CN104466293B

CN104466293B - The renovation process of lithium ion cell anode material lithium cobaltate waste material

Info

Publication number: CN104466293B
Application number: CN201410834033.6A
Authority: CN
Inventors: 陈怀敬; 王大辉; 文豪
Original assignee: Lanzhou University of Technology
Current assignee: Lanzhou University of Technology
Priority date: 2014-12-30
Filing date: 2014-12-30
Publication date: 2016-08-31
Anticipated expiration: 2034-12-30
Also published as: CN104466293A

Abstract

The renovation process of lithium ion cell anode material lithium cobaltate waste material, the steps include: to carry out used Li ion cell discharging, disassembling the useless positive plate of acquisition, and useless positive plate roasting, water dissolution, filtration obtain useless cobalt acid lithium powder；Roasting after useless cobalt acid lithium powder is mixed by a certain percentage with potassium acid sulfate, product of roasting water logging goes out, then filter after adding solution of potassium carbonate in solution, filtering residue supplements its ball milling after a certain amount of lithium carbonate, compress, put into resistance kiln roasting, regain the lithium cobaltate cathode material that chemical property is good.The potassium acid sulfate that filtrate obtains after adjusting pH value with sulphuric acid and carry out crystallization treatment can be reused.

Description

The renovation process of lithium ion cell anode material lithium cobaltate waste material

Technical field

The present invention relates to the regeneration techniques of lithium ion cell anode material lithium cobaltate waste material.

Background technology

Lithium ion battery is the secondary cell of new generation developed rapidly the nineties in 20th century, is widely used in miniature portable Formula telecommunications product and electric vehicle.According to statistics, within 2009, China's lithium ion battery yield reaches 18.7 hundred million, 2010 The yield of China's lithium ion battery reaches 26.8 hundred million.Owing to the service life of lithium ion battery is generally 2-3, therefore, report Environmental pollution and problem of resource waste that used Li ion cell brings also become increasingly conspicuous, and the most rationally dispose waste lithium ion Problem can not be ignored.Recycling to resources such as Co, Ni, Mn, Li, Al and Cu in used Li ion cell, both gram Take discarding method and disposed scrap lithium ion battery pollution on the environment, the most also made limited resource be circulated profit With, not only there is great economic benefit, be also significant in terms of environmental conservation.

The positive electrode that lithium ion battery uses is one of critical material manufacturing lithium ion battery, in lithium ion battery Occupy core status.The positive electrode of commercial application the most mainly has cobalt acid lithium, LiMn2O4, cobalt nickel lithium manganate ternary material And LiFePO4, wherein, cobalt acid lithium is still mainstay material, be mainly used in the small-sized high-energy density lithium of high-end electronic product from Sub-field of batteries.

