CN104485494B - The renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell - Google Patents

Abstract

A method for regenerating positive active materials in lithium cobaltate spent lithium-ion batteries, the steps of which are: discharging and disassembling the spent lithium-ion batteries to obtain spent positive plates, roasting the spent positive plates, dissolving in water, and filtering to obtain spent lithium cobaltate powder; Mix the waste lithium cobaltate powder and sodium pyrosulfate in a certain proportion and then roast it, leaching the roasted product with water, then add sodium carbonate solution to the solution and filter it, add a certain amount of lithium carbonate to the filter residue, ball mill it, compact it, put it Putting it into a resistance furnace for roasting, to regain the lithium cobalt oxide positive electrode material with good electrochemical performance. The filtrate was adjusted with sulfuric acid and then crystallized to obtain sodium bisulfate.

Description

Regeneration method of positive electrode active material in lithium cobalt oxide spent lithium ion battery

technical field

The invention relates to the regeneration technology of positive electrode active materials in lithium cobalt oxide waste lithium ion batteries.

Background technique

Lithium-ion batteries are a new generation of secondary batteries developed rapidly in the 1990s, and are widely used in small portable electronic communication products and electric vehicles. According to statistics, in 2009, the output of lithium-ion batteries in my country reached 1.87 billion, and in 2010, the output of lithium-ion batteries in my country reached 2.68 billion. Since the service life of lithium-ion batteries is generally 2-3 years, the problems of environmental pollution and resource waste caused by discarded lithium-ion batteries have become increasingly prominent. The problem of how to properly dispose of discarded lithium-ion batteries cannot be ignored. The recycling and reuse of resources such as Co, Ni, Mn, Li, Al, and Cu in waste lithium-ion batteries not only overcomes the environmental pollution caused by the disposal of waste lithium-ion batteries by discarding methods, but also enables the recycling of limited resources. It not only has great economic benefits, but also has great significance in environmental protection.

The positive electrode material used in lithium-ion batteries is one of the key materials for manufacturing lithium-ion batteries, and occupies a core position in lithium-ion batteries. At present, the positive electrode materials that have been industrialized mainly include lithium cobalt oxide, lithium manganese oxide, nickel-cobalt lithium manganese oxide ternary materials, and lithium iron phosphate. Among them, lithium cobalt oxide is still the mainstream material, mainly used in high-end electronic products. Energy density in the field of lithium-ion batteries.

