-based positive electrode material can be directly used as a lithium ion battery positive electrode material and has good electrochemical performance.
The first-cycle discharge capacity of the lithium-rich manganese-based positive electrode material obtained in the example is 265.3mAh/g under the discharge rate of 0.2C, and the capacity retention rate is 77.5% after 100 cycles of circulation, which indicates that the lithium-rich manganese-based positive electrode material can be directly used as a lithium ion battery positive electrode material and has good electrochemical performance.
Claims (8)
1. A method for regenerating a lithium-rich manganese-based positive electrode from mixed waste lithium batteries is characterized by comprising the following steps:
(1) waste LiNixCoyMnzO2And LiCoO2Directly crushing the mixed pole piece raw materials, and performing alkaline leaching to obtain a leaching solution rich in Li, Ni and Co and leaching residues containing a large amount of Mn elements;
(2) taking leaching residues containing a large amount of Mn element in the step (1) and directly crushed waste LiMn2O4Mechanically mixing the pole pieces, dissolving the mixed powder by adopting inorganic acid to obtain leachate rich in lithium and manganese, and removing impurities of aluminum and iron in the leachate;
(3) mixing the leachate obtained in the step (1) and the leachate obtained after impurity removal in the step (2), adding corresponding metal salt for regulation according to the molar ratio of lithium, nickel, cobalt and manganese in the mixed solution, and hydrothermally synthesizing a lithium-rich manganese-based positive electrode material precursor in an inert atmosphere;
(4) calcining the precursor of the lithium-rich manganese-based positive electrode material obtained in the step (3) in a muffle furnace to obtain the lithium-rich manganese-based positive electrode material Li1.2Mn0.54Ni0.13Co0.13O2。
2. The method for regenerating a lithium-rich manganese-based positive electrode from a mixed waste lithium battery according to claim 1, characterized in that the waste LiNi in the step (1) isxCoyMnzO2And LiCoO2And crushing the mixed pole piece by using a crusher to obtain uniformly dispersed powder with the particle size of 45-200 meshes.
3. The method for regenerating the lithium-rich manganese-based positive electrode from the mixed waste lithium battery as claimed in claims 1-2, wherein the method comprises the following steps: the alkaline leaching agent in the step (1) is composed of ammonia, a reducing agent and a pH buffering agent, wherein the reducing agent is one or more of sodium sulfite, hydrogen peroxide and hydrazine hydrate, the pH buffering agent is one or more of ammonium carbonate, ammonium bicarbonate and ammonium sulfate, the concentration of ammonia is 1-5M, the concentration of the reducing agent is 0.5-3M, the concentration of the pH buffering agent is 0-3M, the solid-liquid ratio of waste powder to leachate is 5-30 g/L, the reaction temperature is 50-90 ℃, and the reaction time is 0.5-12 h.
4. The method for regenerating the lithium-rich manganese-based positive electrode from the mixed waste lithium battery as claimed in claims 1 to 3, wherein the method comprises the following steps: in the step (2), the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid, the concentration of the inorganic acid is 0.5-5M, the solid-to-liquid ratio of the leached powder to the inorganic acid leachate is 5-30 g/L, the reaction temperature is 50-90 ℃, and the reaction time is 0.5-12 h.
5. The method for regenerating the lithium-rich manganese-based positive electrode from the mixed waste lithium battery as claimed in claims 1 to 4, wherein the method comprises the following steps: removing impurities of aluminum and iron in the leachate in the step (2), wherein an impurity removing agent consists of sodium sulfate and sodium carbonate, the mass concentration of the sodium sulfate is 3-5 g/L, the mass concentration of the sodium carbonate is 80-200 g/L, the pH value of the solution is 4.0-5.0, the reaction temperature is 60-80 ℃, and the reaction time is 0.5-2 h.
6. The method for regenerating the lithium-rich manganese-based positive electrode from the mixed waste lithium battery as claimed in claims 1 to 5, wherein the method comprises the following steps: in the step (3), corresponding metal salt is added into the mixed solution to adjust the molar concentration of lithium, nickel, cobalt and manganese to be 1.2:0.13:0.13:0.54, wherein the corresponding metal lithium, nickel, cobalt and manganese salt is any one of sulfate, chloride, nitrate and acetate.
7. The method for regenerating the lithium-rich manganese-based positive electrode from the mixed waste lithium battery as claimed in claims 1 to 6, wherein the method comprises the following steps: in the step (3), the inert atmosphere is any one of argon and nitrogen, the aeration time is 2-64 h, the hydrothermal synthesis temperature is 100-300 ℃, and the reaction time is 2-64 h.