The renovation process of the lithium ion cell anode material lithium cobaltate waste material disclosing report mainly has, Zhang P W Salt Ore Leaching lithium-ion electric is used Deng reporting in " Hydrometallurgy " Vol.47 No.2-3,1998,259-271 Pond anode waste, then obtain cobaltous sulfate and lithium carbonate through operations such as extraction, precipitations.Wu Fang is at " China YouSe Acta Metallurgica Sinica " Vol.14 No.4,2004,697-701 reports the anode waste employing obtained in used Li ion cell at high temperature use Sulphuric acid and hydrogen peroxide Ore Leaching, then obtain cobaltous sulfate and lithium carbonate through extraction, precipitation operation.Myoung J etc. are at " Journal Of Power Sources " Vol.112,2002,639-642 reports dissolve in used Li ion cell with hot nitric acid and obtain Anode waste, be then passed through after electro-deposition operation, low temperature calcination obtaining Co₃O₄.Patent [CN201210491084] reports one Plant from waste and old lithium ion battery, produce Co₃O₄Method, by scrap lithium ion battery positive pole impregnate in organic solvent, just make Pole powder body material and aluminum foil current collector are separated, then add roasting after organic fluorocompound in positive pole powder material, obtain Co₃O₄ Material.Patent [CN201180048492] reports a kind of method for reclaiming Li ion, by introducing one or more rings Siloxanes, so that lithium ion forms one or more cyclosiloxane-Li ionic complex, then will be containing cyclosiloxane-Li ion The organic facies of coordination compound is separated from the water.Patent [CN200910117702] reports by by useless LiCoO₂Powder and alkali metal Roasting at a temperature of higher after the salt mixing of sodium and potassium, product of roasting is going out with water logging, and leachate is through heavy cobalt and sinker operation Obtain cobalt oxalate and lithium carbonate.Patent [CN200910093727] reports one and utilizes waste and old lithium ion battery recovery to prepare cobalt The method of acid lithium, by by waste and old lithium ion battery electric eliminating, split, pulverize, NMP process, calcining, obtain waste and old LiCoO₂Material Material, then by LiCoO₂Material mix with natural organic acids and hydrogen peroxide after ball milling, and obtain Li⁺、Co²⁺Solution, at solution Middle dropping ammonia prepares xerogel and secondary clacining obtains cobalt acid lithium electrode material.Patent [CN200910039217] discloses one Plant recovery and the regeneration method of waste lithium ion battery cathode material, by being broken by used Li ion cell cathode waste Broken, grind, except aluminum, acidleach, extraction copper, chemical subtraction, precipitate, add lithium source secondary high-temperature baking operation, it is achieved cathode material is again Raw.Patent [CN200810028730] discloses a kind of method reclaiming from waste and old lithium ion battery, preparing cobalt acid lithium.Pass through After lithium ion battery positive plate pulverizing, screening, it is thus achieved that useless cobalt acid lithium；Binding agent, conduction is removed in constant temperature resistance furnace Agent acetylene black, allocates the lithium carbonate of proper proportion into, the cobalt acid lithium battery material that high temperature sintering synthesis is active in Muffle furnace. Patent [CN200710057623] discloses a kind of waste lithium ion cell anode material lithium cobaltate activating process.By waste and old lithium from Sub-cell positive material at high temperature removes binding agent PVDF, at high temperature calcining cobalt acid lithium, makes inefficacy cobalt acid lithium produce crystallization Reaction, possesses layer structure again.Patent [CN200510018601] reports a kind of positive pole material from waste and old lithium ion battery The method of separating and recovering cobalt in material cobalt acid lithium.Waste and old lithium ion battery carries out after physics is disassembled, calcined, organic solvent soaks, To useless cobalt acid lithium, being placed under acid condition of useless cobalt acid lithium is used H₂O₂Or Na₂S₂O₃As reducing agent, dissolve and obtain containing Co²⁺ And Li⁺Solution, then with NaOH solution as precipitant, by the Co in solution²⁺Ion conversion becomes Co (OH)₂Precipitation.Patent [CN200510015078] discloses a kind of recovery from the lithium ion battery scrapped and prepares Li_xCoO₂Method.By used Li ion Cell positive material is cut into fractionlet and is immersed in METHYLPYRROLIDONE liquid, separates and obtains active substance Li_xCoO₂ Black powder, then black powder is scattered in salpeter solution or hydrochloric acid solution, then through filtration, precipitation operation, it is blue heavy to obtain Form sediment, precipitate at high temperature roasting, obtain Li_xCoO₂Powder body.

At present it has been reported that lithium ion cell anode material lithium cobaltate waste material renovation process in use sulphuric acid to add dioxygen Water, sodium thiosulfate, hydrochloric acid, nitric acid dissolve useless LiCoO₂Cobalt acid lithium is regained again, leaching through remove impurity, precipitation, calcination operation It is inevitably generated during going out containing acid gas, Cl₂Or NO_xWaste gas, it is dirty that removal process causes serious secondary to environment Dye.Additionally, the subsequent treatment operation of leachate is many, long flow path causes cost recovery high；Leaching process is in order to improve metal recovery Rate and shortening extraction time the most all have employed higher acid concentration and extraction temperature, and leaching equipment antiseptical is required the highest by this. Use useless LiCoO₂Powder mix with the salt of alkali metallic sodium and potassium after the method for roasting, also exist in roasting process alkali metallic sodium and The salt consumption of potassium is big, precipitant oxalates consumption is many in removal process, causes the shortcoming that cost recovery is high；Use useless LiCoO₂Material , there is removal process and easily make ball-grinding machine be corroded and introduce in ball grinding technique after expecting to mix with natural organic acids and hydrogen peroxide The shortcoming of impurity.Positive active material under peeling off on used Li ion cell positive plate is at high temperature calcined and is regained cobalt Cobalt acid lithium electrochemical performance prepared by the method for acid lithium can not meet performance of lithium ion battery requirement.

