CN110277602B - Repairing and regenerating method of lithium iron phosphate anode material in waste battery - Google Patents
Repairing and regenerating method of lithium iron phosphate anode material in waste battery Download PDFInfo
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- CN110277602B CN110277602B CN201810219378.9A CN201810219378A CN110277602B CN 110277602 B CN110277602 B CN 110277602B CN 201810219378 A CN201810219378 A CN 201810219378A CN 110277602 B CN110277602 B CN 110277602B
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- 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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which comprises the steps of calcining a lithium iron phosphate positive electrode piece obtained by disassembly to obtain waste lithium iron phosphate; dispersing waste lithium iron phosphate into deionized water, adding a surfactant, a soluble ferric salt and hydrogen peroxide, and stirring to obtain a solution containing the lithium iron phosphate; adding an ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring, and drying to obtain iron phosphate-coated lithium iron phosphate powder; mixing iron phosphate-coated lithium iron phosphate powder with lithium salt, and calcining to obtain a repaired and regenerated lithium iron phosphate positive material; therefore, the invention adopts a coating technology, coats a layer of lithium iron phosphate of the material on the surface of the material, and finally obtains the lithium iron phosphate anode material for repairing and regeneration by lithium supplement and high temperature calcination, thereby achieving the purpose of coating while realizing repairing and regeneration, and further improving the cycle performance of the recycled lithium iron phosphate anode material.
Description
Technical Field
The invention belongs to the technical field of waste battery recycling, and particularly relates to a method for repairing and regenerating a lithium iron phosphate positive material in a waste battery.
Background
The recycling of common lithium iron phosphate anode materials mainly comprises two types of valuable metal extraction and restoration regeneration.
In the prior art, the extraction of valuable metals usually adopts an acid leaching mode to dissolve a positive electrode material to obtain a solution of valuable metal ions, and finally, inorganic salts of the valuable metals are obtained through impurity removal and precipitation; the extraction method of the valuable metal is simple and easy to implement, is the most common method for recycling the waste batteries at present, but has high treatment cost, needs to consume a large amount of acid and alkali, can generate a large amount of three wastes, and causes serious pollution to the environment.
The repair regeneration is to implement the recovery of physical and chemical indexes of the material by lithium supplement of the separated anode material, so as to achieve the purpose of repair regeneration; the repair regeneration technology is a new technology, and is currently in laboratory research and development, the repair regeneration of materials can be realized by simply supplementing lithium, but compared with a battery material obtained by direct preparation, as impurities exist in the battery material for repair regeneration, and the impurities in the material can generate side reaction with electrolyte in the process of charging and discharging, the cycle performance of the material is affected, so that the electrochemical performance of the battery material obtained by the method is far different, and the battery material is difficult to compare with a commercial material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery.
The invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, calcining the disassembled lithium iron phosphate positive pole piece at 200-600 ℃ for 2-8 h, then carrying out ultrasonic treatment, and finally sieving and washing to obtain waste lithium iron phosphate;
step 2, dispersing the waste lithium iron phosphate obtained in the step 1 in deionized water to obtain an intermediate solution, adding a surfactant, a soluble ferric salt and hydrogen peroxide into the intermediate solution, and stirring to obtain a solution containing lithium iron phosphate;
step 3, adding an ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate obtained in the step 2, stirring and drying to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding a lithium salt into the iron phosphate-coated lithium iron phosphate powder obtained in the step 3 to adjust the lithium iron ratio of the iron phosphate-coated lithium iron phosphate powder, and calcining under an inert atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
In the above scheme, the surfactant in step 2 is at least one of sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate, and hexadecyl trimethyl ammonium bromide.
In the scheme, the mass of the added surfactant in the step 2 is 1-5% of the mass of the waste lithium iron phosphate.
In the above scheme, the soluble iron salt in step 2 is at least one of a sulfate, a chloride and a nitrate of ferrous iron and/or ferric iron.
In the scheme, the mass of the soluble ferric salt added in the step 2 is 1-10% of the mass of the waste lithium iron phosphate.
In the scheme, the stirring speed in the step 2 is 100-500 r/min, and the stirring time is 4-8 h.
In the scheme, the mass of the ammonium dihydrogen phosphate solution added in the step 3 is 1-10% of the mass of the solution containing the lithium iron phosphate.
In the scheme, the stirring time in the step 3 is 1-4 h, the drying temperature is 100-150 ℃, and the drying time is 4-8 h.