The methods that have been publicly reported to recover valuable metals from waste lithium-ion batteries using lithium cobaltate as the positive electrode material mainly include, ZhangPW et al. reported in "Hydrometallurgy" Vol.47No.2-3, 1998, 259-271 Lithium-ion battery positive electrode waste is leached with hydrochloric acid, and then cobalt sulfate and lithium carbonate are obtained through extraction, precipitation and other operations. Wu Fang reported in "Chinese Journal of Nonferrous Metals" Vol.14No.4, 2004, 697-701 that the positive electrode waste obtained from the waste lithium-ion battery was obtained by leaching with sulfuric acid and hydrogen peroxide at high temperature, and then extracted and precipitated. Cobalt Sulfate and Lithium Carbonate. MyoungJ et al reported in "Journal of Power Sources" Vol.112, 2002, 639-642 that hot nitric acid was used to dissolve positive electrode waste obtained from spent lithium-ion batteries, and then Co ₃ O ₄ was obtained after electrodeposition and low-temperature calcination. The patent [CN201210491084] reports a method for producing Co ₃ O ₄ from waste lithium-ion batteries. The positive electrode of the waste lithium-ion battery is immersed in an organic solvent to separate the positive electrode powder material from the aluminum foil current collector, and then to the positive electrode The powder material is added with fluorine-containing organic matter and then roasted to obtain the Co ₃ O ₄ material. The patent [CN201210167969] reports a method for efficiently intensifying the leaching of metals in waste lithium-ion batteries. By adding lithium cobalt oxide powder to the dilute acid solution, controlling the solid-liquid ratio and adding ferrous sulfate, and applying DC voltage, the cobalt acid Lithium leaching efficiency. Patent [CN201180048492] reports a method for recovering Li ions by introducing one or more cyclosiloxanes so that lithium ions form one or more cyclosiloxane-Li ion complexes, and then The organic phase containing the cyclosiloxane-Li ion complex was separated from the aqueous phase. Patent [CN201010523257] reports a method for reclaiming lithium from waste lithium-ion batteries and waste pole pieces, by leaching it with acid and reducing agent, and removing impurities such as iron, copper, and aluminum in the leachate by chemical methods, and then using The fluoride salt precipitates the lithium in the leaching solution to obtain the lithium fluoride product. The patent [ _{CN200910117702} ] reports that the waste LiCoO2 powder is mixed with alkali metal sodium and potassium salts and roasted at a higher temperature, the roasted product is leached with water, and the leaching solution is subjected to cobalt and lithium precipitation operations to obtain cobalt oxalate and lithium carbonate . The patent [CN200910093727] reports a method for preparing lithium cobalt oxide by recycling waste lithium ion batteries. The waste LiCoO ₂ material is obtained by dissipating the waste lithium ion batteries, dismantling, crushing, NMP treatment, and calcining, and then LiCoO ₂ The material is mixed with natural organic acid and hydrogen peroxide and then ball-milled to obtain a solution of Li ⁺ and Co ²⁺ . Ammonia water is added dropwise to the solution to prepare a xerogel and calcined twice to obtain a lithium cobaltate electrode material. Patent [CN200910039217] discloses a method for recycling and regenerating waste lithium-ion battery cathode materials, by crushing the waste lithium-ion battery cathode waste, grinding, removing aluminum, acid leaching, extracting copper, chemically removing impurities, precipitating, adding Secondary high-temperature roasting operation of lithium source to realize cathode material regeneration. The patent [CN200810028730] discloses a method for recovering and preparing lithium cobaltate from waste lithium-ion batteries. Obtain waste lithium cobalt oxide by crushing and sieving the positive electrode of waste lithium-ion batteries; remove the binder and conductive agent acetylene black in a constant temperature resistance furnace, mix in an appropriate proportion of lithium carbonate, and sinter in a muffle furnace at high temperature Synthesis of active lithium cobalt oxide battery materials. The patent [CN200710057623] discloses a process for activating lithium cobalt oxide, a positive electrode material of a waste lithium ion battery. The binder PVDF is removed from the positive electrode material of the waste lithium-ion battery at high temperature, and lithium cobalt oxide is calcined at high temperature, so that the invalid lithium cobalt oxide produces a crystallization reaction and regains a layered structure. Patent [CN200510018601] reports a method for separating and recovering cobalt from lithium cobalt oxide, the positive electrode material of waste lithium ion batteries. After the waste lithium-ion battery is physically disassembled, calcined, and soaked in an organic solvent, the waste lithium cobalt oxide is obtained, and the waste lithium cobalt oxide is placed under acidic conditions with H ₂ O ₂ or Na ₂ S ₂ O ₃ as a reducing agent, dissolved A solution containing Co ²⁺ and Li ⁺ is obtained, and NaOH solution is used as a precipitating agent to convert Co ²⁺ ions in the solution into Co(OH) ₂ for precipitation. Patent [CN200510015078] discloses a method for recovering and preparing Li _x CoO ₂ from discarded lithium-ion batteries. Cut the positive electrode material of the waste lithium ion battery into small pieces and soak it in N-methyl-2-pyrrolidone liquid, separate and obtain the active material Li _x CoO ₂ black powder, then disperse the black powder in nitric acid solution or hydrochloric acid solution, and then After filtration and precipitation operations, a blue precipitate was obtained, and the precipitate was roasted at high temperature to obtain Li _x CoO ₂ powder.

The regeneration method of positive electrode active material in lithium cobaltate waste lithium ion battery that has been reported so far uses sulfuric acid plus hydrogen peroxide, sodium thiosulfate, hydrochloric acid, nitric acid to dissolve waste LiCoO ₂ , and acid-containing gas, Cl ₂ are inevitably generated during the leaching process Or _NOx waste gas, the recovery process has caused serious secondary pollution to the environment. In addition, there are many follow-up processing procedures and long processes for the leaching solution, resulting in high recovery costs; in the leaching process, high acid concentration and leaching temperature are used in order to improve the metal recovery rate and shorten the leaching time, which requires high anti-corrosion requirements for leaching equipment. The electrochemical performance of lithium cobaltate prepared by the method of re-obtaining lithium cobaltate from the positive active material peeled off from the positive electrode sheet of the spent lithium ion battery by calcining at high temperature cannot meet the performance requirements of lithium ion battery. The method of roasting after mixing the waste LiCoO2 powder with the salt of alkali metal _sodium and potassium has the problem that the amount of salt of alkali metal sodium and potassium in the roasting process is large, and the amount of precipitant oxalate in the recovery process is large, resulting in high recovery costs. Disadvantages: The use of ball milling technology after mixing waste LiCoO ₂ materials with natural organic acids and hydrogen peroxide has the disadvantage that the ball milling equipment will be easily corroded during the recycling process and produce wastewater containing organic matter.