Summary of the invention

It is an object of the invention to provide the renovation process of a kind of lithium ion cell anode material lithium cobaltate waste material.

The present invention is the renovation process of lithium ion cell anode material lithium cobaltate waste material, the steps include:

Step (1): by collect come do the scrap lithium ion battery of positive electrode with cobalt acid lithium and be at room temperature positioned over The sodium hydrate aqueous solution of 0.1-1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium-ion electric that will scrap Pond is disassembled, it is thus achieved that positive plate；Collect and do, with cobalt acid lithium, the positive pole limit that the lithium ion battery manufacture process of positive electrode produces Corner material, positive pole relic, it is thus achieved that positive plate；

Step (2): by the positive plate that obtains in step (1) by the ratio of the quality of positive plate and the volume of ceramic crucible- G/mL is that positive plate is loaded in ceramic crucible by the ratio of 1:10-1:15, is subsequently placed in chamber type electric resistance furnace and starts with 5 from room temperature DEG C/heating rate of min makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h, then make chamber type electric resistance furnace power-off, naturally cool to room Temperature；Take out through the positive plate of roasting, be that 1:40-1:70 will just according to the quality of positive plate with the ratio-g/mL of the volume of water Pole piece is put into equipped with stirring 5-30min in the container of water and with motor stirrer, and in whipping process, the temperature of water is 20-50 DEG C, Mixing speed is 10-200r/min；After stopping stirring, the screen cloth of the mixture 10-20 mesh in container is sieved, on sieve Thing is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying； Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；

Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in box resistance Stove make furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；

Step (4): useless cobalt acid lithium powder step (3) obtained and potassium acid sulfate-g/g in mass ratio are 1:0.4-1:2 Ratio mixing after put into ceramic mortar be fully ground mix homogeneously, the mixture after grinding loads ceramic crucible and adds pottery Porcelain lid covers, and is then placed in roasting in chamber type electric resistance furnace, makes furnace temperature be raised to 400-650 DEG C also with the heating rate of 3-10 DEG C/min Insulation 10-60min；

Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, Extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, by 1.0- The solution of potassium carbonate of 3.0mol/L is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes Li, Co in filtering residue Content, supplements a certain amount of lithium carbonate toward filtering residue, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt Abundant spheroidal graphite in grinding machine, Ball-milling Time is 0.5-2h, and rotating speed is 200-500r/min, then by it under the pressure of 0.1-100MPa Compress, put in clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, then be warming up to 900 DEG C of insulations It is slowly cooled to room temperature after 10h, the sample comminution after firing, grinding, crosses 500 mesh sieves, it is thus achieved that the cobalt acid that chemical property is good Lithium anode material；

Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, Then crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystallization Thing is dried under 50-80 DEG C and 0.2-3h and obtains potassium acid sulfate, it is thus achieved that potassium acid sulfate return in step (4) and use.

The present invention has that technological process is short, cost recovery is low compared with the prior art, easy operation, to equipment anticorrosion requirement Low, regeneration cobalt acid lithium electrochemical is functional, the advantage that do not produces secondary pollution in processing procedure.

Detailed description of the invention

Renovation process in accordance with the above, the potassium acid sulfate described in step (4) is: the chemical products of potassium acid sulfate or The potassium acid sulfate obtained in step (6) or the two mixture being mixed to form with arbitrary proportion；

The mixing ratio of renovation process in accordance with the above, the useless cobalt acid lithium powder described in step (4) and potassium acid sulfate Example is: mass ratio-g/g is 1:0.4-1:2.

Renovation process in accordance with the above, the process conditions of resistance kiln roasting in step (4): heating rate is 3-10 DEG C/min, sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.

Renovation process in accordance with the above, the extraction temperature described in step (5) is 20-50 DEG C, extraction time 5- 30min, solid-to-liquid ratio-g/mL are 1:10-1:50.

