CN114759282A - Regeneration method for simply and accurately regulating target elements to repair waste lithium ion battery anode waste - Google Patents

Regeneration method for simply and accurately regulating target elements to repair waste lithium ion battery anode waste Download PDF

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CN114759282A
CN114759282A CN202210353371.2A CN202210353371A CN114759282A CN 114759282 A CN114759282 A CN 114759282A CN 202210353371 A CN202210353371 A CN 202210353371A CN 114759282 A CN114759282 A CN 114759282A
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lithium ion
ion battery
additive
waste
lithium
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李丽
林娇
陈人杰
张晓东
吴锋
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Beijing Institute of Technology BIT
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

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Abstract

The invention discloses a regeneration method for accurately regulating and controlling target elements to repair anode waste materials of waste lithium ion batteries, which comprises the following steps: placing the waste and old lithium ion battery anode waste, a lithium additive, a nickel additive, a cobalt additive, a manganese additive, an aluminum additive and an iron additive into an aqueous solution, carrying out ultrasonic mixing and then carrying out high-temperature solid-phase synthesis treatment, and realizing restoration and regeneration after the treatment. The lithium ion battery anode material obtained by the repairing and regenerating method has accurate element proportion and good structural stability, and the repairing method is simple and environment-friendly. The repaired and regenerated material is used as the anode material of the lithium ion battery, and the lithium ion battery is assembled, so that the good circulation stability is shown, and the capacity retention rate of the battery is high; the method has short flow, saves the recovery cost and is easy to realize industrial application.

Description

Regeneration method for simply and accurately regulating target elements to repair waste lithium ion battery anode waste
Technical Field
The invention relates to the field of chemical engineering of resource recycling, in particular to a regeneration method for simply and accurately regulating and controlling target elements to repair waste lithium ion battery anode waste materials.
Background
The lithium ion battery is taken as a rechargeable battery with high energy density and environmental protection (without heavy metals such as lead, mercury and the like), and shows great potential as a power source of an electric automobile and a power grid energy storage device. If the large-scale decommissioning and scrapping of the lithium ion battery are not properly treated, the problems of resource shortage and environmental pollution are caused. Therefore, reasonable disposal of the retired lithium ion battery can not only effectively reduce mining of mineral resources to support sustainable development of the lithium ion battery industry, but also effectively reduce environmental pollution and realize the 3R (reduction, reuse and recycling) target of green chemistry.
At present, the method for repairing the anode material of the waste lithium ion battery generally comprises the steps of firstly carrying out pretreatment such as disassembly on the waste lithium ion battery to obtain an anode plate containing active substances, separating an aluminum foil to obtain the anode material, adding lithium salt, and then repairing the electrochemical performance of the anode material by a solid-phase synthesis technology of high-temperature roasting or a hydrothermal synthesis method. The repair technology needs to strictly control the proportion of the added Li salt and the transition metal, and the material ratio of the repaired material is different from that of the original commercial material due to the fact that the proportion of the component elements is difficult to accurately determine, so that the electrochemical performance of the repaired material is poor, and the requirements of practical application cannot be met. In addition, the components in different failure positive electrode materials are complex, such as the phenomenon of manganese deficiency in lithium manganate and nickel cobalt lithium manganate. The prior art repair techniques involve little supplementation of the transition metals. Therefore, a new recovery strategy is urgently needed to be developed, and a regeneration method for simply and accurately regulating and controlling target elements to repair the anode materials of the waste lithium ion batteries is researched and developed.
