CN116425213A - Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary positive electrode materials - Google Patents

Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary positive electrode materials Download PDF

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CN116425213A
CN116425213A CN202310293006.1A CN202310293006A CN116425213A CN 116425213 A CN116425213 A CN 116425213A CN 202310293006 A CN202310293006 A CN 202310293006A CN 116425213 A CN116425213 A CN 116425213A
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ternary
nickel
cobalt
positive electrode
manganese
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张娟
赵明才
汪炜
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Jiangsu Zaichi Technology Co ltd
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    • 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
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Abstract

The invention provides a method for recycling valuable metals of waste lithium ion batteries and regenerating ternary cathode materials, which comprises the following steps: discharging, disassembling and removing impurities from the waste lithium ion battery to obtain a positive plate, and removing the conductive agent and the binder in the positive plate at high temperature to obtain a waste ternary positive material; the first regeneration route can leach valuable metal ions through organic acid or eutectic solvent added with a reducing agent, crosslink the metal ions by adopting sodium alginate solution to form gel with an egg-box structure with a three-dimensional network structure, and obtain the regenerated ternary positive electrode material after calcination, and the second regeneration route is beneficial to lithium ion entering the inside of particles through ball milling nanocrystallization to repair lithium, repair uneven surfaces of the gel and obtain the regenerated ternary positive electrode material after calcination. The two regeneration routes are simple and easy to operate, the steps of separating and purifying valuable metal ions are avoided, the method is novel, the cost is low, industrialization is easy to realize, and the prepared material has excellent electrochemical performance.

Description

Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary positive electrode materials
Technical Field
The invention relates to a method for recycling valuable metals of waste lithium ion batteries and regenerating ternary cathode materials, and belongs to the technical field of recycling and regenerating waste lithium ion batteries.
Background
In lithium ion batteries, particularly in vehicular power battery cost structures, the material cost is nearly 75%. And in the material cost, the positive electrode material accounts for 41 percent. The market scale market of the NCM ternary cathode material in China is rapidly increased, the market scale of the NCM ternary cathode material in China in 2018 reaches 230 hundred million yuan, and the market scale is increased by 33.72% in the same ratio. The market-scale market of the NCM ternary cathode material in China shows rapid growth, and is mainly beneficial to the rapid development of application markets of domestic vehicle power batteries, 3C batteries, electric tools, electric bicycles and the like, so that the continuous growth of the market demand of the NCM ternary cathode material is driven. The market size of the NCM ternary positive electrode material in 2022 is expected to break through 600 billion yuan. However, the explosion-type growth of the waste ternary lithium ion battery is caused, so that the recovery of the ternary lithium ion battery electrode material becomes a new focus of the battery industry. When the waste lithium ion battery is recycled, different types of anode materials are difficult to classify at present, the waste anode obtained after disassembly and separation often contains various anode materials, leaching liquid contains valuable metals such as nickel, cobalt, manganese, lithium and the like, the nickel, cobalt and manganese account for 90% of the cost of the anode materials, the metals are difficult to mine, the resource reserves in China are less, the cobalt resource is 95% dependent on import, 70% lithium ore is imported, the valuable metals in the waste lithium ion battery are recycled green and high-efficiently, considerable economic benefit and social benefit are brought, and the shortage of the resources such as cobalt, lithium and the like in China can be effectively relieved.
At present, the recovery of waste lithium ion battery materials is mainly divided into two main methods of pyrometallurgy and hydrometallurgy. The pyrometallurgy is to directly extract metal or metal oxide in the electrode by adopting a high-temperature treatment method, the process is simple, but the purity of the recovered material is low, the high-temperature treatment time is long, the energy consumption is high, and organic matters such as electrolyte, adhesive and the like in the waste batteries can generate harmful gas due to high-temperature reaction, and the secondary waste gas treatment is carried out by installing supporting facilities. The hydrometallurgy is to disassemble the battery shell, crush and screen the battery shell to obtain electrode materials, leach valuable metals in the electrode materials in acid or biological solution, and then perform precipitation separation or extraction separation to obtain corresponding salts or oxides of the metals, wherein the process is complex, a large amount of chemical reagents are needed, the cost is high, and environmental pollution is easy to cause although different valuable metals can be effectively recovered.