Contents of the invention

The object of the present invention is to provide a method for regenerating positive electrode active materials in lithium cobalt oxide waste lithium ion batteries.

The present invention is the regeneration method of positive active material in lithium cobalt oxide waste lithium ion battery, and its steps are:

Step (1): Place the collected scrap lithium-ion battery with lithium cobaltate as positive electrode material in 0.1-1.0mol/L sodium hydroxide aqueous solution at room temperature for 1-3h discharge treatment; after discharge treatment, Disassemble the scrapped lithium-ion battery to obtain the positive electrode sheet; collect the positive electrode scraps and positive electrode scraps generated during the manufacturing process of the lithium-ion battery with lithium cobaltate as the positive electrode material to obtain the positive electrode sheet;

Step (2): Put the positive electrode sheet obtained in step (1) into the ceramic crucible according to the ratio of the mass of the positive electrode sheet to the volume of the ceramic crucible - g/mL is 1:10-1:15, Then put it in a box-type resistance furnace from room temperature to 550°C at a heating rate of 5°C/min and keep it warm for 0.5-1h, then turn off the power of the box-type resistance furnace and cool it down to room temperature naturally; take out the roasted positive electrode According to the ratio of the mass of the positive electrode sheet to the volume of water - g/mL is 1:40-1:70, put the positive electrode sheet into a container filled with water and stir it with an electric stirrer for 5-30min. The temperature is 20-50°C, and the stirring speed is 10-200r/min; after the stirring is stopped, the mixture in the container is sieved with a 10-20 mesh screen. solution; the aluminum foil was washed with water for 1-3 times, and the aluminum foil was obtained by natural drying; the undersieve was subjected to suction filtration, and the supernatant was washed with water for 1-3 times to obtain the positive electrode active material;

Step (3): Put the positive electrode active material obtained in step (2) into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 500-700°C at a heating rate of 5°C/min and keep it warm for 0.5 -3h, obtain waste lithium cobalt oxide powder;

Step (4): Mix the waste lithium cobaltate powder obtained in step (3) with sodium pyrosulfate at a mass ratio of -g/g in a ratio of 1:0.3-1:1.7, then put it into a ceramic mortar, grind and mix well, Put the ground mixture into a ceramic crucible and cover it with a ceramic cover, then put it into a box-type resistance furnace for roasting, raise the furnace temperature to 400-650°C at a heating rate of 3-10°C/min and keep it warm for 10-60min ; In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical product purchased;

Step (5): After the calcination, the material in the crucible is leached with water at 20-50°C under the condition of stirring, the leaching time is 5-30min, and the solid-liquid ratio-g/mL is 1:10-1:50 Then the leachate is heated to 95-98°C, 1.0-3.0mol/L sodium carbonate solution is slowly added to the leachate, then filtered, the filter residue is washed and dried, and the content of Li and Co in the filter residue is analyzed, according to the molar ratio of lithium to cobalt To meet the requirements of 1.05:1, add a certain amount of lithium carbonate to the filter residue, and then fully spheroidize the ball in the planetary ball mill. The ball milling time is 0.5-2h, the speed is 200-500r/min, and then it is pressed under the pressure of 0.1-100MPa Put it into a clean ceramic crucible, keep the temperature at 650-700°C for 2-6h in the air atmosphere, then raise the temperature to 900°C for 10h, then cool slowly to room temperature, crush and grind the fired samples, and pass through a 500-mesh sieve , to obtain lithium cobalt oxide positive electrode material with good electrochemical performance;

Step (6): Filter the solution obtained in step (5) to adjust the composition with concentrated sulfuric acid so that the pH of the solution is 0.5-1.0, and then crystallize in an evaporation crystallizer. The crystallization control conditions are vacuum degree 0.012-0.015MPa, temperature 120 -140°C, dry the crystals at 50-80°C for 0.2-3h to obtain sodium bisulfate.

Compared with the prior art, the present invention has the advantages of short process flow, low recycling cost, easy operation, low requirements on equipment anticorrosion, excellent performance of the regenerated lithium cobaltate cathode material, and no secondary pollution during the process.

detailed description

The present invention is the regeneration method of positive active material in lithium cobalt oxide waste lithium ion battery, and its steps are:

Step (1): Place the collected scrap lithium-ion battery with lithium cobaltate as positive electrode material in 0.1-1.0mol/L sodium hydroxide aqueous solution at room temperature for 1-3h discharge treatment; after discharge treatment, Disassemble the scrapped lithium-ion battery to obtain the positive electrode sheet; collect the positive electrode scraps and positive electrode scraps generated during the manufacturing process of the lithium-ion battery with lithium cobaltate as the positive electrode material to obtain the positive electrode sheet;