Disclosure of Invention
In view of the above, the invention aims to provide a regeneration method for simply and accurately regulating and controlling a target element to repair waste lithium ion battery anode waste, and the anode material obtained by utilizing the regeneration method has accurate element proportion and good structural stability, and is simple in repair method and environment-friendly; the prepared material is used as a lithium ion battery anode material, and shows good charge-discharge cycle performance after the lithium ion battery is assembled, and the capacity retention rate of the battery is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a regeneration method for simply and accurately regulating and controlling target elements to repair waste lithium ion battery anode waste, which comprises the following steps:
placing the waste and old lithium ion battery anode waste, a lithium additive, a nickel additive, a cobalt additive, a manganese additive, an aluminum additive and an iron additive into an aqueous solution, uniformly mixing, and then carrying out high-temperature solid-phase synthesis treatment, thereby realizing restoration and regeneration after the treatment. The lithium ion battery anode material obtained by the repairing and regenerating method has accurate element proportion and good structural stability, and the repairing method is simple and environment-friendly.
The following technical solutions are preferred technical solutions of the present invention, but the technical objects and advantages of the present invention can be better achieved and achieved by the following technical solutions.
Preferably, the waste material of the positive electrode of the waste lithium ion battery is any one of or a combination of at least two of lithium cobaltate waste, lithium manganate waste, lithium iron phosphate waste, lithium nickel cobalt manganese ternary waste and lithium nickel cobalt aluminum ternary waste.
Preferably, the lithium additive is any one of lithium carbonate, lithium acetate, lithium oxalate, lithium hydroxide, lithium phosphate and lithium fluoride or a combination of at least two of the above;
preferably, the nickel additive is any one of nickel oxide, nickel sulfate, nickel carbonate, nickel hydroxide, nickel oxalate and nickel nitrate or a combination of at least two of the nickel oxide, the nickel sulfate, the nickel carbonate, the nickel hydroxide, the nickel oxalate and the nickel nitrate.
Preferably, the cobalt additive is any one of cobalt sulfate, cobalt carbonate, cobalt hydroxide, cobalt oxalate and cobalt nitrate or a combination of at least two of them.
Preferably, the manganese additive is any one of manganese sulfate, manganese acetate, manganese carbonate, manganese hydroxide, manganese oxalate and manganese nitrate or a combination of at least two of the manganese sulfate, the manganese acetate, the manganese carbonate, the manganese hydroxide, the manganese oxalate and the manganese nitrate.
Preferably, the aluminum additive is any one of aluminum sulfate, aluminum carbonate, aluminum hydroxide, aluminum oxalate and aluminum nitrate or a combination of at least two of the same.
Preferably, the iron additive is any one of ferrous sulfate, ferric carbonate, ferric hydroxide, ferric oxalate and ferric nitrate or a combination of at least two of the above.
Preferably, the molar ratio of the lithium ion battery positive electrode scrap to the lithium additive is 1 (0.01-1), for example, 1:0.01, 1:0.05, 1:0.09, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, or 1:0.8, but not limited to the recited values, and other values not recited within the range of values are also applicable, and 1 (0.1-0.5), for example, 1 (0.1-0.4), 1 (0.1-0.2), 1 (0.2-0.4), 1:0.1, 1:0.2, or 1:0.4 is preferred.
Preferably, the molar ratio of the lithium ion battery positive electrode scrap to the nickel additive is 1 (0.01-1), for example, 1:0.01, 1:0.05, 1:0.09, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, or 1:0.8, but not limited to the recited values, and other values not recited within the range of values are also applicable, and 1 (0.1-0.5), for example, 1 (0.1-0.3), 1 (0.1-0.2), 1 (0.2-0.3), 1:0.1, 1:0.2, or 1:0.3 is preferred.
Preferably, the molar ratio of the lithium ion battery positive electrode scrap to the cobalt additive is 1 (0.01-1), for example, 1:0.01, 1:0.05, 1:0.09, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, or 1:0.8, but not limited to the recited values, and other values not recited within the range of values are also applicable, and 1 (0.1-0.5), for example, 1 (0.1-0.3), 1 (0.1-0.2), 1 (0.2-0.3), 1:0.1, 1:0.2, or 1:0.3 is preferred.