Disclosure of Invention
The invention provides a method for recycling valuable metals of waste lithium ion batteries and regenerating ternary anode materials, which can be composed of two routes: one is: the recovery of valuable metals of the waste lithium ion battery is organically combined with the preparation of the ternary positive electrode material, and sodium alginate crosslinked metal ions directly enter the production link of the new electrode material, so that the recycling of the valuable metal materials is realized. And the second is: the method comprises the steps of carrying out nanocrystallization on the obtained waste nickel cobalt lithium manganate ternary positive electrode material in a mechanical grinding mode, then taking the nanocrystallized waste ternary positive electrode material as a core, assembling ternary positive electrode material precursors on the surface of the ternary positive electrode material by using a sol-gel method, and then sintering the ternary positive electrode material at a high temperature to obtain the repaired and regenerated ternary positive electrode material. The waste ternary positive electrode material is nanocrystallized by adopting mechanical grinding, so that lithium ions can easily enter the particle to supplement lithium, however, the mechanical grinding can cause the surface roughness of the particle to increase the specific surface area, so that the consumption of lithium ions is caused, and the ternary positive electrode material is assembled on the surface of the nanoparticle, so that the adverse effects can be eliminated.
The specific technical scheme is as follows:
a method for recycling waste lithium ion battery regenerated ternary cathode material comprises the following steps:
s11, pre-treating the waste lithium ion batteries, and removing the conductive agent and the binder in the positive plate at high temperature;
then respectively according to any one of the following two process routes:
a first route:
s12, adding the battery material obtained in the step S11 into the first extracting solution or the second extracting solution, and leaching transition metal ions; the first extracting solution is organic acid added with a reducing agent, and the second extracting solution is eutectic solvent;
s13, adding sodium alginate solution into the leaching solution obtained in the step S12, performing a crosslinking reaction with transition metal ions to obtain gel, and calcining the gel to obtain a regenerated ternary anode material;
second route:
s22, ball milling the positive electrode material obtained in the step S11;
s23, adding a soluble lithium source, a nickel source, a cobalt source and a manganese source into the solution containing the ball-milled nano particles obtained in the step S22, repairing and assembling a ternary positive electrode material precursor on the surface of the nano particles by a sol-gel method by taking the nano particles as cores;
and S24, calcining the material to obtain the positive electrode material.
In one embodiment, the transition metal ion refers to nickel ion, cobalt ion, or manganese ion.
In one embodiment, the spent lithium ion battery is one or more of lithium cobaltate, lithium manganate, lithium nickelate, or a nickel cobalt manganese ternary battery.
In one embodiment, in step S11, the pretreatment refers to one or more steps of discharging, disassembling, or removing impurities from the battery.
In one embodiment, in step S11, the high temperature condition means that the treatment temperature is 500-1000 ℃, the treatment time is 0.5-5h, and the treatment atmosphere is air or oxygen.
In one embodiment, in the first extracting solution, the added reducing agent is selected from one or more of sodium thiosulfate, hydrogen peroxide, glucose, anthraquinone, hydrazine hydrate, sodium borohydride and thiourea dioxide; the organic acid is selected from one or more of sulfamic acid, ascorbic acid, maleic acid, acetic acid, oxalic acid, gluconic acid and tartaric acid.
In one embodiment, the second extract comprises a eutectic solvent composed of a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is generally selected from one or more of choline chloride, methyltriphenylphosphoryl bromide, benzyltriphenylhydrogen bromide, choline bromide, and betaine; the hydrogen bond acceptor is one or more of urea, glycol, glycerol, amino acid, acetamide and lactic acid.
In one embodiment, in step S12, after the leaching solution is obtained, transition metal ions and/or lithium ions are added to the leaching solution according to a set ion concentration ratio; lithium was added to the leach solution: nickel: cobalt: the molar ratio of manganese is one of 3:1:1:1, 1:0.5:0.2:0.3, 1:0.6:0.2:0.2, 1:0.8:0.1:0.1.
In one embodiment, in step S12, in the step of supplementing the corresponding metal ions, wherein the lithium source is selected from one or more of lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide; the nickel source is selected from one or more of nickel carbonate, nickel nitrate, nickel acetate and nickel hydroxide; the cobalt source is selected from one or more of cobalt carbonate, cobalt nitrate, cobalt acetate and cobalt hydroxide; the manganese source is selected from one or more of manganese carbonate, manganese nitrate, cobalt acetate and manganese hydroxide.
In one embodiment, in the step S13, the concentration of the sodium alginate solution is 0.1-5%, the viscosity is 5000-100000cP at 25 ℃, the amount of the sodium alginate solution is 2.0-2.4 times of the total molar amount of nickel cobalt manganese metal ions, and the crosslinking time is controlled to be 0.5-6 h.
In one embodiment, in step S13, the calcination temperature is 500-1000 ℃, the calcination time is 1-20 hours, and the calcination atmosphere is air or oxygen.
In one embodiment, in the step S22, the ball milling process is to mix the positive electrode material, water and a dispersing agent, wherein the added dispersing agent accounts for 1-5% of the mass of the positive electrode material, and the solid content of the positive electrode material is 10-30%; the mass ratio of the grinding balls to the ternary cathode material added in the ball milling process is 2-5:1, the rotating speed in the ball milling process is 1500-2500r/min, and the grinding time is 2-40h.