Step (2): Put the positive electrode sheet obtained in step (1) into the ceramic crucible according to the ratio of the mass of the positive electrode sheet to the volume of the ceramic crucible - g/mL is 1:10-1:15, Then put it in a box-type resistance furnace from room temperature to 550°C at a heating rate of 5°C/min and keep it warm for 0.5-1h, then turn off the power of the box-type resistance furnace and cool it down to room temperature naturally; take out the roasted positive electrode According to the ratio of the mass of the positive electrode sheet to the volume of water - g/mL is 1:40-1:70, put the positive electrode sheet into a container filled with water and stir it with an electric stirrer for 5-30min. The temperature is 20-50°C, and the stirring speed is 10-200r/min; after the stirring is stopped, the mixture in the container is sieved with a 10-20 mesh screen. solution; the aluminum foil was washed with water for 1-3 times, and the aluminum foil was obtained by natural drying; the undersieve was subjected to suction filtration, and the supernatant was washed with water for 1-3 times to obtain the positive electrode active material;

Step (3): Put the positive electrode active material obtained in step (2) into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 500-700°C at a heating rate of 5°C/min and keep it warm for 0.5 -3h, obtain waste lithium cobalt oxide powder;

Step (4): Mix the waste lithium cobaltate powder obtained in step (3) with sodium pyrosulfate at a mass ratio of -g/g in a ratio of 1:0.3-1:1.7, then put it into a ceramic mortar, grind and mix well, Put the ground mixture into a ceramic crucible and cover it with a ceramic cover, then put it into a box-type resistance furnace for roasting, raise the furnace temperature to 400-650°C at a heating rate of 3-10°C/min and keep it warm for 10-60min ; In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical product purchased;

Step (5): After the calcination, the material in the crucible is leached with water at 20-50°C under the condition of stirring, the leaching time is 5-30min, and the solid-liquid ratio-g/mL is 1:10-1:50 Then the leachate is heated to 95-98°C, 1.0-3.0mol/L sodium carbonate solution is slowly added to the leachate, then filtered, the filter residue is washed and dried, and the content of Li and Co in the filter residue is analyzed, according to the molar ratio of lithium to cobalt To meet the requirements of 1.05:1, add a certain amount of lithium carbonate to the filter residue, and then fully spheroidize the ball in the planetary ball mill. The ball milling time is 0.5-2h, the speed is 200-500r/min, and then it is pressed under the pressure of 0.1-100MPa Put it into a clean ceramic crucible, keep the temperature at 650-700°C for 2-6h in the air atmosphere, then raise the temperature to 900°C for 10h, then cool slowly to room temperature, crush and grind the fired samples, and pass through a 500-mesh sieve , to obtain lithium cobalt oxide positive electrode material with good electrochemical performance;

Step (6): Filter the solution obtained in step (5) to adjust the composition with concentrated sulfuric acid so that the pH of the solution is 0.5-1.0, and then crystallize in an evaporation crystallizer. The crystallization control conditions are vacuum degree 0.012-0.015MPa, temperature 120 -140°C, dry the crystals at 50-80°C for 0.2-3h to obtain sodium bisulfate.

According to the regeneration method described above, the mixing ratio of the spent lithium cobaltate powder and sodium pyrosulfate in step (4) is: the mass ratio -g/g is 1:0.3-1:1.7.

According to the regeneration method described above, the process conditions for calcination in a resistance furnace in step (4): the heating rate is 3-10°C/min, the calcination temperature is 400-650°C, and the holding time is 10-60min.

According to the regeneration method described above, the leaching temperature in step (5) is 20-50°C, the leaching time is 5-30min, and the solid-to-liquid ratio-g/mL is 1:10-1:50.

Example 1

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:1.14 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 2

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:1.14 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 550°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 3