Preferably, the molar ratio of the lithium ion battery positive electrode scrap to the manganese additive is 1 (0.01-1), for example, 1:0.01, 1:0.05, 1:0.09, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, or 1:0.8, but not limited to the enumerated values, and other non-enumerated values within this range are equally applicable, preferably 1 (0.1-0.5), for example, 1 (0.1-0.3), 1 (0.1-0.2), 1 (0.2-0.3), 1:0.1, 1:0.2, or 1: 0.3.
Preferably, the molar ratio of the lithium ion battery positive electrode scrap to the aluminum additive is 1 (0.01-1), for example, 1:0.01, 1:0.05, 1:0.09, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, or 1:0.8, but not limited to the recited values, and other values not recited within the range of values are also applicable, and 1 (0.1-0.5), for example, 1 (0.1-0.3), 1 (0.1-0.2), 1 (0.2-0.3), 1:0.1, 1:0.2, or 1:0.3 is preferred.
Preferably, the molar ratio of the lithium ion battery positive electrode scrap to the iron additive is 1 (0.01-1), for example, 1:0.01, 1:0.05, 1:0.09, 1:0.1, 1:0.2, 1:0.3, 1:0.5, 1:0.7, or 1:0.8, but not limited to the recited values, and other values not recited within the range of values are also applicable, and 1 (0.1-0.5), for example, 1 (0.1-0.3), 1 (0.1-0.2), 1 (0.2-0.3), 1:0.1, 1:0.2, or 1:0.3 is preferred.
Preferably, the solid-to-liquid ratio of the lithium ion battery positive electrode waste material to water is 1 (10 to 200), for example, 1:10, 1:20, 1:50, 1:70, 1:90, 1:110, 1:50, 1:70, 1:90, or 1:200, but not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable, and preferably 1 (50 to 150), for example, 1 (50 to 60), 1 (80 to 90), 1:50, 1:60, or 1: 70.
Preferably, the mixing means comprises ultrasound or stirring.
Preferably, the sonication time is between 1 and 72 hours, such as 1 hour, 5 hours, 10 hours, 15 hours, 24 hours, 32 hours, 48 hours or 72 hours, etc., but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably between 12 and 24 hours, such as 12 hours, 20 hours, 40 or 60 hours.
Preferably, the stirring time is from 1 to 72 hours, such as 1 hour, 5 hours, 10 hours, 15 hours, 24 hours, 32 hours, 48 hours or 72 hours, etc., but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably from 12 to 70 hours, such as 12 hours, 20 hours, 40 or 60 hours.
Preferably, the stirring speed is 50-700rpm, such as 50rpm, 100rpm, 200rpm, 400rpm, 500rpm or 700rpm, but not limited to the recited values, and other non-recited values within this range are equally applicable, preferably 400rpm and 600rpm, such as 400rpm, 500rpm or 600 rpm.
Preferably, the high temperature solid phase synthesis is performed under vacuum or in an atmosphere; typical but non-limiting examples of such combinations are: a combination of air and oxygen, a combination of oxygen and nitrogen, a combination of neon, argon and argon, a combination of air, nitrogen and argon, and the like. Preferably, the atmosphere is any one of air, oxygen, nitrogen, neon, argon or a combination of at least two of them.
Preferably, the temperature of the high temperature solid phase synthesis is 100 to 1000 ℃, such as 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 1000 ℃, but is not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 300 to 800 ℃, such as 500 to 700 ℃, 500 ℃ or 700 ℃.
Preferably, the high temperature solid phase treatment time is 0.1 to 24 hours, such as 0.1 hour, 4 hours, 7 hours, 12 hours, 15 hours, 18 hours, 21 hours or 24 hours, but not limited to the recited values, and other values within the range are also applicable, preferably 5 to 12 hours, such as 8 to 12 hours, 8 to 10 hours, 10 to 12 hours, 8 hours, 10 hours or 12 hours.
The invention further provides a positive electrode material, which is prepared by any one of the above methods for repairing and regenerating the positive electrode material of the waste lithium ion battery.
