CN113764762A - Method for synthesizing high-performance lithium ion battery anode material by using waste lithium ion battery - Google Patents

Method for synthesizing high-performance lithium ion battery anode material by using waste lithium ion battery Download PDF

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CN113764762A
CN113764762A CN202110936558.0A CN202110936558A CN113764762A CN 113764762 A CN113764762 A CN 113764762A CN 202110936558 A CN202110936558 A CN 202110936558A CN 113764762 A CN113764762 A CN 113764762A
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ion battery
lithium ion
lithium
anode material
waste
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孙永明
王文宇
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
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    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention belongs to the field of lithium ion battery recovery and lithium ion battery anode material synthesis, and discloses a method for synthesizing a high-performance lithium ion battery anode material by using waste lithium ion batteries, which comprises the following steps: (1) processing to obtain a waste lithium ion battery anode material; (2) detecting the content of each metal element; (3) adding other raw materials to supplement elements according to the preset composition of the target lithium ion battery anode material matrix; (4) soaking the material with the regulated components in a surface treating agent, fully stirring, heating for evaporation, and calcining to obtain the lithium ion battery anode material product with the regulated components and the surface treated simultaneously. The invention realizes the recycling of the retired battery anode material based on component regulation and surface treatment by improving the overall process design of the method, simplifies the process flow, avoids secondary pollution, and the synthesized material has more excellent electrochemical performance than the original material before retirement.

Description

Method for synthesizing high-performance lithium ion battery anode material by using waste lithium ion battery
Technical Field
The invention belongs to the field of lithium ion battery recovery and lithium ion battery anode material synthesis, and particularly relates to a method for synthesizing a high-performance lithium ion battery anode material by using waste lithium ion batteries.
Background
The lithium ion battery has high energy density and power density, and is widely applied to the fields of consumer electronics products, large-scale energy storage, electric automobiles, 5G and the like. With the development of the above-mentioned fields, the demand for lithium ion batteries has also sharply increased year by year. The average service life of the lithium ion battery is 3-5 years, a large amount of retired lithium ion batteries can be generated in the future along with the development of various industries, and the recycling of battery materials has great environmental protection value and economic benefit.
The conventional method for recovering the key materials of the waste lithium ion batteries mainly comprises element recovery, and the anode materials of the retired batteries are converted into upstream raw materials in the field of lithium batteries by a hydrometallurgy and pyrometallurgy method to be reused for producing the anode materials. In addition, a partial regeneration method exists, the invention with the application number of 201310007896.1 is named as a method for directly recovering and repairing the lithium ion battery anode material, the anode is subjected to calcination repair or hydrothermal repair in an element supplement mode, the method only supplements elements of the material without further treatment, and the repaired material has limited performance and can only be recovered to the initial level. The invention with the application number of 201910142179.7 is named as 'a regenerated anode material and a preparation method thereof and a lithium ion battery containing the regenerated anode material', the method utilizes alkali liquor to treat anode materials, and then reacts with boric acid and additives for calcination, and the environment is polluted due to the large use of the alkali liquor; the element proportion is supplemented only according to the original proportion of the initial material, and the change of the element proportion cannot be further considered to obtain the cathode material with more excellent performance. The invention with the application number of 202011395335.X is named as a 'regeneration method of a lithium ion battery anode material, an anode material and a lithium ion battery', and the method directly crushes an anode piece to obtain an anode material and a current collector fragment mixture (the current collector is aluminum), and the mixture is calcined to obtain a precursor, and then lithium supplement calcination is carried out to obtain a regenerated anode material doped with aluminum; the method only realizes the doping modification of aluminum elements, does not realize the doping modification of other elements, only adds a lithium source, and cannot realize the regulation and control of other metal elements. The invention with the application number of 201510242512.3 is named as metal-doped nickel cobalt lithium manganate synthesized by lithium ion battery anode waste materials and a preparation method and application thereof, the method also repairs the performance of an anode material through element supplement and doping, the material interface is not regulated, and the interface has important influence on the electrochemical performance of the anode material.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention aims to provide a method for synthesizing a high-performance lithium ion battery cathode material from waste lithium ion batteries, wherein the recycling of the retired battery cathode material is realized based on component regulation and surface treatment by improving the overall process design of the method. Compared with the traditional wet recovery and dry recovery, the method for recycling the anode material of the retired battery takes the anode material of the retired lithium ion battery as a raw material, and can synthesize the anode material with excellent electrochemical performance by adding elements such as lithium, nickel, cobalt, manganese and the like and carrying out surface treatment on the elements, thereby solving the problems of complex recovery process, secondary pollution and the like compared with the prior art; based on the principle of component regulation and surface treatment, the invention adopts a simple heat treatment method to synthesize a brand-new high-performance anode material by taking the retired lithium ion battery anode material as a raw material, the anode material consists of an anode material matrix of the lithium ion battery with element composition meeting the preset target and a coating layer positioned on the surface of the matrix, the process flow is simplified, secondary pollution is avoided, and the synthesized material has more excellent electrochemical performance than the original material before retirement.