Collect positive electrode scraps and positive electrode residues produced in the lithium-ion battery manufacturing process with lithium cobalt oxide as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace In the process, the furnace temperature was raised to 600° C. at a heating rate of 5° C./min and kept for 30 minutes to obtain waste lithium cobaltate powder; the waste lithium cobaltate powder obtained by recycling and sodium pyrosulfate in mass ratio (g/g) was The ratio of 1:1.14 was put into a ceramic mortar and thoroughly ground and mixed evenly, then the ground mixture was put into a ceramic crucible and covered with a ceramic cover, and placed in a box-type resistance furnace at a heating rate of 5°C/min. Raise to 500°C and keep it warm for 30min; after the roasting, leaching the contents of the crucible with 50°C water under stirring conditions with a solid-to-liquid ratio (g/mL) of 1:20 for 30min; then raise the temperature of the leaching solution to 98°C , 3.0mol/L sodium carbonate solution is slowly added to the leachate to produce a precipitate, the gained precipitate is filtered, washed and dried, and the content of Li and Co in the precipitate is analyzed, according to the molar ratio of lithium to cobalt is 1.05:1 It is required to add a certain amount of lithium carbonate to the sediment, and then fully spheroidize it at a speed of 400r/min in a planetary ball mill for 2 hours, then press it under a pressure of 10MPa, put it into a clean ceramic crucible, and place it in an air atmosphere. Keep the temperature at 650°C for 6 hours, then raise the temperature to 900°C for 10 hours, then cool slowly to room temperature, grind and grind the fired samples, and pass through a 500-mesh sieve to obtain a lithium cobaltate cathode material with good electrochemical performance; filter the The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C for 2 hours to obtain sodium bisulfate .

Example 4

Collect positive electrode scraps and positive electrode residues produced in the lithium-ion battery manufacturing process with lithium cobalt oxide as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace In the process, the furnace temperature was raised to 600° C. at a heating rate of 5° C./min and kept for 30 minutes to obtain waste lithium cobaltate powder; the waste lithium cobaltate powder obtained by recycling and sodium pyrosulfate in mass ratio (g/g) was The ratio of 1:1.14 was put into a ceramic mortar and thoroughly ground and mixed evenly, then the ground mixture was put into a ceramic crucible and covered with a ceramic cover, and placed in a box-type resistance furnace at a heating rate of 5°C/min. Raise to 450°C and keep it warm for 30 minutes; after the roasting, leaching the contents of the crucible with 50°C water under stirring conditions at a solid-to-liquid ratio (g/mL) of 1:20 for 30 minutes; then raise the temperature of the leaching solution to 98°C , 3.0mol/L sodium carbonate solution is slowly added to the leachate to produce a precipitate, the gained precipitate is filtered, washed and dried, and the content of Li and Co in the precipitate is analyzed, according to the molar ratio of lithium to cobalt is 1.05:1 It is required to add a certain amount of lithium carbonate to the sediment, and then fully spheroidize it at a speed of 400r/min in a planetary ball mill for 2 hours, then press it under a pressure of 10MPa, put it into a clean ceramic crucible, and place it in an air atmosphere. Keep the temperature at 650°C for 6 hours, then raise the temperature to 900°C for 10 hours, then cool slowly to room temperature, grind and grind the fired samples, and pass through a 500-mesh sieve to obtain a lithium cobaltate cathode material with good electrochemical performance; filter the The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C for 2 hours to obtain sodium bisulfate .

Example 5

Collect positive electrode scraps and positive electrode residues produced in the lithium-ion battery manufacturing process with lithium cobalt oxide as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace In the process, the furnace temperature was raised to 600° C. at a heating rate of 5° C./min and kept for 30 minutes to obtain waste lithium cobaltate powder; the waste lithium cobaltate powder obtained by recycling and sodium pyrosulfate in mass ratio (g/g) was The ratio of 1:0.68 was put into a ceramic mortar and thoroughly ground and mixed evenly, then the ground mixture was put into a ceramic crucible and covered with a ceramic cover and placed in a box-type resistance furnace at a heating rate of 5°C/min. Raise to 600°C and keep it warm for 30min; after roasting, leaching the contents of the crucible with 50°C water with a solid-to-liquid ratio (g/mL) of 1:20 for 30min while stirring; then raise the temperature of the leaching solution to 98°C , 3.0mol/L sodium carbonate solution is slowly added to the leachate to produce a precipitate, the gained precipitate is filtered, washed and dried, and the content of Li and Co in the precipitate is analyzed, according to the molar ratio of lithium to cobalt is 1.05:1 It is required to add a certain amount of lithium carbonate to the sediment, and then fully spheroidize it at a speed of 400r/min in a planetary ball mill for 2 hours, then press it under a pressure of 10MPa, put it into a clean ceramic crucible, and place it in an air atmosphere. Keep the temperature at 650°C for 6 hours, then raise the temperature to 900°C for 10 hours, then cool slowly to room temperature, grind and grind the fired samples, and pass through a 500-mesh sieve to obtain a lithium cobaltate cathode material with good electrochemical performance; filter the The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C for 2 hours to obtain sodium bisulfate .