The invention also provides a manufacturing method of the lithium ion battery, which comprises the following steps: the anode material is prepared by utilizing any one of the repairing and regenerating methods, and the lithium ion battery is assembled.
Preferably, the step of assembling the lithium ion battery is as follows:
mixing the positive electrode material, the conductive agent, the binder and the organic solvent, and uniformly stirring to obtain viscous paste; coating the obtained adhesive slurry on a current collector, and drying to obtain an electrode plate;
the electrode plate is used as a positive electrode, the metal lithium is used as a negative electrode, and LiPF6And assembling the solution as an electrolyte and the polypropylene as a diaphragm to obtain the lithium ion battery.
Preferably, the conductive agent is acetylene black; the binder is polyvinylidene fluoride; the mass ratio of the repair material to the conductive agent to the binder is 8:1: 1;
preferably, the organic solvent is 1-methyl-2-pyrrolidone; the addition amount of the organic solvent is controlled to be 5-20% of the solid content of the mixed solution of the repairing material, the conductive agent, the binder and the organic solvent, such as 10-15%, 10% or 15%, but not limited to the recited values, and other values not recited in the range of the values are also applicable;
Preferably, the LiPF6The concentration of the solution was 1.0mol/L and the solvent consisted of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 1.
The lithium ion battery manufactured by the manufacturing method of the lithium ion battery is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lithium ion battery anode material obtained by the repairing and regenerating method has accurate element proportion and good structural stability, and the repairing method is simple and environment-friendly; the repaired and regenerated material is used as the anode material of the lithium ion battery, and the lithium ion battery is assembled, so that the good cycle stability is shown, and the capacity retention rate of the battery is high;
(2) the method has short flow, saves the recovery cost and is easy to realize industrial application.
Drawings
FIG. 1 is an X-ray diffraction pattern of positive electrode scrap before repair in example 1 of the present invention.
Fig. 2 is an X-ray diffraction pattern of the anode material after repair in example 1 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The method for separating the waste lithium ion battery anode waste material from the waste lithium ion battery in the following embodiment comprises the following specific steps: the waste lithium ion battery is discharged and disassembled, and the waste positive plate is dissolved and filtered by water after being roasted to obtain the positive waste powder.
Example 1 repair of cathode Material of spent lithium manganate batteries and Assembly of lithium ion batteries
Repairing and recycling waste lithium manganate battery anode waste materials and assembling a lithium ion battery according to the following steps:
(1) placing the waste lithium manganate battery positive electrode waste material, lithium hydroxide and manganese oxalate with the molar ratio of 1:0.05:0.2 into water according to the solid-to-liquid ratio of 1:50, carrying out ultrasonic mixing for 24 hours, and then carrying out high-temperature solid-phase synthesis treatment in an air atmosphere, wherein the roasting treatment temperature is 700 ℃, the roasting treatment time is 10 hours, and obtaining the repair material after the treatment is finished;
(2) mixing and uniformly stirring a repairing material, a conductive agent (acetylene black), a binder (polyvinylidene fluoride) and an organic solvent (1-methyl-2-pyrrolidone), wherein the mass ratio of the repairing material to the conductive agent to the binder is 8:1:1, and the adding amount of the organic solvent is controlled to be 10% of the solid content in the mixed solution, so as to obtain viscous slurry; coating the obtained adhesive slurry on a current collector (aluminum foil) for vacuum drying at the drying temperature of 80 ℃ for 12h to obtain an electrode plate; the obtained electrode sheet was used as a positive electrode, and metallic lithium was used as a negative electrode (diameter: 15.8mm, thickness: 1mm) of 1.0mol/L LiPF 6The lithium ion battery is assembled by using a solution (dissolved with ethylene carbonate/dimethyl carbonate (EC/DMC, 1: 1, v/v)) as an electrolyte and polypropylene as a diaphragm.