In order to achieve the above object, according to the present invention, there is provided a method for synthesizing a positive electrode material of a lithium ion battery from a waste positive electrode material of the lithium ion battery, comprising the steps of:
(1) obtaining a positive pole piece needing to be recycled and regenerated from a waste lithium ion battery to obtain a waste lithium ion battery positive pole material;
(2) detecting the content of each metal element contained in the anode material of the waste lithium ion battery obtained in the step (1) to obtain the molar ratio of each metal element;
(3) according to the preset composition of a target lithium ion battery anode material matrix and the mole ratio of each metal element measured in the step (2), adding other raw materials into the waste lithium ion battery anode material obtained in the step (1) to supplement elements, and then uniformly mixing to obtain a material with regulated and controlled components; in the material regulated and controlled by the components, the molar ratio of each metal element meets the preset nominal chemical dose ratio of each metal element in the matrix of the target lithium ion battery anode material; wherein the other raw materials are at least one of lithium source raw materials, cobalt source raw materials, nickel source raw materials, manganese source raw materials, aluminum source raw materials and doping raw materials;
(4) soaking the material obtained in the step (3) after the component regulation and control in a surface treating agent, fully stirring, and then heating and evaporating to obtain solid powder; then, calcining the solid powder to obtain a lithium ion battery anode material product which realizes component regulation and surface treatment at the same time; the product of the lithium ion battery anode material consists of a target lithium ion battery anode material matrix and a coating layer positioned on the surface of the matrix.
As a further preferable aspect of the present invention, in the step (4), the solute component contained in the surface treatment agent includes at least one of a lithium-supplementing component and a coating component; wherein the lithium supplement component is selected from: indene lithium, anthracene lithium, naphthalene lithium, phenanthrene lithium, pyrene lithium, 1-methylnaphthalene lithium, 2-methylnaphthalene lithium, benzophenone lithium, biphenyl lithium, lithium acetate, lithium carbonate, lithium hydroxide and lithium oxide; the coating component is nitrate, sulfate, chloride, acetate, phosphate, carbonate, fluoride, ethyl compound, ethoxy compound, ester compound or hydroxide of a target coating element, and the target coating element is selected from Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb, Fe, Ni, Co, Mn, Si and La;
preferably, when the solute component contained in the surface treatment agent contains a coating component, the surface treatment agent also contains a reaction component, wherein the reaction component is one or more of silicic acid, ammonium dihydrogen phosphate, ammonia water, citric acid, acetic acid, sodium hydroxide, sodium carbonate, lithium hydroxide, diammonium hydrogen phosphate and ammonium hydrogen carbonate;
the solvent component contained in the surface treating agent is one or more of an ester solvent, an alcohol solvent, a carboxylic acid solvent, an amide solvent, a sulfone solvent and water; more preferably one or more of tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, acetonitrile, N-dimethylformamide, dimethyl sulfoxide and water.
In a further preferred embodiment of the present invention, in the step (4), the total content of Li, Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb, Fe, Ni, Co, Mn, Si, and La elements in the coating layer is not more than 10% by mass of the target lithium ion battery positive electrode material matrix.
As a further preferred aspect of the present invention, in the step (2), the detection is specifically performed by atomic emission spectroscopy ICP, X-ray fluorescence spectroscopy XRF, or X-ray energy spectroscopy EDS.
As a further preferred aspect of the present invention, in the step (3), the lithium source raw material is one or more of lithium oxide, lithium carbonate, lithium hydroxide, lithium oxalate, and lithium acetate;
the cobalt source raw material is one or more of cobalt oxide, cobalt carbonate, cobalt hydroxide, cobalt oxalate and cobalt acetate;
the nickel source raw material is one or more of nickel oxide, nickel carbonate, nickel hydroxide and nickel oxalate;
the manganese source raw material is one or more of manganese oxide, manganese carbonate, manganese hydroxide and manganese oxalate;
the aluminum source raw material is one or more of aluminum oxide, aluminum hydroxide and aluminum oxalate;
the doping raw material is one or more of compounds containing Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb and La elements.
As a further preferred of the present invention, in the step (4), the temperature of the heating evaporation is 40-150 ℃, and the atmosphere condition is one or more of air, oxygen, argon, nitrogen or vacuum;
the calcining temperature is 300-1500 ℃, the treatment time is 1-12 h, and the atmosphere condition is one or more of air, oxygen, argon and nitrogen;
preferably, before the solid powder is calcined, a lithium-containing compound, specifically one or more of lithium carbonate, lithium hydroxide, lithium oxide, lithium acetate, and lithium oxalate, is further added to the solid.
As a further preferable aspect of the present invention, in the step (3), the material after the composition adjustment and control is further subjected to a heat treatment, the heat treatment temperature is 300 ℃ or more, the heat treatment time is 1h to 10h, and the atmosphere condition is one or more of nitrogen, argon, air, and oxygen.
As a further preferred aspect of the present invention, in the step (1), the waste lithium ion battery is at least one of a lithium cobaltate waste lithium ion battery, a lithium manganate waste lithium ion battery, a lithium nickelate waste lithium ion battery, a waste ternary lithium ion battery, and a waste quaternary lithium ion battery;
preferably, in the step (1), the waste lithium ion battery positive electrode material is further subjected to separation treatment, so that the conductive agent and the binder in the waste lithium ion battery positive electrode material are separated, and only the positive electrode active material in the waste lithium ion battery positive electrode material is retained.
As a further preferred aspect of the present invention, in the step (4), the atmosphere condition of the stirring is one or more of air, oxygen, argon, and nitrogen.
Compared with the prior art, the method for recycling the retired battery anode material takes the retired lithium ion battery anode material as a raw material, adds elements such as lithium, nickel, cobalt and manganese, and performs surface treatment on the elements, can synthesize the anode material with excellent electrochemical performance, has high capacity, and the electrochemical performance of the obtained recycled anode material is superior to that of a brand new anode material before retirement.