Embodiment 1:

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the potassium acid sulfate chemical industry of purchase Product (g/g) in mass ratio is that the ratio of 1:1.39 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 600 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, is slowly added to the solution of potassium carbonate of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to lithium and cobalt The requirement that mol ratio is 1.05:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant spheroidal graphite 2h of min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at air atmosphere In in 650 DEG C of constant temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps Adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 2

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the potassium acid sulfate chemical industry of purchase Product (g/g) in mass ratio is that the ratio of 1:1.39 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 550 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, is slowly added to the solution of potassium carbonate of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to lithium and cobalt The requirement that mol ratio is 1.05:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant spheroidal graphite 2h of min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at air atmosphere In in 650 DEG C of constant temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps Adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 3

Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and purchase Potassium acid sulfate chemical products (g/g) in mass ratio are that the ratio of 1:1.39 is put into and is fully ground mix homogeneously in ceramic mortar, so After will grind after mixture load ceramic crucible adding and on ceramic cap lid, put in chamber type electric resistance furnace the intensification speed with 5 DEG C/min Rate makes furnace temperature be raised to 500 DEG C and be incubated 30min；After roasting terminates, by the material in crucible stirring under conditions of with 50 DEG C Water is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, by the solution of potassium carbonate of 3.0mol/L Be slowly added to leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze containing of Li, Co in precipitate Amount, supplements a certain amount of lithium carbonate toward precipitate, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt With the speed abundant spheroidal graphite 2h of 400r/min in grinding machine, then it is compressed under the pressure of 10MPa, put into clean ceramic crucible In, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample after firing Product are pulverized, are ground, and cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Above-mentioned steps will be filtrated to get Solution concentrated sulphuric acid adjusting component make the pH value of solution be 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is Vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 4

Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and purchase Potassium acid sulfate chemical products (g/g) in mass ratio are that the ratio of 1:1.39 is put into and is fully ground mix homogeneously in ceramic mortar, so After will grind after mixture load ceramic crucible adding and on ceramic cap lid, put in chamber type electric resistance furnace the intensification speed with 5 DEG C/min Rate makes furnace temperature be raised to 450 DEG C and be incubated 30min；After roasting terminates, by the material in crucible stirring under conditions of with 50 DEG C Water is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, by the solution of potassium carbonate of 3.0mol/L Be slowly added to leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze containing of Li, Co in precipitate Amount, supplements a certain amount of lithium carbonate toward precipitate, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt With the speed abundant spheroidal graphite 2h of 400r/min in grinding machine, then it is compressed under the pressure of 10MPa, put into clean ceramic crucible In, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample after firing Product are pulverized, are ground, and cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Above-mentioned steps will be filtrated to get Solution concentrated sulphuric acid adjusting component make the pH value of solution be 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is Vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 5

Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the present invention The ratio that potassium acid sulfate (g/g) in mass ratio is 1:0.97 obtained in step (6) is put into and is fully ground mixing in ceramic mortar Uniformly, the mixture after then grinding loads ceramic crucible adding and puts on ceramic cap lid in chamber type electric resistance furnace with 5 DEG C/min Heating rate make furnace temperature be raised to 600 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring With the water of 50 DEG C with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by the carbon of 3.0mol/L Acid potassium solution is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze Li in precipitate, The content of Co, supplements a certain amount of lithium carbonate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt toward precipitate, is then expert at With the speed abundant spheroidal graphite 2h of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, fire After sample comminution, grinding, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；By mistake in above-mentioned steps The solution concentrated sulphuric acid adjusting component that filter obtains makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, cerium sulphate crystal Condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 6

Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the present invention The ratio that potassium acid sulfate (g/g) in mass ratio is 1:0.97 obtained in step (6) is put into and is fully ground mixing in ceramic mortar Uniformly, the mixture after then grinding loads ceramic crucible adding and puts on ceramic cap lid in chamber type electric resistance furnace with 5 DEG C/min Heating rate make furnace temperature be raised to 550 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring With the water of 50 DEG C with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by the carbon of 3.0mol/L Acid potassium solution is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze Li in precipitate, The content of Co, supplements a certain amount of lithium carbonate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt toward precipitate, is then expert at With the speed abundant spheroidal graphite 2h of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, fire After sample comminution, grinding, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；By mistake in above-mentioned steps The solution concentrated sulphuric acid adjusting component that filter obtains makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, cerium sulphate crystal Condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 7