In the embodiment, the loss rate of manganese in the step (1) is calculated to be 20% (before repair) through inductively coupled plasma emission spectroscopy (ICP-OES) detection; after X-ray diffraction (XRD) and ICP-OES analysis (figure 1 and figure 2), the material repaired in the step (1) is spinel lithium manganate oxide with a perfect crystal structure, the purity of the spinel lithium manganate oxide is 99.9%, and the electrochemical composition of the spinel lithium manganate oxide is LiMn2O4Electrochemical tests show that the first-cycle discharge capacity of the assembled lithium ion battery can reach 190mAh/g, and the cycle stability of the assembled lithium ion battery can reach 80% after the lithium ion battery is cycled for 100 weeks under 1C (1C: 148 mAh/g).
Example 2 repair of waste lithium cobalt oxide battery cathode waste and assembly of lithium ion battery
Repairing and recycling the waste anode waste material of the waste lithium cobalt oxide battery and assembling the lithium ion battery according to the following steps:
(1) placing the waste lithium cobaltate battery anode waste, lithium hydroxide and cobalt oxalate with the molar ratio of 1:0.6:0.1 into water according to the solid-to-liquid ratio of 1:30, carrying out ultrasonic mixing for 18 hours, and then carrying out high-temperature solid-phase synthesis treatment in the air atmosphere, wherein the roasting treatment temperature is 850 ℃, the roasting treatment time is 12 hours, and obtaining the repair material after the treatment is finished;
(2) Mixing and uniformly stirring a repairing material, a conductive agent (acetylene black), a binder (polyvinylidene fluoride) and an organic solvent (1-methyl-2-pyrrolidone), wherein the mass ratio of the repairing material to the conductive agent to the binder is 8:1:1, and the adding amount of the organic solvent is controlled to be 10% of the solid content in the mixed solution, so as to obtain viscous slurry; coating the obtained adhesive slurry on a current collector (aluminum foil) for vacuum drying at the drying temperature of 80 ℃ for 12h to obtain an electrode plate after drying, taking the obtained electrode plate as a positive electrode, taking metal lithium as a negative electrode (the diameter is 15.8mm, the thickness is 1mm) and 1.0mol/L LiPF6The lithium ion battery is assembled by using a solution (dissolved with ethylene carbonate/dimethyl carbonate (EC/DMC, 1:1, v/v)) as an electrolyte and polypropylene as a diaphragm.
In the embodiment, the deficiency rate of lithium in the step (1) is calculated and obtained to be 40% (before repair) through inductively coupled plasma emission spectroscopy (ICP-OES) detection; by X-ray diffraction (XRD) and ICP-OES analysis, the material repaired in the step (1) is a layered lithium cobaltate oxide with a perfect crystal structure, the purity of the layered lithium cobaltate oxide is 99.9 percent, and the layered lithium cobaltate oxide has an electrochemical composition of LiCoO2Electrochemical tests show that the first-cycle discharge capacity of the assembled lithium ion battery can reach 170mAh/g, and the cycle stability of the assembled lithium ion battery can reach 80% after the lithium ion battery is cycled for 100 weeks under 1C (1C is 150 mAh/g).