The surface treatment step in the present invention can form a coating layer (i.e., interface coating) on the surface of the recovered positive electrode material substrate, and functions to improve stability, improve the interface, and the like. In the method, the solute component of the surface treating agent used for forming the coating layer comprises at least one of a lithium supplement component and a coating component (the coating component can be additionally matched with a reaction component), wherein the lithium supplement component is a lithium compound and mainly used for compensating lithium lost by a positive electrode material; the coating component is a compound capable of doping a target element having a favorable effect in the coating layer, and can be used alone or in combination with a reaction component (the reaction component is a compound capable of reacting with the coating component in the coating process to help the favorable element form a uniform coating layer on the surface of the positive electrode material particle). In the solution phase environment, when the lithium supplement component and the coating component exist simultaneously, part of the lithium supplement component may react with part of the coating component to affect the coating performance, therefore, in the subsequent calcining process, some lithium sources may be added for reaction, that is, during the high-temperature calcining, a proper amount of lithium-containing compound (such as one or more of lithium carbonate, lithium hydroxide, lithium oxide, lithium acetate and lithium oxalate) is added, and the lithium-containing compound forms a lithium-containing compound with the surface coating layer during the calcining, so that the ionic and electronic conductivity of the surface coating layer can be further improved, and the surface treatment effect can be further improved.
The invention relates to a method for regenerating a battery, which comprises the steps of converting an anode material of a retired battery into an upstream material (such as lithium carbonate, nickel oxide, cobalt oxide, aluminum oxide, manganese oxide and other lithium, nickel, cobalt, manganese, aluminum and other element compounds or simple substances) for synthesizing the anode material through complex steps, and then synthesizing the anode material of the battery.
Specifically, the method for regenerating the retired lithium ion battery cathode material can achieve the following effective effects:
1. the invention utilizes the anode material of the retired battery as a raw material, and synthesizes a brand-new anode material with excellent electrochemical performance by component regulation and surface treatment. The traditional recovery method converts the anode material into the lithium ion battery upstream material by a complex physical and chemical means, and then the lithium ion battery anode material is produced again by using the upstream material, so that the process is complex.
2. The existing heat treatment recycling process restores the lithium content of the cathode material to the conventional level by compensating lithium element, for example, LiNi is used as the original material0.5Co0.2Mn0.3O2After long circulation, the material is converted into Li after the loss of lithium ions0.5Ni0.5Co0.2Mn0.3O2The prior method restores the element into LiNi through element regulation0.5Co0.2Mn0.3O2(ii) a The method takes the retired battery anode material as a raw material to synthesize the anode material, wherein the regulation and control of the components can be carried out according to the requirement that the original proportion of the original material is the same as that of the original material, and can also be carried out according to the requirement of a newly set proportion; when the component regulation is carried out according to the new set proportion requirement, the initial battery anode material is LiNi0.5Co0.2Mn0.3O2For example, after long cycling, the material undergoes ion loss and is converted to Li0.5Ni0.5Co0.2Mn0.3O2The element can be converted into LiNi through element regulation and control0.8Co0.1Mn0.1O2The electrochemical performance is superior to that of the original anode material before retirement, the process is simple, the economic benefit is high, and the performance can be further improved by matching with a coating layer formed on the surface.
3. The invention can realize the functions of isolating water and oxygen by the coating layer, stabilizing the crystal structure and the like by treating the surface of the material while realizing the performance improvement through component regulation and control, and can improve the stability and the electrochemical performance of the material.
The invention can combine the component regulation and the surface treatment, so that the material can exert more excellent performance. Still as the starting material LiNi0.5Co0.2Mn0.3O2(NCM523) for example, after a long cycle, a loss of lithium occurs, converting to Li0.5Ni0.5Co0.2Mn0.3O2Based on the method of the invention, firstly, the lithium element can be supplemented and the proportion of other elements can be regulated and controlled by the components to convert the lithium element into LiNi0.8Co0.1Mn0.1O2(NCM811)，NCMThe capacity of 811 is higher than that of NCM523, so that the performance of the material after component regulation is superior to that of the original material, but as the proportion of Ni in the material system increases, the instability of the material increases, and as Ni ions are easily separated from the material and dissolved out in water to cause structural damage, the higher the Ni content is, the more sensitive the material is to water and oxygen in the air, and the more easily damaged the crystal structure, so that the invention combines surface treatment while performing component regulation, coats a suitable element compound on the surface, can isolate water and oxygen and stabilize the surface structure, keeps the integrity of the internal crystal structure, and thus realizes the comprehensive improvement of the performance.
4. The invention uses the heat treatment method to recycle the anode material of the retired battery, does not need to use a large amount of acid liquor and alkali liquor, and can effectively reduce the emission of pollutants.
5. According to the method provided by the invention, a proper amount of elements are added according to the actual condition of the anode material of the retired battery, so that the electrochemical performance of the anode material can be effectively improved, and the generation of solid wastes can be reduced.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a diagram of a decommissioned battery anode material LiNi0.5Co0.2Mn0.3O2And LiNbO having excellent electrochemical properties synthesized from the charge-discharge curve of (A) and (B)3Coated LiNi0.5Co0.2Mn0.3O2Charge and discharge curves of the positive electrode material.