Example 6

Collect positive electrode scraps and positive electrode residues produced in the lithium-ion battery manufacturing process with lithium cobalt oxide as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace In the process, the furnace temperature was raised to 600° C. at a heating rate of 5° C./min and kept for 30 minutes to obtain waste lithium cobaltate powder; the waste lithium cobaltate powder obtained by recycling and sodium pyrosulfate in mass ratio (g/g) was The ratio of 1:0.68 was put into a ceramic mortar and thoroughly ground and mixed evenly, then the ground mixture was put into a ceramic crucible and covered with a ceramic cover and placed in a box-type resistance furnace at a heating rate of 5°C/min. Raise to 550°C and keep it warm for 30 minutes; after the roasting, leaching the contents of the crucible with 50°C water under stirring conditions at a solid-to-liquid ratio (g/mL) of 1:20 for 30 minutes; then raise the temperature of the leaching solution to 98°C , 3.0mol/L sodium carbonate solution is slowly added to the leachate to produce a precipitate, the gained precipitate is filtered, washed and dried, and the content of Li and Co in the precipitate is analyzed, according to the molar ratio of lithium to cobalt is 1.05:1 It is required to add a certain amount of lithium carbonate to the sediment, and then fully spheroidize it at a speed of 400r/min in a planetary ball mill for 2 hours, then press it under a pressure of 10MPa, put it into a clean ceramic crucible, and place it in an air atmosphere. Keep the temperature at 650°C for 6 hours, then raise the temperature to 900°C for 10 hours, then cool slowly to room temperature, grind and grind the fired samples, and pass through a 500-mesh sieve to obtain a lithium cobaltate cathode material with good electrochemical performance; filter the The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C for 2 hours to obtain sodium bisulfate .

Example 7

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:0.68 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 500°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 8

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:0.68 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 400°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 3.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 9

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:1.7 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:30; then the leachate was heated to 98°C, and 3.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 10

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:0.3 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is loaded Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 40°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 95°C, and 3.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 11

Collect positive electrode scraps and positive electrode residues produced in the lithium-ion battery manufacturing process with lithium cobalt oxide as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace In the process, the furnace temperature was raised to 600° C. at a heating rate of 5° C./min and kept for 30 minutes to obtain waste lithium cobaltate powder; the waste lithium cobaltate powder obtained by recycling and sodium pyrosulfate in mass ratio (g/g) was The ratio of 1:1.14 was put into a ceramic mortar and thoroughly ground and mixed evenly, then the ground mixture was put into a ceramic crucible and covered with a ceramic cover, and placed in a box-type resistance furnace at a heating rate of 5°C/min. Raise to 600°C and keep it warm for 20 minutes; after the roasting, leaching the contents of the crucible with 50°C water with a solid-to-liquid ratio (g/mL) of 1:20 for 30 minutes while stirring; then raise the temperature of the leaching solution to 98°C 1.0mol/L sodium carbonate solution is slowly added to the leachate to produce a precipitate. After the gained precipitate is filtered, washed and dried, the content of Li and Co in the precipitate is analyzed. It is required to add a certain amount of lithium carbonate to the sediment, and then fully spheroidize it at a speed of 400r/min in a planetary ball mill for 2 hours, then press it under a pressure of 10MPa, put it into a clean ceramic crucible, and place it in an air atmosphere. Keep the temperature at 650°C for 6 hours, then raise the temperature to 900°C for 10 hours, then cool slowly to room temperature, grind and grind the fired samples, and pass through a 500-mesh sieve to obtain a lithium cobaltate cathode material with good electrochemical performance; filter the The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C for 2 hours to obtain sodium bisulfate .