In the above scheme, the lithium salt in step 4 is at least one of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium fluoride, lithium bromide, lithium iodide and lithium dihydrogen phosphate, and the addition amount of the lithium salt is such that the ratio of lithium to iron added to the iron phosphate-coated lithium iron phosphate powder is 1 (1-1.05).
In the scheme, the calcining temperature in the step 4 is 600-1000 ℃, and the calcining time is 4-8 h.
Compared with the prior art, the invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which comprises the steps of calcining a lithium iron phosphate positive electrode piece obtained by disassembly to obtain waste lithium iron phosphate; dispersing waste lithium iron phosphate into deionized water, adding a surfactant, a soluble ferric salt and hydrogen peroxide, and stirring to obtain a solution containing the lithium iron phosphate; adding an ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring, and drying to obtain iron phosphate-coated lithium iron phosphate powder; mixing iron phosphate-coated lithium iron phosphate powder with lithium salt, and calcining to obtain a repaired and regenerated lithium iron phosphate positive material; thus, the invention adopts a coating technology, a layer of ferric phosphate is coated on the surface of the waste lithium iron phosphate material, and finally the lithium-supplementing high-temperature calcination is carried out to obtain the lithium iron phosphate anode material for repairing and regeneration, so that the aim of coating is achieved while the repairing and regeneration are realized, and the cycle performance of the recovered lithium iron phosphate anode material is improved; although the lithium iron phosphate anode material obtained by the invention is pure lithium iron phosphate, the surface of the lithium iron phosphate anode material is coated with a layer of new lithium iron phosphate, and the new lithium iron phosphate coated on the outer layer has better electrochemical performance compared with the original lithium iron phosphate on the inner layer; in addition, compared with the traditional coating (oxide coating, conductive polymer coating and the like), the coating method adopted by the invention can be realized simultaneously on the basis of improving the integral specific capacity of the material, the coating process is simpler, namely, the coating is realized simultaneously on the basis of repairing and regenerating, and the coating material has higher specific capacity.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following 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.
The embodiment of the invention provides a method for repairing and regenerating a lithium iron phosphate positive material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at the temperature of 200-600 ℃ for 2-8 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, dispersing waste lithium iron phosphate into deionized water to obtain an intermediate solution, adding a surfactant, a soluble ferric salt and hydrogen peroxide into the intermediate solution, and stirring at a rotating speed of 100-500 r/min for 4-8 hours to obtain a solution containing the lithium iron phosphate;
the waste lithium iron phosphate lithium ion battery comprises a waste lithium iron phosphate, a waste lithium iron phosphate and a surfactant, wherein the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate and hexadecyl trimethyl ammonium bromide, and the mass of the added surfactant is 1-5% of that of the waste lithium iron phosphate;
the soluble ferric salt is at least one of sulfate, chloride and nitrate of ferrous iron and/or ferric iron, and the mass of the added soluble ferric salt is 1-10% of that of the waste lithium iron phosphate;
the mass of the added hydrogen peroxide is 1-5% of that of the waste lithium iron phosphate;
step 3, adding an ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 1-4 h at normal temperature, and drying for 4-8 h at 100-150 ℃ to obtain iron phosphate coated lithium iron phosphate powder;
wherein the mass of the added ammonium dihydrogen phosphate solution is 1-10% of the mass of the solution containing the lithium iron phosphate;
step 4, adding a lithium salt into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium salt after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 4-8 hours at 600-1000 ℃ in an inert atmosphere to obtain a repaired and regenerated lithium iron phosphate cathode material;
wherein the lithium salt is at least one of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium fluoride, lithium bromide, lithium iodide and lithium dihydrogen phosphate.
According to the invention, a coating technology is adopted, a layer of ferric phosphate is coated on the surface of the waste lithium iron phosphate material, and finally, the lithium-supplementing high-temperature calcination is carried out to obtain the lithium iron phosphate anode material for repairing and regeneration, so that the aim of coating is achieved while the repairing and regeneration are realized, and the cycle performance of the recovered lithium iron phosphate anode material is improved; although the lithium iron phosphate anode material obtained by the invention is pure lithium iron phosphate, the surface of the lithium iron phosphate anode material is coated with a layer of new lithium iron phosphate, and the new lithium iron phosphate coated on the outer layer has better electrochemical performance compared with the original lithium iron phosphate on the inner layer; in addition, compared with the traditional coating (oxide coating, conductive polymer coating and the like), the coating method adopted by the invention can be realized simultaneously on the basis of improving the integral specific capacity of the material, the coating process is simpler, namely, the coating is realized simultaneously on the basis of repairing and regenerating, and the coating material has higher specific capacity.