8. The method for regenerating the lithium-rich manganese-based positive electrode from the mixed waste lithium battery as claimed in claims 1 to 7, wherein the method comprises the following steps: and (4) calcining the muffle furnace at 700-1000 ℃ for 6-12 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110331503.7A CN113200574A (en) | 2021-03-29 | 2021-03-29 | Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110331503.7A CN113200574A (en) | 2021-03-29 | 2021-03-29 | Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113200574A true CN113200574A (en) | 2021-08-03 |
Family
ID=77025762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110331503.7A Pending CN113200574A (en) | 2021-03-29 | 2021-03-29 | Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113200574A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113904016A (en) * | 2021-10-11 | 2022-01-07 | 格林美股份有限公司 | Method for reconstructing single crystal electrode material from waste lithium ion battery |
| CN115449636A (en) * | 2022-09-05 | 2022-12-09 | 中南大学 | Recovery and regeneration process and equipment for lithium ion battery anode material |
| CN115465899A (en) * | 2022-09-14 | 2022-12-13 | 陕西红马科技有限公司 | Multi-crown multi-element spherical coating precursor, preparation method thereof, chemical coating modified product and chemical coating modification method |
| CN115520909A (en) * | 2022-10-10 | 2022-12-27 | 山东遥米新能源科技有限公司 | Recovery method of ternary cathode material |
| CN115784324A (en) * | 2022-11-29 | 2023-03-14 | 四川蜀矿环锂科技有限公司 | Method for recycling and preparing ternary cathode material precursor by using waste ternary lithium battery |
| CN116093482A (en) * | 2023-03-10 | 2023-05-09 | 四川新能源汽车创新中心有限公司 | Recycling method and application of waste lithium ion battery anode material |
| CN116377249A (en) * | 2023-05-12 | 2023-07-04 | 中南大学 | High-pressure alkaline leaching recovery process and equipment for waste ternary cathode material |
| CN118579857A (en) * | 2024-08-05 | 2024-09-03 | 中国科学院大连化学物理研究所 | Method for regenerating retired power lithium battery recovery material into lithium-rich manganese-based positive electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090087801A (en) * | 2008-02-13 | 2009-08-18 | 닛코 킨조쿠 가부시키가이샤 | Method for recovering valuable metal from lithium battery waste containing co, ni, and mn |
| CN109088115A (en) * | 2018-07-24 | 2018-12-25 | 北京科技大学 | Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method |
| CN109193057A (en) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | A method of positive electrode material precursor is prepared using waste and old ternary lithium battery |
| CN109439904A (en) * | 2018-09-20 | 2019-03-08 | 广东佳纳能源科技有限公司 | A method of the leaching valuable metal from waste lithium cell positive electrode |
| CN109904548A (en) * | 2019-03-22 | 2019-06-18 | 郑州中科新兴产业技术研究院 | A method of synthesizing rich lithium material from waste and old lithium ion battery |
-
2021
- 2021-03-29 CN CN202110331503.7A patent/CN113200574A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090087801A (en) * | 2008-02-13 | 2009-08-18 | 닛코 킨조쿠 가부시키가이샤 | Method for recovering valuable metal from lithium battery waste containing co, ni, and mn |
| CN109088115A (en) * | 2018-07-24 | 2018-12-25 | 北京科技大学 | Waste lithium ion cell anode closed matereial cycle prepares tertiary cathode material method |
| CN109193057A (en) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | A method of positive electrode material precursor is prepared using waste and old ternary lithium battery |
| CN109439904A (en) * | 2018-09-20 | 2019-03-08 | 广东佳纳能源科技有限公司 | A method of the leaching valuable metal from waste lithium cell positive electrode |
| CN109904548A (en) * | 2019-03-22 | 2019-06-18 | 郑州中科新兴产业技术研究院 | A method of synthesizing rich lithium material from waste and old lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 左成等: ""Al2O3包覆Li1.2Mn0.54Ni0.13Co0.13O2富锂正极材料的电化学性能"", 《高等学校化学学报》 * |
| 杨凯等: ""富锂材料Li1.2[Mn0.54Ni0.13Co0.13]O2的Mo掺杂及电化学性能研究 "", 《电子元件与材料》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113904016A (en) * | 2021-10-11 | 2022-01-07 | 格林美股份有限公司 | Method for reconstructing single crystal electrode material from waste lithium ion battery |
| CN115449636A (en) * | 2022-09-05 | 2022-12-09 | 中南大学 | Recovery and regeneration process and equipment for lithium ion battery anode material |
| CN115449636B (en) * | 2022-09-05 | 2023-11-21 | 中南大学 | Recycling and regenerating process of lithium ion battery anode material |