Example 12

Collect positive electrode scraps and positive electrode residues produced in the lithium-ion battery manufacturing process with lithium cobalt oxide as the positive electrode material to obtain the positive electrode sheet; Put the positive electrode piece into a ceramic crucible, and then place it in a box-type resistance furnace to raise the temperature of the furnace to 550 °C at a rate of 5 °C/min from room temperature and keep it for 20 min. Room temperature; take out the positive electrode sheet after roasting, put the positive electrode sheet into a container filled with water according to the ratio of the mass of the positive electrode sheet to the volume of water (g/mL) of 1:50 and stir with an electric stirrer at 50r/min Stir at a high speed for 20 minutes, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, sieve the mixture in the container with a 10-mesh sieve, the sieve is aluminum foil, and the sieve is a solution containing positive active substances; Rinse with water 3 times, and obtain aluminum foil by natural drying; filter the undersieve, and wash the supernatant with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace In the process, the furnace temperature was raised to 600° C. at a heating rate of 5° C./min and kept for 30 minutes to obtain waste lithium cobaltate powder; the waste lithium cobaltate powder obtained by recycling and sodium pyrosulfate in mass ratio (g/g) was The ratio of 1:1.14 was put into a ceramic mortar and thoroughly ground and mixed evenly, then the ground mixture was put into a ceramic crucible and covered with a ceramic cover, and placed in a box-type resistance furnace at a heating rate of 5°C/min. Raise to 550°C and keep it warm for 20 minutes; after the roasting, leaching the contents of the crucible with 50°C water under stirring conditions at a solid-to-liquid ratio (g/mL) of 1:20 for 30 minutes; then raise the temperature of the leaching solution to 98°C 1.0mol/L sodium carbonate solution is slowly added to the leachate to produce a precipitate. After the gained precipitate is filtered, washed and dried, the content of Li and Co in the precipitate is analyzed. It is required to add a certain amount of lithium carbonate to the sediment, and then fully spheroidize it at a speed of 400r/min in a planetary ball mill for 2 hours, then press it under a pressure of 10MPa, put it into a clean ceramic crucible, and place it in an air atmosphere. Keep the temperature at 650°C for 6 hours, then raise the temperature to 900°C for 10 hours, then cool slowly to room temperature, grind and grind the fired samples, and pass through a 500-mesh sieve to obtain a lithium cobaltate cathode material with good electrochemical performance; filter the The obtained solution was adjusted with concentrated sulfuric acid to make the pH value of the solution 1.0, and then crystallized in an evaporative crystallizer. The crystallization control conditions were vacuum degree of 0.015MPa and temperature of 120°C. The crystallized product was dried at 80°C for 2 hours to obtain sodium bisulfate .

Example 13

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:1.14 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 500°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 20 minutes at a solid-to-liquid ratio (g/mL) of 1:20; then the leachate was heated to 98°C, and 1.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 14

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:1.14 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 600°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:40; then the leachate was heated to 98°C, and 1.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900°C and keep it for 10h, then slowly cool to room temperature, after firing The sample is pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobalt oxide positive electrode material with good electrochemical performance; the solution obtained by filtering in the above steps is adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then crystallized in an evaporation crystallizer , the crystallization control conditions are vacuum degree 0.015MPa, temperature 120°C, crystallization is dried at 80°C and 2h to obtain sodium bisulfate.

Example 15

Collect scrap lithium-ion batteries with lithium cobaltate as positive electrode material, place them in 1.0mol/L sodium hydroxide aqueous solution at room temperature for 2h discharge treatment; after discharge treatment, disassemble the scrap lithium-ion batteries to obtain Positive electrode sheet: according to the ratio (g/mL) of the mass of positive electrode sheet and the volume of ceramic crucible, positive electrode sheet is packed in the ratio of 1:15 in the ceramic crucible, is placed in box-type electric resistance furnace then and starts from room temperature with 5 ℃/mL The heating rate of min raised the furnace temperature to 550°C and kept it warm for 20 minutes, then cut off the power of the box-type resistance furnace, and cooled it to room temperature naturally; took out the roasted positive electrode sheet, and according to the ratio of the mass of the positive electrode sheet to the volume of water (g/ mL) is 1:50, put the positive electrode sheet into a container with water and stir it with an electric stirrer at a stirring speed of 50r/min for 20min, and the temperature of the water during the stirring process is 30°C; after the stirring is stopped, the mixture in the container Sieve with a 10-mesh sieve, the oversieve is aluminum foil, and the undersieve is a solution containing positive active substances; the aluminum foil is washed 3 times with water, and the aluminum foil is obtained by natural drying; the undersieve is subjected to suction filtration, and the oversieve is washed with water 3 times to obtain the positive active material; put the obtained positive active material into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 600 ° C at a heating rate of 5 ° C / min and keep it for 30 min to obtain waste cobalt Lithium acid powder; the waste lithium cobaltate powder and sodium pyrosulfate obtained by recycling are put into a ceramic mortar in a ratio of 1:1.14 by mass ratio (g/g), and they are fully ground and mixed evenly, and then the ground mixture is packed Put it into a ceramic crucible and cover it with a ceramic cover, put it into a box-type resistance furnace, raise the temperature of the furnace to 450°C at a heating rate of 5°C/min and keep it warm for 30min; The water at 50°C was leached for 30min at a solid-to-liquid ratio (g/mL) of 1:40; then the leachate was heated to 98°C, and 1.0mol/L sodium carbonate solution was slowly added to the leachate to produce a precipitate, which was filtered, After washing and drying, analyze the content of Li and Co in the precipitate, add a certain amount of lithium carbonate to the precipitate according to the requirement that the molar ratio of lithium to cobalt is 1.05:1, and then in the planetary ball mill at a speed of 400r/min Fully spheroidal ink for 2 hours, then press it under the pressure of 10MPa, put it into a clean ceramic crucible, keep the temperature at 650°C in the air atmosphere for 6h, then raise the temperature to 900 ^° C and keep it for 10h, then slowly cool to room temperature, after firing The samples were pulverized, ground, and passed through a 500-mesh sieve to obtain a lithium cobaltate positive electrode material with good electrochemical properties; the solution obtained by filtering in the above steps was adjusted with concentrated sulfuric acid to make the pH of the solution 1.0, and then in an evaporation crystallizer Crystallization, the crystallization control conditions are vacuum degree of 0.015MPa, temperature of 120°C, and the crystallization is dried at 80°C for 2 hours to obtain sodium bisulfate.