In one embodiment, the ball milling process employs any one of a high-speed stirring mill, a ball mill, a tube mill, a cone mill, a rod mill, and a sand mill.
In one embodiment, the dispersant is selected from one or more combinations of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexyl phosphate, sodium dodecyl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, fatty acid polyglycol esters, cetyltrimethylammonium bromide, polyethylene glycol p-isooctylphenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid, and polyetherimide.
In one embodiment, the ball milling process reduces the particle size of the positive electrode material to 50-300nm.
In one embodiment, in step S23, a soluble lithium source, a nickel source, a cobalt source, and a manganese source, wherein the lithium source is selected from one or more of lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide; the nickel source is selected from one or more of nickel carbonate, nickel nitrate, nickel acetate and nickel hydroxide; the cobalt source is selected from one or more of cobalt carbonate, cobalt nitrate, cobalt acetate and cobalt hydroxide; the manganese source is selected from one or more of manganese carbonate, manganese nitrate, cobalt acetate and manganese hydroxide.
In one embodiment, in step S23, the ratio of the molar amount of lithium ions to the total molar amount of nickel cobalt manganese ions is 1.05-1.1:1, wherein the molar ratio of nickel to cobalt to manganese ions is one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1.
In one embodiment, in step S23, the ratio of the molar amount of citric acid to the total molar amount of three metal ions of nickel cobalt manganese is 1-2:1, and the pH of the solution is adjusted to 7-8 with ammonia.
In one embodiment, in step S24, the high temperature sintering temperature is 700-1000 ℃, the sintering time is 5-20 hours, and the sintering atmosphere is air or oxygen.
Advantageous effects
The technical scheme provided by the invention has the following advantages:
(1) The method adopts the organic acid or the eutectic solvent to leach out the metal ions, is green and environment-friendly, and has higher leaching rate of the metal ions;
(2) And (3) crosslinking transition metal ions by adopting sodium alginate solution with certain viscosity to form gel with an egg-box structure with a three-dimensional network structure, and then directly calcining at high temperature to prepare the ternary cathode material. The preparation method is novel, the process is simple, the PH of the solution is not required to be regulated by adding an alkali solution to obtain the precipitate, and the sodium alginate is a food additive with low cost, safety and easy availability.
(3) The ternary positive electrode material regenerated by the gel method has the characteristics of good crystal form, excellent electrochemical cycle performance and the like, waste lithium ion batteries are turned into wealth, the recycling cost is low, the sustainable development of the environment is facilitated, and the circular economy is developed.
(4) According to the invention, the waste nickel cobalt lithium manganate ternary positive electrode material is subjected to nanocrystallization in a mechanical grinding mode, so that lithium ions can enter the particles to supplement lithium.
(5) The ternary positive electrode material precursor assembled on the surface of the nanometer waste ternary positive electrode material by using a sol-gel method can repair the uneven particle surface formed by mechanical grinding, and reduce the consumption of lithium ions in the charge and discharge process.
(6) The method is simple and easy to operate, does not need to leach and recycle metal ions, shortens the process flow, has low cost, is easy to realize industrialization, and the prepared material has excellent electrochemical performance.
Drawings
FIG. 1 is a regenerated LiNi prepared in example 3 0.6 Co 0.2 Mn 0.2 O 2 An electron microscope image of the ternary positive electrode material;
FIG. 2 is a regenerated LiNi prepared in example 5 and example 6 0.8 Co 0.1 Mn 0.1 O 2 XRD pattern of ternary positive electrode material.
Detailed Description
The two technical routes of the invention will be further described in connection with the specific embodiments, which are only some of the embodiments of the invention, but the scope of the invention is not limited to the description
Example 1
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 700 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. Weighing 50g of waste ternary cathode material, placing the waste ternary cathode material in a 500ml beaker, adding water to adjust the mass volume ratio of the cathode material to the water to be 1:5, then adding acetic acid with the molar concentration of 2mol/L and reducing agent sodium thiosulfate with the molar concentration of 1mol/L, reacting the mixed solution for 4 hours under the magnetic stirring condition at 80 ℃, and filtering to obtain filtrate rich in valuable metal ions. The content of lithium ions and transition metal ions (nickel ions, cobalt ions and manganese ions) in the filtrate is measured by ICP-OES, and the molar ratio of lithium elements, nickel elements, manganese elements and cobalt elements is 1:0.5:0.2:0.3 according to the product requirement ratio, so that the chemical formula of the obtained ternary material is LiNi 0.5 Co 0.2 Mn 0.3 O 2 And calculating the amount of the lithium salt or the transition metal salt to be added, and magnetically stirring for 4 hours to obtain a nickel cobalt manganese lithium precursor solution. Preparing sodium alginate solution with mass fraction of 0.5%, stirring to obtain uniform transparent solution, and weighing seaweedThe amount of the sodium acid solution is 2.0 times of the total molar amount of nickel cobalt manganese metal ions, then the nickel cobalt manganese lithium precursor solution is slowly added into the sodium alginate solution for crosslinking reaction for 2 hours to obtain gel with a three-dimensional net structure and an egg-box structure, and the gel is placed in a high-temperature tube furnace and calcined for 6 hours in an air atmosphere at 800 ℃ to obtain regenerated LiNi 0.5 Co 0.2 Mn 0.3 O 2 Ternary positive electrode material.