Example 1
The embodiment 1 of the invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 200 ℃ for 8 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 2% of sodium dodecyl benzene sulfonate, 5% of ferrous nitrate and 2% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 200r/min for 6 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding a 5% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 2 hours at normal temperature, and drying for 6 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium carbonate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium carbonate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 8 hours at 800 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.7 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.3 mAh/g.
Example 2
The embodiment 2 of the invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 5 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 2% of sodium dodecyl benzene sulfonate, 5% of ferrous nitrate and 2% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 200r/min for 6 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding a 5% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 2 hours at normal temperature, and drying for 6 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium carbonate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium carbonate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 8 hours at 800 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.3 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 136.3 mAh/g.
Example 3
The embodiment 3 of the invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 600 ℃ for 2 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 2% of sodium dodecyl benzene sulfonate, 5% of ferrous nitrate and 2% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 200r/min for 6 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding a 5% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 2 hours at normal temperature, and drying for 6 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium carbonate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium carbonate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 8 hours at 800 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.6mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.2% after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.5 mAh/g.
Example 4
The embodiment 4 of the invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 6 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 1% of sodium hexadecyl sulfate, 1% of ferrous sulfate and 1% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 100r/min for 8 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 6% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 3 hours at normal temperature, and drying for 5 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium acetate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium acetate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 800 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.4mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.7 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.7 mAh/g.
Example 5
Embodiment 5 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 6 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 1% of sodium hexadecyl sulfate, 6% of ferrous chloride and 2% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 300r/min for 6 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 6% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 3 hours at normal temperature, and drying for 5 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium acetate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium acetate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 800 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 153.1mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.2% after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.3 mAh/g.
Example 6
Embodiment 6 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 6 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 1% of sodium hexadecyl sulfate, 10% of ferric chloride and 5% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 500r/min for 8 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 6% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 3 hours at normal temperature, and drying for 5 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium acetate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium acetate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 800 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.6mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.4 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.9 mAh/g.
Example 7
Embodiment 7 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 6 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 3% of hexadecyl trimethyl ammonium bromide, 4% of ferrous nitrate and 3% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 200r/min for 8 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 1% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 1 hour at normal temperature, and drying for 8 hours at 100 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium oxalate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium oxalate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 820 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.6mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.6 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.4 mAh/g.
Example 8
Embodiment 8 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 6 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 3% of hexadecyl trimethyl ammonium bromide, 4% of ferrous nitrate and 3% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 200r/min for 8 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding a 5% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 2.5 hours at normal temperature, and drying for 6 hours at 120 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium oxalate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium oxalate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 820 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.7 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 136.3 mAh/g.
Example 9
Embodiment 9 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 400 ℃ for 6 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 3% of hexadecyl trimethyl ammonium bromide, 4% of ferrous nitrate and 3% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 200r/min for 8 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding a 10% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 4 hours at normal temperature, and drying for 4 hours at 150 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium oxalate into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium oxalate after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 820 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.9mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.2% after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.5 mAh/g.
Example 10
The embodiment 10 of the invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 500 ℃ for 4 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 2% of sodium dodecyl benzene sulfonate, 6% of ferrous nitrate and 3% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 360r/min for 5 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 6% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 3 hours at normal temperature, and drying for 6 hours at 130 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium hydroxide into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium hydroxide after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 4 hours at 600 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.4mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.9 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 136.1 mAh/g.
Example 11
Embodiment 11 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 500 ℃ for 4 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 2% of sodium dodecyl benzene sulfonate, 6% of ferrous nitrate and 3% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 360r/min for 5 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 6% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 3 hours at normal temperature, and drying for 6 hours at 130 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium hydroxide into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium hydroxide after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 6 hours at 880 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 152.3mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.8% after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 136.3 mAh/g.