FIG. 3 is a diagram of a decommissioned battery anode material LiNi0.5Co0.2Mn0.3O2And LiNbO having excellent electrochemical properties synthesized from the charge-discharge curve of (A) and (B)3Coated LiNi0.8Co0.1Mn0.1O2Charge and discharge curves of the positive electrode material.
FIG. 4 shows the utilization of the LiNi as the anode material of a retired battery0.5Co0.2Mn0.3O2And Co synthesized from the charge-discharge curve of (A) and the Co having excellent electrochemical properties3O4Coated LiNi0.6Co0.121Mn0.272Al0.007O2Charge and discharge curves of the positive electrode material.
FIG. 5 shows the ex-service battery positive electrode material LiCoO2And LiNbO having excellent electrochemical properties synthesized from the charge-discharge curve of (A) and (B)3Coated LiNi0.5Co0.2Mn0.3O2Charge and discharge curves of the positive electrode material.
FIG. 6 shows the use of the LiNi anode material of a decommissioned battery0.5Co0.2Mn0.3O2Synthesized LiNbO with excellent electrochemical performance3Coated LiNi0.5Co0.2Mn0.3O2Cycle curve of the positive electrode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The method of the invention, as shown in figure 1, specifically comprises the following steps:
s1: the method comprises the following steps of firstly disassembling the waste lithium ion battery (namely, the retired lithium ion battery), and obtaining a positive pole piece needing to be recycled and regenerated from the waste lithium ion battery, for example, the retired power battery can be disassembled and shelled, the positive pole material on the positive pole piece is separated and screened, and the recycled positive pole material powder contains a positive active substance, a conductive agent and a binder; considering that the proportion of the conductive agent and the binder in the anode material powder is not high, generally about 2 wt% -5 wt%, the subsequent steps can be directly carried out without further treatment on the anode material powder; of course, according to actual needs, if a purer target product is expected to be recovered, the cathode material powder can be further separated, the conductive agent and the binder are separated from the cathode material powder, and only the cathode active substance is reserved;
s2: then, obtaining the element proportion of the anode material of the waste battery by means of element analysis (such as ICP, XRF and EDS);
s3: then, adding a lithium source, a cobalt source, a nickel source, a manganese source, an aluminum source, doping raw materials and the like into the waste battery anode material according to the element composition proportion of the target product, and uniformly mixing; the component regulation and control can be carried out according to the same requirement as the original proportion of the initial material (for example, the original electrode material is LiNi)0.5Co0.2Mn0.3O2Can be continuously maintained as LiNi during component regulation0.5Co0.2Mn0.3O2) Or according to the newly set proportion requirement;
s4: and (4) soaking the material collected in the step (S3) in a surface treating agent, fully stirring, heating and evaporating to obtain solid powder, and finally calcining at high temperature, thereby finally recovering and obtaining the cathode material which realizes component regulation and surface treatment at the same time. The calcination temperature can be 300-1500 ℃, the treatment time can be 1-12 h, the calcination atmosphere can be air or oxygen, and can also be a non-oxygen environment (such as argon and nitrogen), because the oxygen element of the anode material is generally less lost during the use of the lithium ion battery.
In step S4, the solute component contained in the surface treatment agent may be a lithium supplement component, a coating component, or a mixture of the two; the solvent component contained in the surface treating agent is one or more of ester solvent, alcohol solvent, carboxylic acid solvent, amide solvent, sulfone solvent and water. Wherein the lithium supplement component is selected from: indene lithium, anthracene lithium, naphthalene lithium, phenanthrene lithium, pyrene lithium, 1-methylnaphthalene lithium, 2-methylnaphthalene lithium, benzophenone lithium, biphenyl lithium, lithium acetate, lithium carbonate, lithium hydroxide and lithium oxide; the coating component is nitrate, sulfate, chloride, acetate, phosphate, carbonate, fluoride, ethyl compound, ethoxy compound, ester compound or hydroxide of target coating elements, and the target coating elements are selected from Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb, Fe, Ni, Co, Mn, Si and La; the surface coating layer of the invention can not only isolate water and oxygen, but also has better ion electron conductivity, and the compound of the elements can meet the requirement, thereby improving the performance of the battery anode material. The coating component can also be used in combination with a reaction component (in this case, the solute component contained in the surface treatment agent will include both the coating component and the reaction component), and the reaction component is one or more of silicic acid, ammonium dihydrogen phosphate, ammonia water, citric acid, acetic acid, sodium hydroxide, sodium carbonate, lithium hydroxide, diammonium hydrogen phosphate, and ammonium hydrogen carbonate.
In addition, after the step S3 is completed, the mixture may be further subjected to a heat treatment, for example, the heat treatment temperature may be 300 ℃ or higher, the heat treatment time may be 1h to 10h, and the atmosphere may be one or more of nitrogen, argon, air, and oxygen; the heat treatment can remove a small amount of residual conductive agent and binder in the cathode material of the retired battery.
The method is suitable for various waste lithium ion batteries, such as lithium ion batteries with capacity loss more than 20%, and the system is not limited; for example, the decommissioned battery cathode material may correspond to virgin lithium cobaltate (LiCoO)2) Lithium manganate (LiMnO)2) Lithium nickelate (LiNiO)2) Ternary materials (e.g., LiNi)xCoyMnzO2、LiNixCoyAlzO2In the chemical general formula, x, y and z are positive numbers and satisfy x + y + z ═ 1), quaternary material (such as LiNi)wCoxMnyAlzO2Wherein w, x, y and z are positive numbers in the chemical formula, and satisfy w + x + y + z ═ 1) after long-term charge-discharge cycle.