Example 2
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 600 ℃ for 4 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 30g of waste ternary anode material is weighed and placed in a 500ml beaker, water is added to adjust the mass volume ratio of the anode material to the water to be 1:3, then maleic acid with the molar concentration of 2mol/L and reducing agent hydrazine hydrate with the molar concentration of 1mol/L are added, the mixed solution reacts for 4 hours under the magnetic stirring condition at 80 ℃, and the filtrate rich in valuable metal ions is obtained through filtration. The content of lithium ions and transition metal ions (nickel ions, cobalt ions and manganese ions) in the filtrate is measured by ICP-OES, and the molar ratio of lithium elements, nickel elements, manganese elements and cobalt elements is 0.5:0.2:0.3:1 according to the product requirement ratio, so that the chemical formula of the obtained ternary material is LiNi 0.5 Co 0.2 Mn 0.3 O 2 And calculating the amount of the lithium salt or the transition metal salt to be added, and magnetically stirring for 4 hours to obtain a nickel cobalt manganese lithium precursor solution. Preparing sodium alginate solution with the mass fraction of 0.5%, stirring to obtain a uniform transparent solution, weighing sodium alginate solution with the amount which is 2.0 times of the total molar amount of nickel cobalt manganese metal ions, slowly adding nickel cobalt manganese lithium precursor solution into the sodium alginate solution for crosslinking reaction for 2 hours to obtain gel with an egg-box structure with a three-dimensional network structure, placing the gel in a high-temperature tube furnace, calcining for 6 hours in an air atmosphere at 800 ℃ to obtain regenerated LiNi 0.5 Co 0.2 Mn 0.3 O 2 Ternary positive electrode material.
Example 3
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtainAnd (3) the positive plate, namely placing the positive plate into a muffle furnace at 600 ℃ for treatment for 4 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. Weighing 50g of waste ternary anode material, placing the waste ternary anode material in a 500ml beaker, adding water to adjust the mass volume ratio of the anode material to the water to be 1:3, then adding maleic acid with the molar concentration of 2mol/L and reducing agent hydrazine hydrate with the molar concentration of 1mol/L, reacting the mixed solution for 4 hours under the magnetic stirring condition at 80 ℃, and filtering to obtain filtrate rich in valuable metal ions. The content of lithium ions and transition metal ions (nickel ions, cobalt ions and manganese ions) in the filtrate is measured by ICP-OES, and the molar ratio of lithium elements, nickel elements, manganese elements and cobalt elements is 1:0.6:0.2:0.2 according to the product requirement ratio, so that the chemical formula of the obtained ternary material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 And calculating the amount of the lithium salt or the transition metal salt to be added, and magnetically stirring for 4 hours to obtain a nickel cobalt manganese lithium precursor solution. Preparing sodium alginate solution with the mass fraction of 1%, stirring to obtain a uniform transparent solution, weighing sodium alginate solution with the amount which is 2.0 times of the total molar amount of nickel cobalt manganese metal ions, slowly adding nickel cobalt manganese lithium precursor solution into the sodium alginate solution for crosslinking reaction for 4 hours to obtain gel with an egg-box structure with a three-dimensional network structure, placing the gel in a high-temperature tube furnace, calcining for 5 hours in an air atmosphere at 900 ℃ to obtain regenerated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material.