Example 3 repair of cathode waste of waste lithium iron phosphate batteries and assembly of lithium ion batteries
Repairing and recovering the lithium iron phosphate battery positive electrode waste material and assembling the lithium ion battery according to the following steps:
(1) mixing the waste positive electrode waste of the waste lithium iron phosphate battery, lithium hydroxide and ferric oxalate in a molar ratio of 1:0.3:0.1, placing the mixture into water according to a solid-to-liquid ratio of 1:80, performing ultrasonic mixing for 18 hours, and performing high-temperature solid-phase synthesis treatment in an air atmosphere at the roasting treatment temperature of 700 ℃ for 12 hours to obtain a repair material after the treatment is finished;
(2) mixing and uniformly stirring a repairing material, a conductive agent (acetylene black), a binder (polyvinylidene fluoride) and an organic solvent (1-methyl-2-pyrrolidone), wherein the mass ratio of the repairing material to the conductive agent to the binder is 8:1:1, and the adding amount of the organic solvent is controlled to be 10% of the solid content in the mixed solution, so as to obtain viscous slurry; coating the obtained adhesive slurry on a current collector (aluminum foil) for vacuum drying at the drying temperature of 80 ℃ for 10h to obtain an electrode plate after drying, taking the obtained electrode plate as a positive electrode, taking metal lithium as a negative electrode (the diameter is 15.8mm, the thickness is 1mm) and 1.0mol/L LiPF6The lithium ion battery is assembled by using a solution (dissolved with ethylene carbonate/dimethyl carbonate (EC/DMC, 1:1, v/v)) as an electrolyte and polypropylene as a diaphragm.
In the embodiment, the deficiency rate of lithium in the step (1) is calculated and obtained by detecting inductively coupled plasma emission spectroscopy (ICP-OES) and is 30% (before repair); through X-ray diffraction (XRD) and ICP-OES analysis, the repaired material in the step (1) is spinel lithium iron phosphate oxide with a perfect crystal structure, and the purity of the repaired material is 99.8%. Electrochemical tests show that the first-week discharge capacity of the assembled lithium ion battery can reach 160mAh/g, and the cycle stability after 100-week circulation can reach 82%.
Example 4 repair of Positive electrode waste of waste lithium Nickel cobalt manganese ternary batteries and Assembly of lithium ion batteries
The method comprises the following steps of repairing and recycling waste nickel-cobalt-manganese ternary battery anode waste materials and assembling the lithium ion battery:
(1) mixing the waste nickel-cobalt-manganese ternary battery positive electrode waste material, lithium carbonate, nickel oxalate, cobalt oxalate and manganese carbonate in a molar ratio of 1:0.5:0.1:0.2:0:2, placing the mixture in water according to a solid-to-liquid ratio of 1:40, performing ultrasonic mixing for 12 hours, and performing high-temperature solid-phase synthesis treatment in an air atmosphere, wherein the roasting treatment temperature is 850 ℃, the roasting treatment time is 12 hours, and obtaining the repair material after the treatment is finished;
(2) mixing and uniformly stirring a repair material, a conductive agent (acetylene black), a binder (polyvinylidene fluoride) and an organic solvent (1-methyl-2-pyrrolidone), wherein the mass ratio of the repair material to the conductive agent to the binder is 8:1:1, and the adding amount of the organic solvent is controlled to be 10% of the solid content in the mixed solution, so as to obtain viscous paste; coating the obtained slurry on a current collector (aluminum foil) for vacuum drying at 60 ℃ for 10h to obtain an electrode plate, taking the obtained electrode plate as a positive electrode, taking metal lithium as a negative electrode (the diameter is 15.8mm, the thickness is 1mm) and 1.0mol/L of LiPF 6The lithium ion battery is assembled by using the solution (dissolved with ethylene carbonate/dimethyl carbonate (EC/DMC, 1: 1, v/v)) as an electrolyte.
In the embodiment, the deficiency rate of lithium in the step (1) is calculated and obtained to be 40% (before repair) through inductively coupled plasma emission spectroscopy (ICP-OES) detection; through X-ray diffraction (XRD) and ICP-OES analysis, the repaired material in the step (1) is a layered lithium-nickel-cobalt-manganese ternary oxide with a perfect crystal structure, and the purity of the repaired material is 99.8%. Electrochemical tests show that the first-week discharge capacity of the assembled lithium ion battery can reach 220mAh/g, and the cycle stability can reach 80% after 100-week circulation.