In step S3, the mixed material may be further subjected to a heat treatment at a temperature above 300 ℃ for 1h to 10h in one or more of nitrogen, argon, air and oxygen, which can remove a small amount of the conductive agent and the binder remaining in the material of the out-of-service battery positive electrode and can diffuse the elements added in step (3) in the bulk phase to make the mixing more uniform.
In step S3, the composition and ratio of the target chemical elements of the target product can be preset, for example:
if the lithium ion battery anode material before retirement does not contain aluminum, a lithium source, a nickel source, a cobalt source, a manganese source and doping elements can be added, and the proportion of the addition amount to the content of the elements in the original material is required to meet the requirement that Li: Co: Ni: Mn: X is 1: X: y: z (1-X-y-z) (capital X represents doping elements, the specific doping element types can be preset, and the specific values of X, y, z and 1-X-y-z can also be preset);
if the lithium ion battery anode material before retirement contains aluminum, a lithium source, a nickel source, a cobalt source, an aluminum source and doping elements can be added, and the proportion of the addition amount to the content of the elements in the original material is required to meet the requirement that Li: Co: Ni: Al: X is 1: X: y: z (1-X-y-z) (capital X represents the doping elements, the specific doping element types can be preset, and the specific values of X, y, z and 1-X-y-z can also be preset).
In addition, whether a certain element is a doped element or not is judged according to a preset target lithium ion battery anode material matrix; taking Al as an example, Al in NCM can be used as a doping element, and Al in NCA can be used as a matrix element.
The following are specific examples:
example one
Waste ternary LiNi0.5Co0.2Mn0.3O2Discharging the battery until the voltage is 2.5V, disassembling the battery to obtain components of a positive electrode piece, a negative electrode piece, a diaphragm and the like of the battery, separating positive active substance powder to obtain positive material powder 100g, detecting the element ratio of the positive material to Li, Ni, Co and Mn to be 0.5:0.5:0.2:0.3 through atomic emission spectroscopy (ICP), adding lithium carbonate to the positive material powder to enable the element ratio of Li, Ni, Co and Mn to be 1:0.5:0.2:0.3, performing ball milling and uniform mixing, placing the positive material powder in an oxygen atmosphere, and treating the positive material powder for 12 hours at 1100 ℃ to obtain LiNi0.5Co0.2Mn0.3O2Positive electrode material, LiNi will be obtained subsequently0.5Co0.2Mn0.3O2Adding niobium ethoxide (coating component) into the ethanol, wherein the mass of the Nb is LiNi0.5Co0.2Mn0.3O23 percent of the total amount of the active carbon, stirring overnight, drying the liquid in a vacuum oven at 60 ℃, calcining for 5 hours at 700 ℃ in an oxygen atmosphere to obtain the LiNbO3Surface breadCoated LiNi0.5Co0.2Mn0.3O2(LiNbO3The surface coating layer is formed by heating and calcining niobium ethoxide on the surface to form niobium oxide, and the niobium oxide can spontaneously react with a trace amount of lithium in the matrix to form lithium niobate).
Example two
Waste ternary LiNi0.5Co0.2Mn0.3O2Discharging the battery to a voltage of 2.5V, disassembling the battery to obtain components of a positive electrode piece, a negative electrode piece, a diaphragm and the like of the battery, separating positive active material powder to obtain positive material powder 100g, detecting the element ratio of the positive material to Li, Ni, Co and Mn to be 0.5:0.5:0.2:0.3 through atomic emission spectroscopy (ICP), adding lithium carbonate, nickel oxide and cobaltous oxide to the positive material powder to ensure that the element ratio of the Li, Ni, Co and Mn to be 1:0.6:0.2:0.2, performing ball milling and mixing uniformly, adding the uniformly mixed powder to an absolute ethyl alcohol solution of tetrabutyl titanate (naturally, the tetrabutyl titanate can be replaced by an ester compound of a target coating element Ti such as isopropyl titanate) and then slowly dropwise adding an ethyl alcohol/water mixture to the mixture, wherein the mass of the Ti is the target product LiNi0.6Co0.2Mn0.2O23 percent of the mass, stirring for 3h after the reaction is finished, drying in a vacuum oven at 80 ℃, mixing the dried product with lithium hydroxide (the molar ratio of Ti in the dried product to Li in the lithium hydroxide is 0.8-1.2), and calcining at 600 ℃ for 12h in an oxygen atmosphere to obtain the lithium hydroxide4Ti5O12Surface-coated LiNi0.6Co0.2Mn0.2O2。
EXAMPLE III
Waste ternary LiNi0.5Co0.2Mn0.3O2Discharging the battery until the voltage is 2.5V, disassembling the battery to obtain components of a positive electrode plate, a negative electrode plate, a diaphragm and the like of the battery, separating positive active substance powder to obtain positive material powder 100g, detecting the element ratio of the positive material to Li, Ni, Co and Mn to be 0.5:0.5:0.2:0.3 by atomic emission spectroscopy (ICP), adding lithium carbonate, nickel oxide and cobaltous oxide into the positive material powder to ensure that the element ratio of the Li, Ni, Co and Mn to be 1:0.8:0.1:0.1, uniformly mixing the materials by ball milling, and 7 percent in air atmosphereHeat treating at 00 deg.c for 3 hr, adding the product and niobium ethoxide into ethanol, and adding Nb in the mass of LiNi0.8Co0.1Mn0.1O23 percent of the total amount of the active carbon, stirring overnight, drying the liquid in a vacuum oven at 60 ℃, calcining for 5 hours at 700 ℃ in an oxygen atmosphere to obtain the LiNbO3Surface-coated LiNi0.8Co0.1Mn0.1O2。