Example 4
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 800 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. Choline chloride and urea are prepared into transparent uniform eutectic solvent under magnetic stirring at 80 ℃ according to the mol ratio of 1:2. And then weighing 20g of waste ternary cathode material, adding the waste ternary cathode material into the prepared eutectic solvent, leaching the mixture for 12 hours at the temperature of 150 ℃ under magnetic stirring, and filtering to obtain filtrate rich in valuable metal ions, wherein the mass volume ratio of the cathode material to the eutectic solvent is 1:3. Determination of lithium ion and transition metal ion (Nickel ion) in filtrate by ICP-OESCobalt ion, manganese ion) and the molar ratio of lithium element, nickel element, manganese element and cobalt element is 1:0.6:0.2:0.2 according to the product requirement, so that the chemical formula of the obtained ternary material is LiNi 0.6 Co 0.2 Mn 0.2 O 2 And calculating the amount of the lithium salt or the transition metal salt to be added, and magnetically stirring for 4 hours to obtain a nickel cobalt manganese lithium precursor solution. Preparing sodium alginate solution with the mass fraction of 1%, stirring to obtain a uniform transparent solution, weighing sodium alginate solution with the amount which is 2.0 times of the total molar amount of nickel cobalt manganese metal ions, slowly adding nickel cobalt manganese lithium precursor solution into the sodium alginate solution for crosslinking reaction for 3 hours to obtain gel with an egg-box structure with a three-dimensional network structure, placing the gel in a high-temperature tube furnace, calcining for 5 hours in an air atmosphere at 900 ℃ to obtain regenerated LiNi 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material.
Example 5
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 800 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. The choline chloride and the glycerol are prepared into transparent uniform eutectic solvent under magnetic stirring at 180 ℃ according to the mol ratio of 1:2. And then weighing 20g of waste ternary cathode material, adding the waste ternary cathode material into the prepared eutectic solvent, leaching the mixture for 8 hours at the temperature of 150 ℃ under magnetic stirring, and filtering to obtain filtrate rich in valuable metal ions, wherein the mass volume ratio of the cathode material to the eutectic solvent is 1:5. The content of lithium ions and transition metal ions (nickel ions, cobalt ions and manganese ions) in the filtrate is measured by ICP-OES, and the molar ratio of lithium elements, nickel elements, manganese elements and cobalt elements is 1:0.8:0.1:0.1 according to the product requirement ratio, so that the chemical formula of the obtained ternary material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 And calculating the amount of the lithium salt or the transition metal salt to be added, and magnetically stirring for 4 hours to obtain a nickel cobalt manganese lithium precursor solution. Preparing sodium alginate solution with mass fraction of 2%, stirring to obtain uniform transparent solution, weighing sodium alginate solution with amount of 2.0 times of total molar amount of nickel cobalt manganese metal ions, and thenSlowly adding the nickel-cobalt-manganese-lithium precursor solution into the sodium alginate solution for crosslinking reaction for 6 hours to obtain gel with an egg-box structure of a three-dimensional network structure, and calcining the gel in a high-temperature tube furnace at the air atmosphere of 1000 ℃ for 5 hours to obtain regenerated LiNi 0.8 Co 0.1 Mn 0.1 O 2 Ternary positive electrode material.
Example 6
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 800 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. Betaine and malonic acid are prepared into transparent uniform eutectic solvent under magnetic stirring at 180 ℃ according to the mol ratio of 1:5. And then weighing 20g of waste ternary cathode material, adding the waste ternary cathode material into the prepared eutectic solvent, leaching the mixture for 8 hours at the temperature of 150 ℃ under magnetic stirring, and filtering to obtain filtrate rich in valuable metal ions, wherein the mass volume ratio of the cathode material to the eutectic solvent is 1:5. The content of lithium ions and transition metal ions (nickel ions, cobalt ions and manganese ions) in the filtrate is measured by ICP-OES, and the molar ratio of lithium elements, nickel elements, manganese elements and cobalt elements is 1:0.8:0.1:0.1 according to the product requirement ratio, so that the chemical formula of the obtained ternary material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 And calculating the amount of the lithium salt or the transition metal salt to be added, and magnetically stirring for 4 hours to obtain a nickel cobalt manganese lithium precursor solution. Preparing sodium alginate solution with the mass fraction of 1.5%, stirring to obtain a uniform transparent solution, weighing sodium alginate solution with the amount which is 2.0 times of the total molar amount of nickel cobalt manganese metal ions, slowly adding nickel cobalt manganese lithium precursor solution into the sodium alginate solution for crosslinking reaction for 6 hours to obtain gel with an egg-box structure with a three-dimensional network structure, placing the gel in a high-temperature tube furnace, calcining for 5 hours in an air atmosphere at the temperature of 1000 ℃ to obtain regenerated LiNi 0.8 Co 0.1 Mn 0.1 O 2 Ternary positive electrode material.
Example 7
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 700 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 500g of ternary positive electrode material and 5g of dispersing agent sodium dodecyl sulfate are weighed and added into a sand mill, an aqueous solution is added to adjust the mass solid content of the ternary positive electrode material to be 10%, then 1Kg of grinding balls with the diameter of 1mm are added, the rotation speed of an instrument is adjusted to 2500r/min, the sand milling time is 8 hours, and the ternary positive electrode material slurry with the D50 of 100nm is obtained.