Example 5 repair of Positive electrode scrap of waste lithium Nickel cobalt aluminum ternary batteries and Assembly of lithium ion batteries
The method comprises the following steps of repairing and recycling waste nickel-cobalt-aluminum ternary battery anode waste materials and assembling a lithium ion battery:
(1) mixing the waste nickel-cobalt-aluminum ternary battery positive electrode waste material, lithium carbonate, nickel oxalate, cobalt oxalate and aluminum carbonate in a molar ratio of 1:0.5:0.1:0.2:0:2, placing the mixture in water according to a solid-to-liquid ratio of 1:40, performing ultrasonic mixing for 40 hours, and performing high-temperature solid-phase synthesis treatment in an air atmosphere, wherein the roasting treatment temperature is 850 ℃, the roasting treatment time is 15 hours, and obtaining the repair material after the treatment is finished;
(2) Mixing and uniformly stirring a repair material, a conductive agent (acetylene black), a binder (polyvinylidene fluoride) and an organic solvent (1-methyl-2-pyrrolidone), wherein the mass ratio of the repair material to the conductive agent to the binder is 8:1:1, and the adding amount of the organic solvent is controlled to ensure that the solid content in the mixed solution is the solid content10 percent of adhesive paste is obtained, the obtained adhesive paste is coated on a current collector (aluminum foil) to be dried in vacuum at the drying temperature of 90 ℃ for 12 hours, an electrode plate is obtained after drying, the obtained electrode plate is used as a positive electrode, metal lithium is used as a negative electrode (the diameter is 15.8mm, the thickness is 1mm), and LiPF of 1.0mol/L6The lithium ion battery is assembled by using a solution (dissolved with ethylene carbonate/dimethyl carbonate (EC/DMC, 1:1, v/v)) as an electrolyte and polypropylene as a diaphragm.
In the embodiment, the deficiency rate of lithium in the step (1) is calculated and obtained to be 40% (before repair) through inductively coupled plasma emission spectroscopy (ICP-OES) detection; through X-ray diffraction (XRD) and ICP-OES analysis, the repaired material in the step (1) is a layered lithium-nickel-cobalt-aluminum ternary oxide with a perfect crystal structure, and the purity of the repaired material is 99.8%. Electrochemical tests show that the first-week discharge capacity of the assembled lithium ion battery can reach 220mAh/g, and the cycle stability can reach 80% after 100-week cycle.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It will be apparent to those skilled in the art that any modification, equivalent substitution of materials for the invention, addition of additional materials, selection of specific means, etc., which are apparent to those skilled in the art are intended to be within the scope and disclosure of the invention.

Claims (12)

1. A regeneration method for simply and accurately regulating and controlling target elements to repair waste lithium ion battery anode waste materials comprises the following steps:
placing the waste anode waste of the waste lithium ion battery and the additive into an aqueous solution, carrying out high-temperature solid-phase synthesis treatment after ultrasonic or stirring mixing, and realizing restoration and regeneration after the treatment.
2. The method of claim 1, wherein: the lithium additive is any one or the combination of at least two of lithium carbonate, lithium acetate, lithium oxalate, lithium hydroxide, lithium phosphate and lithium fluoride;
preferably, the nickel additive is any one of nickel sulfate, nickel carbonate, nickel hydroxide, nickel oxalate and nickel nitrate or a combination of at least two of the nickel sulfate, the nickel carbonate, the nickel hydroxide, the nickel oxalate and the nickel nitrate;
Preferably, the cobalt additive is any one of cobalt sulfate, cobalt carbonate, cobalt hydroxide, cobalt oxalate and cobalt nitrate or a combination of at least two of the cobalt additive;
preferably, the manganese additive is any one of manganese sulfate, manganese acetate, manganese carbonate, manganese hydroxide, manganese oxalate and manganese nitrate or a combination of at least two of the manganese sulfate, the manganese acetate, the manganese carbonate, the manganese hydroxide, the manganese oxalate and the manganese nitrate;
preferably, the aluminum additive is any one of aluminum sulfate, aluminum carbonate, aluminum hydroxide, aluminum oxalate and aluminum nitrate or a combination of at least two of the aluminum sulfate, the aluminum carbonate, the aluminum hydroxide, the aluminum oxalate and the aluminum nitrate;
preferably, the iron additive is any one of ferrous trioxide, ferric carbonate, ferric hydroxide, ferric oxalate and ferric nitrate or a combination of at least two of the foregoing.