Example four
Waste ternary LiNi0.5Co0.2Mn0.3O2Discharging the battery until the voltage of the battery is 2.5V, disassembling the battery to obtain components of a positive electrode plate, a negative electrode plate, a diaphragm and the like of the battery, separating positive active substance powder to obtain positive material powder 100g, detecting the element proportion of the positive material to Li, Ni, Co and Mn to be 0.5, 0.2 and 0.3 through atomic emission spectroscopy (ICP), and adding lithium carbonate, nickel oxide, cobaltous oxide and aluminum oxide into the positive material powder to ensure that the proportion of Li, Ni, Co, Mn: al 1:0.6:0.121:0.272:0.007, ball milling and mixing evenly, heat treating for 3 hours at 700 ℃ in air atmosphere, dispersing the product into deionized water, adding ammonium bicarbonate, stirring at normal temperature, slowly dropping Co (NO) into the mixture3)2·6H2O aqueous solution is added into the solution, and the mass of Co is LiNi0.6Co0.121Mn0.272Al0.007O23 percent of the total weight of the raw materials, stirring at normal temperature, washing for 3 times by using a centrifugal machine, drying in a vacuum oven at 80 ℃ overnight, and calcining for 4 hours at 600 ℃ in an oxygen atmosphere to obtain the product of Co3O4Surface-coated LiNi0.6Co0.121Mn0.272Al0.007O2。
EXAMPLE five
Waste LiCoO2Discharging the battery until the voltage is 2.5V, disassembling the battery to obtain components of a positive electrode plate, a negative electrode plate, a diaphragm and the like of the battery, separating positive active material powder to obtain positive material powder 100g, detecting the element ratio of the positive material to Li to Co to be 0.5:1 through atomic emission spectroscopy (ICP), adding lithium carbonate, nickel oxide and manganese dioxide to ensure that Li to Ni to Co to Mn to be 1:0.5:0.2:0.3, uniformly mixing by ball milling, carrying out heat treatment at 700 ℃ for 3 hours in an air atmosphere, and obtaining LiNi0.5Co0.2Mn0.3O2Adding niobium ethoxide into ethanol, wherein the mass of Nb is LiNi0.5Co0.2Mn0.3O23 percent of the total amount of the active carbon, stirring overnight, drying the liquid in a vacuum oven at 60 ℃, calcining for 5 hours at 700 ℃ in an oxygen atmosphere to obtain the LiNbO3Surface-coated LiNi0.5Co0.2Mn0.3O2。
EXAMPLE six
Waste LiNi1/3Co1/3Mn1/3O2Discharging the battery until the voltage is 2.5V, disassembling the battery to obtain components of a positive electrode piece, a negative electrode piece, a diaphragm and the like of the battery, separating positive active material powder to obtain positive material powder 100g, detecting the element ratio of the positive material to Li, Ni, Co and Mn to be 0.5:1:1:1 by atomic emission spectroscopy (ICP), adding lithium carbonate, nickel oxide and manganese dioxide to the positive material powder to enable the element ratio of Li, Ni, Co and Mn to be 1:0.5:0.2:0.3, uniformly mixing by ball milling, carrying out heat treatment at 300 ℃ for 3 hours in an air atmosphere, and obtaining LiNi0.5Co0.2Mn0.3O2Adding silicic acid into water, wherein the mass of Si is LiNi0.5Co0.2Mn0.3O25 percent of the total amount of the lithium silicate, stirring the mixture overnight, drying the liquid in a vacuum oven at 60 ℃, adding lithium hydroxide (the molar ratio of lithium element in the lithium hydroxide added in the step to silicon element in a dried product is 2-2.2) in an oxygen atmosphere, and calcining the mixture for 12 hours at 300 ℃ to obtain LiNi coated with the surface of the lithium silicate0.5Co0.2Mn0.3O2The lithium silicate can realize the protection effect on the surface, improve the crystal face and improve the performance.
The performance of the positive electrode material of the waste battery and the product obtained by recycling treatment used in the above embodiment are respectively detected, and the results are shown in fig. 2 to 6, where:
FIG. 2 is a schematic representation of the utilization of ex-service battery LiNi0.5Co0.2Mn0.3O2Anode material and brand new ternary anode material LiNbO synthesized by taking same as raw material3Coated LiNi0.5Co0.2Mn0.3O2(i.e., product obtained in example one) Charge/discharge Curve, Ex-service Battery Positive electrodeThe capacity of the material is 120mAh g-1New synthetic LiNbO3Coated LiNi0.5Co0.2Mn0.3O2The capacity is 170mAh g-1The method is obviously improved.
FIG. 3 is a graph of the utilization of ex-service battery LiNi0.5Co0.2Mn0.3O2Anode material and brand new ternary anode material LiNbO synthesized by taking same as raw material3Coated LiNi0.8Co0.1Mn0.1O2(i.e., the product obtained in example three) shows a charge-discharge curve, and the capacity of the cathode material of the retired battery is 120mAh g-1New synthetic LiNbO3Coated LiNi0.8Co0.1Mn0.1O2The capacity is 210mAh g-1The method is obviously improved.