Claims (1)

1. the regeneration method of cathode active material in lithium cobalt oxide waste lithium ion battery, it is characterized in that, the method may further comprise the steps: Step (1): Place the collected scrap lithium-ion battery with lithium cobaltate as positive electrode material in 0.1-1.0mol/L sodium hydroxide aqueous solution at room temperature for 1-3h discharge treatment; after discharge treatment, Disassemble the scrapped lithium-ion battery to obtain the positive electrode sheet; collect the positive electrode scraps and positive electrode scraps generated during the manufacturing process of the lithium-ion battery with lithium cobaltate as the positive electrode material to obtain the positive electrode sheet; Step (2): Put the positive electrode sheet obtained in step (1) into the ceramic crucible according to the ratio of the mass of the positive electrode sheet to the volume of the ceramic crucible - g/mL is 1:10-1:15, Then put it in a box-type resistance furnace from room temperature to 550°C at a heating rate of 5°C/min and keep it warm for 0.5-1h, then turn off the power of the box-type resistance furnace and cool it down to room temperature naturally; take out the roasted positive electrode According to the ratio of the mass of the positive electrode sheet to the volume of water - g/mL is 1:40-1:70, put the positive electrode sheet into a container filled with water and stir it with an electric stirrer for 5-30min. The temperature is 20-50°C, and the stirring speed is 10-200r/min; after the stirring is stopped, the mixture in the container is sieved with a 10-20 mesh screen. solution; the aluminum foil was washed with water for 1-3 times, and the aluminum foil was obtained by natural drying; the undersieve was subjected to suction filtration, and the supernatant was washed with water for 1-3 times to obtain the positive electrode active material; Step (3): Put the positive electrode active material obtained in step (2) into a ceramic crucible, and then place it in a box-type resistance furnace to raise the furnace temperature to 500-700°C at a heating rate of 5°C/min and keep it warm for 0.5 -3h, obtain waste lithium cobalt oxide powder; Step (4): Mix the waste lithium cobaltate powder obtained in step (3) with sodium pyrosulfate at a mass ratio of -g/g in a ratio of 1:0.3-1:1.7, then put it into a ceramic mortar, grind and mix well, Put the ground mixture into a ceramic crucible and cover it with a ceramic cover, then put it into a box-type resistance furnace for roasting, raise the furnace temperature to 400-650°C at a heating rate of 3-10°C/min and keep it warm for 10-60min ; In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical product purchased; Step (5): After the calcination, the material in the crucible is leached with water at 20-50°C under the condition of stirring, the leaching time is 5-30min, and the solid-liquid ratio-g/mL is 1:10-1:50 Then the leachate is heated to 95-98°C, 1.0-3.0mol/L sodium carbonate solution is slowly added to the leachate, then filtered, the filter residue is washed and dried, and the content of Li and Co in the filter residue is analyzed, according to the molar ratio of lithium to cobalt To meet the requirements of 1.05:1, add a certain amount of lithium carbonate to the filter residue, and then fully spheroidize the ball in the planetary ball mill. The ball milling time is 0.5-2h, the speed is 200-500r/min, and then it is pressed under the pressure of 0.1-100MPa Put it into a clean ceramic crucible, keep the temperature at 650-700°C for 2-6h in the air atmosphere, then raise the temperature to 900°C for 10h, then cool slowly to room temperature, crush and grind the fired samples, and pass through a 500-mesh sieve , to obtain lithium cobalt oxide positive electrode material with good electrochemical performance; Step (6): Filter the solution obtained in step (5) to adjust the composition with concentrated sulfuric acid so that the pH of the solution is 0.5-1.0, and then crystallize in an evaporation crystallizer. The crystallization control conditions are vacuum degree 0.012-0.015MPa, temperature 120 -140°C, dry the crystals at 50-80°C for 0.2-3h to obtain sodium bisulfate.