Example 12
Embodiment 12 of the present invention provides a method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery, which is implemented by the following steps:
step 1, cleaning and discharging waste lithium ion batteries, disassembling and sorting lithium iron phosphate positive pole pieces, calcining the lithium iron phosphate positive pole pieces obtained through disassembly at 500 ℃ for 4 hours, then carrying out ultrasonic treatment on the positive pole pieces obtained after calcination, and finally sieving and washing the positive pole pieces by adopting a 50-200-mesh sieve to obtain waste lithium iron phosphate;
step 2, weighing the waste lithium iron phosphate obtained in the step 1, dispersing the waste lithium iron phosphate in deionized water to obtain an intermediate solution, adding 2% of sodium dodecyl benzene sulfonate, 6% of ferrous nitrate and 3% of hydrogen peroxide into the intermediate solution by taking the mass of the waste lithium iron phosphate as a reference, and stirring at a rotating speed of 360r/min for 5 hours to obtain a solution containing lithium iron phosphate;
step 3, weighing the solution containing the lithium iron phosphate obtained in the step 2, adding 6% ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate, stirring for 3 hours at normal temperature, and drying for 6 hours at 130 ℃ to obtain iron phosphate-coated lithium iron phosphate powder;
and 4, adding lithium hydroxide into the lithium iron phosphate powder coated with the iron phosphate according to the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3, stopping adding the lithium hydroxide after the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate is 1 (1-1.05), and finally calcining for 4 hours at 1000 ℃ in an argon/hydrogen atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Compared with the prior art, the repaired and regenerated lithium iron phosphate cathode material prepared by the scheme is used as a positive electrode, a metal lithium sheet is used as a negative electrode to assemble a button cell for charge and discharge tests, and the first discharge specific capacity of the repaired and regenerated lithium iron phosphate cathode material prepared by the method reaches 153mAh/g under the multiplying power of 0.5C; the capacity retention rate can reach 96.7 percent after 100 charge-discharge cycles; under the 2C multiplying power, the discharge specific capacity reaches 135.3 mAh/g.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (7)
1. A method for repairing and regenerating a lithium iron phosphate positive electrode material in a waste battery is characterized by comprising the following steps:
step 1, calcining the disassembled lithium iron phosphate positive pole piece at 200-600 ℃ for 2-8 h, then carrying out ultrasonic treatment, and finally sieving and washing to obtain waste lithium iron phosphate;
step 2, dispersing the waste lithium iron phosphate obtained in the step 1 in deionized water to obtain an intermediate solution, adding a surfactant, a soluble ferric salt and hydrogen peroxide into the intermediate solution, and stirring to obtain a solution containing lithium iron phosphate; the mass of the added surfactant is 1-5% of the mass of the waste lithium iron phosphate; the mass of the added soluble ferric salt is 1-10% of the mass of the waste lithium iron phosphate;
step 3, adding an ammonium dihydrogen phosphate solution into the solution containing the lithium iron phosphate obtained in the step 2, stirring and drying to obtain iron phosphate-coated lithium iron phosphate powder; the mass of the added ammonium dihydrogen phosphate solution is 1-10% of the mass of the solution containing the lithium iron phosphate;
step 4, adding a lithium salt into the lithium iron phosphate powder coated with the iron phosphate obtained in the step 3 to adjust the lithium iron ratio of the lithium iron phosphate powder coated with the iron phosphate, and calcining under an inert atmosphere to obtain a repaired and regenerated lithium iron phosphate cathode material; the addition amount of the lithium salt is that the lithium iron ratio added to the iron phosphate coated lithium iron phosphate powder is 1 (1-1.05).
2. The method for repairing and regenerating the lithium iron phosphate positive electrode material in the waste battery according to claim 1, wherein the surfactant in the step 2 is at least one of sodium dodecyl benzene sulfonate, sodium hexadecyl sulfate and hexadecyl trimethyl ammonium bromide.
3. The method for repairing and regenerating the lithium iron phosphate cathode material in the waste battery according to claim 2, wherein the soluble iron salt in the step 2 is at least one of sulfate, chloride and nitrate of ferrous iron and/or ferric iron.
4. The method for repairing and regenerating the lithium iron phosphate positive electrode material in the waste battery as claimed in claim 2, wherein the stirring speed in the step 2 is 100-500 r/min, and the stirring time is 4-8 h.
5. The method for repairing and regenerating the lithium iron phosphate positive electrode material in the waste battery according to claim 1, wherein the stirring time in the step 3 is 1-4 hours, the drying temperature is 100-150 ℃, and the drying time is 4-8 hours.
6. The method for repairing and regenerating the lithium iron phosphate positive electrode material in the waste battery according to claim 1, wherein the lithium salt in the step 4 is at least one of lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium fluoride, lithium bromide, lithium iodide and lithium dihydrogen phosphate.
7. The method for repairing and regenerating the lithium iron phosphate positive electrode material in the waste battery according to claim 1, wherein the calcining temperature in the step 4 is 600-1000 ℃, and the calcining time is 4-8 hours.
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