FIG. 4 is a graph of the utilization of ex-service battery LiNi0.5Co0.2Mn0.3O2Positive electrode material and brand new ternary positive electrode material Co synthesized by taking same as raw material3O4Coated LiNi0.6Co0.121Mn0.272Al0.007O2(i.e., the product obtained in example four) shows a charge-discharge curve, and the capacity of the cathode material of the retired battery is 120mAh g-1Newly synthesized Co3O4Coated LiNi0.6Co0.121Mn0.272Al0.007O2Capacity 175mAh g-1The method is obviously improved.
FIG. 5 is a LiCoO using retired batteries2Anode material and brand new ternary anode material LiNbO synthesized by taking same as raw material3Coated LiNi0.5Co0.2Mn0.3O2(i.e., the product obtained in example five) shows a charge-discharge curve, and the capacity of the cathode material of the retired battery is 130mAh g-1New synthetic LiNbO3Coated LiNi0.5Co0.2Mn0.3O2The capacity is 168mAh g-1The method is obviously improved.
FIG. 6 is a graph of the utilization of ex-service battery LiNi0.5Co0.2Mn0.3O2Brand new ternary cathode material LiNbO synthesized by taking cathode material as raw material3Coated LiNi0.5Co0.2Mn0.3O2The cycle profile (i.e., the product obtained in example one) was stable for more than 100 cycles.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. A method for synthesizing a lithium ion battery anode material by using a waste lithium ion battery anode material is characterized by comprising the following steps:
(1) obtaining a positive pole piece needing to be recycled and regenerated from a waste lithium ion battery to obtain a waste lithium ion battery positive pole material;
(2) detecting the content of each metal element contained in the anode material of the waste lithium ion battery obtained in the step (1) to obtain the molar ratio of each metal element;
(3) according to the preset composition of a target lithium ion battery anode material matrix and the mole ratio of each metal element measured in the step (2), adding other raw materials into the waste lithium ion battery anode material obtained in the step (1) to supplement elements, and then uniformly mixing to obtain a material with regulated and controlled components; in the material regulated and controlled by the components, the molar ratio of each metal element meets the preset nominal chemical dose ratio of each metal element in the matrix of the target lithium ion battery anode material; wherein the other raw materials are at least one of lithium source raw materials, cobalt source raw materials, nickel source raw materials, manganese source raw materials, aluminum source raw materials and doping raw materials;
(4) soaking the material obtained in the step (3) after the component regulation and control in a surface treating agent, fully stirring, and then heating and evaporating to obtain solid powder; then, calcining the solid powder to obtain a lithium ion battery anode material product which realizes component regulation and surface treatment at the same time; the product of the lithium ion battery anode material consists of a target lithium ion battery anode material matrix and a coating layer positioned on the surface of the matrix.
2. The method for synthesizing the lithium ion battery cathode material by using the waste lithium ion battery cathode material as claimed in claim 1, wherein in the step (4), the solute component contained in the surface treatment agent comprises at least one of a lithium supplement component and a coating component; wherein the lithium supplement component is selected from: indene lithium, anthracene lithium, naphthalene lithium, phenanthrene lithium, pyrene lithium, 1-methylnaphthalene lithium, 2-methylnaphthalene lithium, benzophenone lithium, biphenyl lithium, lithium acetate, lithium carbonate, lithium hydroxide and lithium oxide; the coating component is nitrate, sulfate, chloride, acetate, phosphate, carbonate, fluoride, ethyl compound, ethoxy compound, ester compound or hydroxide of a target coating element, and the target coating element is selected from Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb, Fe, Ni, Co, Mn, Si and La;
preferably, when the solute component contained in the surface treatment agent contains a coating component, the surface treatment agent also contains a reaction component, wherein the reaction component is one or more of silicic acid, ammonium dihydrogen phosphate, ammonia water, citric acid, acetic acid, sodium hydroxide, sodium carbonate, lithium hydroxide, diammonium hydrogen phosphate and ammonium hydrogen carbonate;
the solvent component contained in the surface treating agent is one or more of an ester solvent, an alcohol solvent, a carboxylic acid solvent, an amide solvent, a sulfone solvent and water; more preferably one or more of tetrahydrofuran, diethyl ether, ethylene glycol dimethyl ether, acetonitrile, N-dimethylformamide, dimethyl sulfoxide and water.
3. The method for synthesizing the anode material of the lithium ion battery by using the anode material of the waste lithium ion battery as claimed in claim 2, wherein in the step (4), the total content of Li, Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb, Fe, Ni, Co, Mn, Si, La elements in the coating layer is not more than 10% of the mass of the target matrix of the anode material of the lithium ion battery.
4. The method for synthesizing the lithium ion battery cathode material by using the waste lithium ion battery cathode material according to claim 1, wherein in the step (2), the detection is specifically performed by using atomic emission spectroscopy (ICP), X-ray fluorescence spectroscopy (XRF), or X-ray energy spectroscopy (EDS).
5. The method for synthesizing the positive electrode material of the lithium ion battery by using the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (3), the lithium source raw material is one or more of lithium oxide, lithium carbonate, lithium hydroxide, lithium oxalate and lithium acetate;
the cobalt source raw material is one or more of cobalt oxide, cobalt carbonate, cobalt hydroxide, cobalt oxalate and cobalt acetate;
the nickel source raw material is one or more of nickel oxide, nickel carbonate, nickel hydroxide and nickel oxalate;
the manganese source raw material is one or more of manganese oxide, manganese carbonate, manganese hydroxide and manganese oxalate;
the aluminum source raw material is one or more of aluminum oxide, aluminum hydroxide and aluminum oxalate;
the doping raw material is one or more of compounds containing Mg, Al, Ti, Zr, F, Cr, Nd, Nb, Cd, B, Ta, Zn, Y, Tb, Pr, Nb and La elements.