100g of nano ternary cathode material slurry is weighed and poured into a beaker, and the molar ratio of the slurry to the beaker is 6:2:2 nickel acetate, cobalt acetate, manganese acetate and lithium acetate with the molar weight being 1.1 times of the total molar weight of nickel cobalt manganese ions, adding citric acid solution with the molar weight being 1.2 times of the total molar weight of nickel cobalt manganese ions after complete dissolution, adjusting the PH of the solution to 7 by ammonia water until sol is formed, heating in water bath to form gel, placing the gel in a high-temperature tube furnace, sintering at high temperature for 6h in air atmosphere at 800 ℃ to obtain LiNi with nano waste ternary anode material as a core shell 0.6 Co 0.2 Mn 0.2 O 2 Regenerated ternary positive electrode material.
Example 8
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 600 ℃ for 4 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 500g of ternary positive electrode material and 5g of dispersing agent sodium dodecyl sulfate are weighed and added into a sand mill, an aqueous solution is added to adjust the mass solid content of the ternary positive electrode material to be 10%, then 1Kg of grinding balls with the diameter of 2mm are added, the rotation speed of an instrument is adjusted to be 2000r/min, and the sand milling time is 6h, so that ternary positive electrode material slurry with the D50 of 150nm is obtained.
100g of nano ternary cathode material slurry is weighed and poured into a beaker, and the molar ratio of the slurry to the beaker is 6:2:2, nickel acetate, cobalt acetate and manganese acetate and lithium acetate with a molar weight which is 1.1 times of the total molar weight of nickel cobalt manganese ions, adding citric acid solution with a molar weight which is 1.2 times of the total molar weight of nickel cobalt manganese ions after complete dissolution, adjusting the pH of the solution to 7 with ammonia water until a sol is formed, heating in a water bath to form gel, and placing the gelSintering at high temperature in a high-temperature tube furnace at 700 ℃ under air atmosphere for 6 hours to obtain the LiNi with the nano waste ternary anode material as the core shell 0.6 Co 0.2 Mn 0.2 O 2 Regenerated ternary positive electrode material.
Example 9
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 800 ℃ for 6 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 500g of ternary positive electrode material and 5g of dispersing agent Gul are weighed and added into a sand mill, aqueous solution is added to adjust the mass solid content of the ternary positive electrode material to be 10%, then 1Kg of grinding balls with the diameter of 5mm are added, the rotation speed of an instrument is adjusted to be 2200r/min, and the sand milling time is 6h, so that ternary positive electrode material slurry with the D50 of 200nm is obtained.
100g of nano ternary cathode material slurry is weighed and poured into a beaker, and the molar ratio of the slurry to the beaker is 5:2:3, nickel nitrate, cobalt nitrate, manganese nitrate and lithium nitrate with the molar weight being 1.1 times of the total molar weight of nickel cobalt manganese ions, adding citric acid solution with the molar weight being 1.2 times of the total molar weight of nickel cobalt manganese ions after complete dissolution, adjusting the PH of the solution to 7 by ammonia water until sol is formed, heating in water bath to form gel, placing the gel in a high-temperature tube furnace, sintering at high temperature for 6h in air atmosphere at 900 ℃ to obtain LiNi with nano waste ternary anode material as a core shell 0.5 Co 0.2 Mn 0.3 O 2 Regenerated ternary positive electrode material.
Example 10
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 800 ℃ for 8 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 500g of ternary positive electrode material and 10g of dispersing agent Gul glue are weighed and added into a sand mill, an aqueous solution is added to adjust the mass solid content of the ternary positive electrode material to be 15%, then 2Kg of grinding balls with the diameter of 5mm are added, the rotation speed of an instrument is adjusted to 2500r/min, the sand milling time is 6h, and the ternary positive electrode material slurry with the D50 of 120nm is obtained.
100g of nano ternary material is weighedPouring the positive electrode material slurry into a beaker, and adding the positive electrode material slurry into the beaker with magnetic stirring according to the molar ratio of 5:2:3, adding citric acid solution with the molar quantity being 1.2 times of the total molar quantity of nickel cobalt manganese ions and ammonia water to adjust the PH value of the solution to 7 until sol is formed, heating in water bath to form gel, placing the gel in a high-temperature tube furnace, sintering at high temperature for 8 hours in air atmosphere at 1000 ℃ to obtain LiNi with nano waste ternary anode material as a core shell 0.5 Co 0.2 Mn 0.3 O 2 Regenerated ternary positive electrode material.
Example 11
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 600 ℃ for 4 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 500g of ternary positive electrode material and 10g of dispersant cetyl trimethyl ammonium bromide are weighed and added into a sand mill, an aqueous solution is added to adjust the mass solid content of the ternary positive electrode material to be 10%, then 1Kg of grinding balls with the diameter of 5mm are added, the rotating speed of an instrument is adjusted to be 2200r/min, and the sand milling time is 6h, so that ternary positive electrode material slurry with the D50 of 200nm is obtained.