| CN115465899B (en) * | 2022-09-14 | 2023-09-15 | 陕西红马科技有限公司 | Multi-crown multi-element spherical coating type precursor, preparation method thereof, chemical coating modified product and chemical coating modified method |
| CN115465899A (en) * | 2022-09-14 | 2022-12-13 | 陕西红马科技有限公司 | Multi-crown multi-element spherical coating precursor, preparation method thereof, chemical coating modified product and chemical coating modification method |
| CN115520909A (en) * | 2022-10-10 | 2022-12-27 | 山东遥米新能源科技有限公司 | Recovery method of ternary cathode material |
| CN115784324A (en) * | 2022-11-29 | 2023-03-14 | 四川蜀矿环锂科技有限公司 | Method for recycling and preparing ternary cathode material precursor by using waste ternary lithium battery |
| CN115784324B (en) * | 2022-11-29 | 2024-04-12 | 四川蜀矿环锂科技有限公司 | Method for recycling and preparing ternary positive electrode material precursor by using waste ternary lithium battery |
| CN116093482B (en) * | 2023-03-10 | 2023-07-28 | 四川新能源汽车创新中心有限公司 | Recycling method and application of waste lithium ion battery anode material |
| CN116093482A (en) * | 2023-03-10 | 2023-05-09 | 四川新能源汽车创新中心有限公司 | Recycling method and application of waste lithium ion battery anode material |
| CN116377249A (en) * | 2023-05-12 | 2023-07-04 | 中南大学 | High-pressure alkaline leaching recovery process and equipment for waste ternary cathode material |
| CN116377249B (en) * | 2023-05-12 | 2024-05-17 | 中南大学 | High-pressure alkaline leaching recovery process and equipment for waste ternary cathode material |
| CN118579857A (en) * | 2024-08-05 | 2024-09-03 | 中国科学院大连化学物理研究所 | Method for regenerating retired power lithium battery recovery material into lithium-rich manganese-based positive electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113200574A (en) | Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery | |
| CN111129632B (en) | Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery | |
| CN109088115B (en) | Method for preparing ternary cathode material by recycling waste lithium ion battery cathode material | |
| CN109193057B (en) | Method for preparing positive electrode material precursor by using waste ternary lithium battery | |
| CN103199320B (en) | Method for recycling nickel-cobalt-manganese ternary anode material | |
| CN109065996B (en) | Method for regenerating waste nickel cobalt lithium manganate ternary cathode material | |
| CN104466292B (en) | The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material | |
| CN113120971B (en) | Regeneration method and application of waste ternary cathode material | |
| Fei et al. | Selective lithium extraction of cathode materials from spent lithium-ion batteries via low-valent salt assisted roasting | |
| CN111129487A (en) | Hydrothermal lithium supplement-spray remodeling regeneration method for waste ternary cathode material | |
| WO2020019920A1 (en) | Method for preparing ternary cathode material from laterite nickel ore nitric acid leaching solution | |
| CN104485493B (en) | The reparative regeneration method of lithium cobaltate cathode active material in used Li ion cell | |
| CN112877548B (en) | Method for recovering valuable metals from waste lithium ion battery anode powder | |
| CN113314710A (en) | Method for recovering and regenerating anode material from waste lithium ion battery | |
| CN113548701A (en) | Preparation and application method of lithium ion sieve | |
| WO2022142904A1 (en) | Method for regenerating ternary precursor by using nickel-cobalt-manganese residue | |
| WO2024060547A1 (en) | Waste ternary positive electrode material reclaiming method | |
| CN104600389A (en) | Method for recycling metal from spent lithium ion battery of lithium manganate anode material | |
| CN108878836B (en) | Method for directly preparing lithium zincate modified ternary cathode material by using waste lithium battery cathode material | |
| CN104466293B (en) | The renovation process of lithium ion cell anode material lithium cobaltate waste material | |
| CN111403842B (en) | Recovery method of waste lithium battery anode material, spherical nickel oxide material and application | |
| CN110498434B (en) | Recovery method and application of lithium ion battery positive electrode active material | |
| CN111807388A (en) | Selective lithium leaching process for waste lithium ion battery | |
| CN104485494B (en) | The renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell | |
| CN104600284B (en) | Method for regenerating positive active material in spent lithium manganate lithium ion 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: 20210803 |
|
| RJ01 | Rejection of invention patent application after publication |