6. The method for synthesizing the lithium ion battery cathode material by using the waste lithium ion battery cathode material according to claim 1, wherein in the step (4), the temperature of the heating evaporation is 40-150 ℃, and the atmosphere condition is one or more of air, oxygen, argon and nitrogen or vacuum;
the calcining temperature is 300-1500 ℃, the treatment time is 1-12 h, and the atmosphere condition is one or more of air, oxygen, argon and nitrogen;
preferably, before the solid powder is calcined, a lithium-containing compound, specifically one or more of lithium carbonate, lithium hydroxide, lithium oxide, lithium acetate, and lithium oxalate, is further added to the solid.
7. The method for synthesizing the lithium ion battery anode material by using the waste lithium ion battery anode material according to claim 1, wherein in the step (3), the material subjected to the component regulation and control is further subjected to heat treatment, the heat treatment temperature is more than 300 ℃, the heat treatment time is 1h-10h, and the atmosphere condition is one or more of nitrogen, argon, air and oxygen.
8. The method for synthesizing the positive electrode material of the lithium ion battery by using the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (1), the waste lithium ion battery is at least one of a lithium cobaltate waste lithium ion battery, a lithium manganate waste lithium ion battery, a lithium nickelate waste lithium ion battery, a waste ternary lithium ion battery and a waste quaternary lithium ion battery;
preferably, in the step (1), the waste lithium ion battery positive electrode material is further subjected to separation treatment, so that the conductive agent and the binder in the waste lithium ion battery positive electrode material are separated, and only the positive electrode active material in the waste lithium ion battery positive electrode material is retained.
9. The method for synthesizing the lithium ion battery cathode material by using the waste lithium ion battery cathode material as claimed in claim 1, wherein in the step (4), the stirring is performed under one or more of air, oxygen, argon and nitrogen.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477286A (en) * 2021-12-28 2022-05-13 苏州拉瓦锂能源科技有限公司 Preparation method of lithium molybdate
CN114597532A (en) * 2022-03-15 2022-06-07 清华大学深圳国际研究生院 Method for directly regenerating failed lithium cobaltate positive electrode into high-voltage lithium cobaltate positive electrode and product
CN116315216A (en) * 2023-02-09 2023-06-23 湖南金凯循环科技有限公司 Regeneration method of waste ternary material
CN117594901A (en) * 2024-01-18 2024-02-23 西北工业大学 Dual modification method for regenerating waste nickel-rich cathode into high-magnification nickel-rich cathode

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2730336A1 (en) * 2000-09-13 2002-03-21 Bathium Canada Inc. A method for recycling spent lithium metal polymer rechargeable batteries and related materials
CN103762352A (en) * 2014-01-16 2014-04-30 东莞新能源科技有限公司 Modified lithium nickel-cobalt-manganese ternary positive electrode material and preparation method thereof
CN110010990A (en) * 2019-03-27 2019-07-12 欣旺达电子股份有限公司 There is the method for the nickel-cobalt-manganese ternary material of alumina-coated layer using retired lithium ion battery as raw material preparation
CN112054261A (en) * 2020-07-28 2020-12-08 昆明理工大学 Method for recovering waste lithium battery positive electrode through mechanical activation assisted spray pyrolysis
CN112194201A (en) * 2020-05-08 2021-01-08 江苏载驰科技股份有限公司 Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary cathode materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2730336A1 (en) * 2000-09-13 2002-03-21 Bathium Canada Inc. A method for recycling spent lithium metal polymer rechargeable batteries and related materials
CN103762352A (en) * 2014-01-16 2014-04-30 东莞新能源科技有限公司 Modified lithium nickel-cobalt-manganese ternary positive electrode material and preparation method thereof
CN110010990A (en) * 2019-03-27 2019-07-12 欣旺达电子股份有限公司 There is the method for the nickel-cobalt-manganese ternary material of alumina-coated layer using retired lithium ion battery as raw material preparation
CN112194201A (en) * 2020-05-08 2021-01-08 江苏载驰科技股份有限公司 Method for recycling valuable metals of waste lithium ion batteries and regenerating ternary cathode materials
CN112054261A (en) * 2020-07-28 2020-12-08 昆明理工大学 Method for recovering waste lithium battery positive electrode through mechanical activation assisted spray pyrolysis

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114477286A (en) * 2021-12-28 2022-05-13 苏州拉瓦锂能源科技有限公司 Preparation method of lithium molybdate
CN114597532A (en) * 2022-03-15 2022-06-07 清华大学深圳国际研究生院 Method for directly regenerating failed lithium cobaltate positive electrode into high-voltage lithium cobaltate positive electrode and product
CN116315216A (en) * 2023-02-09 2023-06-23 湖南金凯循环科技有限公司 Regeneration method of waste ternary material
CN116315216B (en) * 2023-02-09 2024-02-13 湖南金凯循环科技股份有限公司 Regeneration method of waste ternary material
CN117594901A (en) * 2024-01-18 2024-02-23 西北工业大学 Dual modification method for regenerating waste nickel-rich cathode into high-magnification nickel-rich cathode

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