100g of nano ternary cathode material slurry is weighed and poured into a beaker, and the molar ratio of the slurry to the beaker is 8:1:1 nickel acetate, cobalt acetate, manganese acetate and lithium acetate with the molar weight being 1.1 times of the total molar weight of nickel cobalt manganese ions, adding citric acid solution with the molar weight being 1.2 times of the total molar weight of nickel cobalt manganese ions after complete dissolution, adjusting the PH of the solution to 7 by ammonia water until sol is formed, heating in water bath to form gel, placing the gel in a high-temperature tube furnace, sintering at high temperature for 6h in air atmosphere at 900 ℃ to obtain LiNi with nano waste ternary anode material as a core shell 0.8 Co 0.1 Mn 0.1 O 2 Regenerated ternary positive electrode material.
Comparative example 1
The difference from example 7 is that: and (3) carrying out grinding treatment on the waste nickel cobalt lithium manganate battery, and then, not carrying out surface sol-gel modification treatment.
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 700 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 500g of ternary positive electrode material and 5g of dispersing agent sodium dodecyl sulfate are weighed and added into a sand mill, aqueous solution is added to adjust the mass solid content of the ternary positive electrode material to be 10%, then 1Kg of grinding balls with the diameter of 1mm are added, the rotation speed of an instrument is adjusted to 2500r/min, the sand milling time is 8 hours, ternary positive electrode material slurry with the D50 of 100nm is obtained, and the ternary positive electrode material slurry is centrifuged and transferred into a vacuum drying oven to be dried for 2 hours at the temperature of 80 ℃ to obtain the nanometer waste ternary positive electrode material.
Comparative example 2
The difference from example 7 is that: and (3) directly assembling a ternary precursor on the surface of the ternary positive electrode material by adopting a sol-gel method without grinding the ternary positive electrode material obtained from the waste nickel cobalt lithium manganate battery.
Discharging, disassembling and removing impurities from the waste nickel cobalt lithium manganate ternary battery to obtain a positive plate, putting the positive plate into a muffle furnace at 700 ℃ for 2 hours, and removing the conductive agent and the binder in the positive plate to obtain the waste ternary positive material. 10g of waste ternary cathode material is weighed and poured into a beaker, an aqueous solution is added to adjust the mass solid content of the ternary cathode material to be 10%, and the molar ratio of the ternary cathode material to the aqueous solution is 6:2:2 nickel acetate, cobalt acetate, manganese acetate and lithium acetate with the molar weight being 1.1 times of the total molar weight of nickel cobalt manganese ions, adding citric acid solution with the molar weight being 1.2 times of the total molar weight of nickel cobalt manganese ions after complete dissolution, adjusting the PH of the solution to 7 by ammonia water until sol is formed, heating in water bath to form gel, placing the gel in a high-temperature tube furnace, sintering at high temperature under the air atmosphere of 800 ℃ for 6 hours to obtain LiNi with waste ternary anode material as a nuclear shell 0.5 Co 0.2 Mn 0.3 O 2 Regenerated ternary positive electrode material.
The positive electrode materials prepared in examples 1 to 11 and comparative examples 1 to 2 were subjected to cycle performance test
The prepared anode material, acetylene black and PVDF binder are mixed according to the weight ratio of 8:1:1 in NMP under magnetic forceThe resulting slurry was coated on an aluminum foil with a doctor blade, dried in an oven at 60 c, rolled and punched into a 13mm diameter small disc, and then dried in a vacuum oven at 120 c for 16 hours, and transferred to a glove box filled with an inert atmosphere. Then, taking a metal lithium sheet as a negative electrode, taking 1mol LiPF6/EC+DMC (volume ratio 1:1) as electrolyte, and adopting Celgard2400 as a diaphragm to assemble the button cell. The assembled button cell is subjected to constant-current charge and discharge test by using a blue cell test system, the charge and discharge voltage interval is 2.8-4.3V, and the cycle performance test current is 0.2C (1C is 150mA g) -1 ). After 50 cycles, the discharge capacity and the discharge capacity retention rate of the ternary cathode material prepared by the two technical routes are shown in tables 1 and 2:
Figure BDA0004142278530000101
TABLE 1
Figure BDA0004142278530000111
TABLE 2
As can be seen from table 1, the obtained ternary cathode material prepared by the regeneration route one has excellent cycle performance. It can be seen from table 2 that by the second regeneration route, the obtained waste nickel cobalt manganese ternary positive electrode material is subjected to nanocrystallization in a mechanical grinding manner, then the ternary positive electrode material precursor is assembled on the surface of the ternary positive electrode material by using a sol-gel method, and the ternary positive electrode material subjected to repairing regeneration is obtained by high-temperature sintering, so that the ternary positive electrode material has excellent electrochemical performance, the first coulomb efficiency and the cycle stability of the material can be improved, the cycle performance of the material can be improved by simply carrying out grinding treatment on the waste nickel cobalt lithium manganate battery without carrying out modification treatment by a surface sol-gel method, but the surface of particles caused by ball milling is uneven, and excessive lithium ions are consumed in the charging and discharging process, so that the first coulomb efficiency of the material is lower. And the obtained waste ternary positive electrode material is not subjected to grinding treatment, and the ternary precursor is directly assembled on the surface of the ternary positive electrode material by adopting a sol-gel method, so that the ternary positive electrode material precursor is assembled on the surface of the ternary positive electrode material due to large material particles, the formed particles have a too large size, lithium ions are not beneficial to embedding lithium ions into the ternary positive electrode material, the circulation stability of the material is also not beneficial, and the capacity retention rate is very low.