3. The method according to claim 1 or 2, characterized in that: the molar ratio of the lithium ion battery anode waste to the lithium additive is 1 (0.01-1);
the molar ratio of the lithium ion battery anode waste to the nickel additive is 1 (0.01-1);
the molar ratio of the lithium ion battery anode waste to the cobalt additive is 1 (0.01-1);
the molar ratio of the lithium ion battery anode waste to the manganese additive is 1 (0.01-1);
the molar ratio of the lithium ion battery anode waste to the aluminum additive is 1 (0.01-1);
The molar ratio of the lithium ion battery anode waste to the iron additive is 1 (0.01-1).
4. The method according to any one of claims 1-3, wherein: the ultrasonic time is 1-72 h.
5. The method according to any one of claims 1-3, wherein: the stirring time is 1-72 h; the stirring speed is 300-600 rpm.
6. The method according to any one of claims 1-3, wherein: the high-temperature solid phase synthesis is carried out under vacuum or atmosphere conditions;
the atmosphere is any one or the combination of at least two of air, nitrogen, neon, argon or argon.
7. The method according to any one of claims 1-6, wherein: the temperature of the high-temperature solid phase synthesis is 100-1000 ℃, and the time is 0.1-24 h.
8. The cathode material is prepared by the method for repairing and regenerating the waste cathode materials of the waste lithium ion batteries in any one of claims 1 to 7.
9. A manufacturing method of a lithium ion battery comprises the following steps: preparing a positive electrode material by using the repairing and regenerating method of any one of claims 1 to 7, and assembling the lithium ion battery.
10. The method for manufacturing a lithium ion battery according to claim 9, wherein: the steps of assembling the lithium ion battery are as follows:
Mixing the positive electrode material, the conductive agent, the binder and the organic solvent, and uniformly stirring to obtain viscous slurry; coating the obtained adhesive slurry on a current collector, and drying to obtain an electrode plate;
the electrode plate is used as a positive electrode, the metal lithium is used as a negative electrode, and LiPF6And assembling the solution as electrolyte and the polypropylene as a diaphragm to form the lithium ion battery.
11. The method of manufacturing of claim 10, wherein: the conductive agent is acetylene black; the binder is polyvinylidene fluoride; the mass ratio of the repair material to the conductive agent to the binder is 8:1: 1;
the organic solvent is 1-methyl-2-pyrrolidone; the adding amount of the organic solvent is controlled to be 5-20% of the solid content of the mixed liquid of the repairing material, the conductive agent, the binder and the organic solvent;
the LiPF6The concentration of the solution is 1.0mol/L, and the solvent consists of ethylene carbonate and dimethyl carbonate in a volume ratio of 1: 1.
12. The lithium ion battery manufactured by the method for manufacturing a lithium ion battery according to any one of claims 9 to 11.
CN202210353371.2A 2022-04-02 2022-04-02 Regeneration method for simply and accurately regulating target elements to repair waste lithium ion battery anode waste Pending CN114759282A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116706050A (en) * 2023-08-07 2023-09-05 江门市科恒实业股份有限公司 Medium-low nickel monocrystal ternary positive electrode material, preparation method thereof and battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116706050A (en) * 2023-08-07 2023-09-05 江门市科恒实业股份有限公司 Medium-low nickel monocrystal ternary positive electrode material, preparation method thereof and battery
CN116706050B (en) * 2023-08-07 2023-11-28 江门市科恒实业股份有限公司 Medium-low nickel monocrystal ternary positive electrode material, preparation method thereof and battery

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