Claims (7)

1. The method for recycling the regenerated ternary cathode material of the waste lithium ion battery is characterized by comprising the following steps of:
s11, pretreating the waste lithium ion battery, and removing the conductive agent and the binder in the positive plate under the high-temperature condition;
s22, ball milling the positive electrode material obtained in the step S11;
s23, adding a soluble lithium source, a nickel source, a cobalt source and a manganese source into the solution containing the ball-milled nano particles obtained in the step S22, repairing and assembling a ternary positive electrode material precursor on the surface of the nano particles by a sol-gel method by taking the nano particles as cores;
and S24, calcining the material to obtain the positive electrode material.
2. The method for recycling waste lithium ion battery regenerated ternary cathode materials according to claim 1, wherein in one embodiment, the added reducing agent is selected from one or more of sodium thiosulfate, hydrogen peroxide, glucose, anthraquinone, hydrazine hydrate, sodium borohydride and thiourea dioxide; the organic acid is selected from one or more of sulfamic acid, ascorbic acid, maleic acid, acetic acid, oxalic acid, gluconic acid and tartaric acid;
in one embodiment, the second extract comprises a eutectic solvent composed of a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is generally selected from one or more of choline chloride, methyltriphenylphosphoryl bromide, benzyltriphenylhydrogen bromide, choline bromide, and betaine; the hydrogen bond acceptor is one or more of urea, glycol, glycerol, amino acid, acetamide and lactic acid.
3. The method for recycling waste lithium ion battery regenerated ternary cathode materials according to claim 1, wherein in one embodiment, in the step S22, the ball milling process is to mix the cathode materials, water and dispersing agent, wherein the added dispersing agent is 1-5% of the mass of the cathode materials, and the solid content of the cathode materials is 10-30%; the mass ratio of the grinding balls to the ternary battery material added in the ball milling process is 2-5:1, the rotating speed in the ball milling process is 1500-2500r/min, and the grinding time is 2-40h;
in one embodiment, the ball milling process employs any one of a high-speed stirring mill, a ball mill, a tube mill, a cone mill, a rod mill, and a sand mill.
4. The method for recycling waste lithium ion battery regenerated ternary cathode material according to claim 1, wherein in one embodiment, the ball milling process reduces the particle size of the cathode material to 50-300nm;
in one embodiment, in step S23, a soluble lithium source, a nickel source, a cobalt source, and a manganese source, wherein the lithium source is selected from one or more of lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide; the nickel source is selected from one or more of nickel carbonate, nickel nitrate, nickel acetate and nickel hydroxide; the cobalt source is selected from one or more of cobalt carbonate, cobalt nitrate, cobalt acetate and cobalt hydroxide; the manganese source is selected from one or more of manganese carbonate, manganese nitrate, cobalt acetate and manganese hydroxide.
5. The method for recycling waste lithium ion battery regenerated ternary cathode material according to claim 1, wherein in one embodiment, in step S23, the ratio of the molar amount of lithium ions to the total molar amount of nickel cobalt manganese ions is 1.05-1.1:1, wherein the molar ratio of nickel to cobalt to manganese ions is one of 1:1:1, 5:2:3, 6:2:2 or 8:1:1.
6. The method for recycling waste lithium ion battery regenerated ternary cathode material according to claim 1, wherein in step S23, the ratio of the mole amount of citric acid to the total mole number of three metal ions of nickel, cobalt and manganese is 1-2:1, and the PH of the solution is adjusted to 7-8 with ammonia water.
7. The method for recycling waste lithium ion battery regenerated ternary cathode materials according to claim 1, wherein in step S24, the high-temperature sintering temperature is 700-1000 ℃, the sintering time is 5-20h, and the sintering atmosphere is air or oxygen.
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