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Useless cobalt acid lithium powder recycling obtained obtains in step of the present invention (6) The ratio that potassium acid sulfate (g/g) in mass ratio is 1:0.97 obtained is put into and is fully ground mix homogeneously in ceramic mortar, then will Mixture after grinding loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make with the heating rate of 5 DEG C/min Furnace temperature is raised to 500 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with Solid-to-liquid ratio (g/mL) is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, by slow for the solution of potassium carbonate of 3.0mol/L Add leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, press The requirement that mol ratio is 1.05:1 according to lithium Yu cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill With the speed of 400r/min abundant spheroidal graphite 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 8

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Useless cobalt acid lithium powder recycling obtained obtains in step of the present invention (6) The ratio that potassium acid sulfate (g/g) in mass ratio is 1:0.97 obtained is put into and is fully ground mix homogeneously in ceramic mortar, then will Mixture after grinding loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make with the heating rate of 5 DEG C/min Furnace temperature is raised to 400 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with Solid-to-liquid ratio (g/mL) is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, by slow for the solution of potassium carbonate of 3.0mol/L Add leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, press The requirement that mol ratio is 1.05:1 according to lithium Yu cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill With the speed of 400r/min abundant spheroidal graphite 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 9

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the potassium acid sulfate chemical industry of purchase Product (g/g) in mass ratio is that the ratio of 1:2 is put into and is fully ground mix homogeneously in ceramic mortar, the mixing after then grinding Thing loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to 600 with the heating rate of 5 DEG C/min DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/mL) 30min is leached for 1:20；Then leachate is warmed up to 98 DEG C, the solution of potassium carbonate of 3.0mol/L is slowly added to leachate and produces Raw precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to rubbing of lithium and cobalt You supplement a certain amount of lithium carbonate toward precipitate, then with 400r/min's in planetary ball mill than the requirement for 1.05:1 Speed abundant spheroidal graphite 2h, then it compressed under the pressure of 10MPa, puts in clean ceramic crucible, in air atmosphere in 650 DEG C of constant temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 500 Mesh sieve, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps is adjusted Being made into point pH value making solution is 1.0, then in crystallizing evaporator crystallize, cerium sulphate crystal condition be vacuum 0.015MPa, Temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 10

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the potassium acid sulfate chemical industry of purchase Product (g/g) in mass ratio is that the ratio of 1:0.4 is put into and is fully ground mix homogeneously in ceramic mortar, mixed after then grinding Compound loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 600 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 40 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:30 leaches 30min；Then leachate is warmed up to 95 DEG C, is slowly added to the solution of potassium carbonate of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to lithium and cobalt The requirement that mol ratio is 1.05:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant spheroidal graphite 2h of min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at air atmosphere In in 650 DEG C of constant temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps Adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 11

Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and the present invention The ratio that potassium acid sulfate (g/g) in mass ratio is 1:1.39 obtained in step (6) is put into and is fully ground mixing in ceramic mortar Uniformly, the mixture after then grinding loads ceramic crucible adding and puts on ceramic cap lid in chamber type electric resistance furnace with 5 DEG C/min Heating rate make furnace temperature be raised to 600 DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring With the water of 50 DEG C with solid-to-liquid ratio (g/mL) be 1:20 leach 30min；Then leachate is warmed up to 98 DEG C, by the carbon of 1.0mol/L Acid potassium solution is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze Li in precipitate, The content of Co, supplements a certain amount of lithium carbonate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt toward precipitate, is then expert at With the speed abundant spheroidal graphite 2h of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, fire After sample comminution, grinding, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；By mistake in above-mentioned steps The solution concentrated sulphuric acid adjusting component that filter obtains makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, cerium sulphate crystal Condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 12

Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The useless cobalt acid lithium powder that recycling is obtained and purchase Potassium acid sulfate chemical products (g/g) in mass ratio are that the ratio of 1:1.39 is put into and is fully ground mix homogeneously in ceramic mortar, so After will grind after mixture load ceramic crucible adding and on ceramic cap lid, put in chamber type electric resistance furnace the intensification speed with 5 DEG C/min Rate makes furnace temperature be raised to 550 DEG C and be incubated 20min；After roasting terminates, by the material in crucible stirring under conditions of with 50 DEG C Water is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, by the solution of potassium carbonate of 1.0mol/L Be slowly added to leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze containing of Li, Co in precipitate Amount, supplements a certain amount of lithium carbonate toward precipitate, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt With the speed abundant spheroidal graphite 2h of 400r/min in grinding machine, then it is compressed under the pressure of 10MPa, put into clean ceramic crucible In, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample after firing Product are pulverized, are ground, and cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Above-mentioned steps will be filtrated to get Solution concentrated sulphuric acid adjusting component make the pH value of solution be 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is Vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 13

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Useless cobalt acid lithium powder recycling obtained obtains in step of the present invention (6) The ratio that potassium acid sulfate (g/g) in mass ratio is 1:1.39 obtained is put into and is fully ground mix homogeneously in ceramic mortar, then will Mixture after grinding loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make with the heating rate of 5 DEG C/min Furnace temperature is raised to 500 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with Solid-to-liquid ratio (g/mL) is that 1:20 leaches 20min；Then leachate is warmed up to 98 DEG C, by slow for the solution of potassium carbonate of 1.0mol/L Add leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, press The requirement that mol ratio is 1.05:1 according to lithium Yu cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill With the speed of 400r/min abundant spheroidal graphite 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 14

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Useless cobalt acid lithium powder recycling obtained obtains in step of the present invention (6) The ratio that potassium acid sulfate (g/g) in mass ratio is 1:1.39 obtained is put into and is fully ground mix homogeneously in ceramic mortar, then will Mixture after grinding loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make with the heating rate of 5 DEG C/min Furnace temperature is raised to 600 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with Solid-to-liquid ratio (g/mL) is that 1:40 leaches 30min；Then leachate is warmed up to 98 DEG C, by slow for the solution of potassium carbonate of 1.0mol/L Add leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, press The requirement that mol ratio is 1.05:1 according to lithium Yu cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill With the speed of 400r/min abundant spheroidal graphite 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Embodiment 15

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Useless cobalt acid lithium powder recycling obtained obtains in step of the present invention (6) The ratio that potassium acid sulfate (g/g) in mass ratio is 1:1.39 obtained is put into and is fully ground mix homogeneously in ceramic mortar, then will Mixture after grinding loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make with the heating rate of 5 DEG C/min Furnace temperature is raised to 450 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with Solid-to-liquid ratio (g/mL) is that 1:40 leaches 30min；Then leachate is warmed up to 98 DEG C, by slow for the solution of potassium carbonate of 1.0mol/L Add leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, press The requirement that mol ratio is 1.05:1 according to lithium Yu cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill With the speed of 400r/min abundant spheroidal graphite 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains potassium acid sulfate.

Claims

1. the renovation process of lithium ion cell anode material lithium cobaltate waste material, it is characterised in that the method comprises the following steps:

Step (1): by collect come do the scrap lithium ion battery of positive electrode with cobalt acid lithium and be at room temperature positioned over 0.1- The sodium hydrate aqueous solution of 1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium ion battery scrapped is entered Row is disassembled, it is thus achieved that positive plate；Collect and make, with cobalt acid lithium, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；

Step (2): be 1:10 in the ratio of the quality of positive plate Yu the volume of ceramic crucible by the positive plate that obtains in step (1) Positive plate is loaded in ceramic crucible by g/mL-1:15 g/mL, is subsequently placed in chamber type electric resistance furnace and starts with 5 DEG C/min from room temperature Heating rate make furnace temperature be raised to 550 DEG C insulation 0.5-1h, then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out Through the positive plate of roasting, it is that 1:40 g/mL-1:70 g/mL is by positive pole according to the quality of positive plate with the ratio of the volume of water Sheet is put into equipped with stirring 5-30min in the container of water and with motor stirrer, and in whipping process, the temperature of water is 20-50 DEG C, stirs Mixing speed is 10-200r/min；After stopping stirring, the screen cloth of the mixture 10-20 mesh in container is sieved, oversize For aluminium foil, siftage is the solution containing positive active material；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying；Sieve Lower thing carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；

Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace Furnace temperature is made to be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；

Step (4): useless cobalt acid lithium powder step (3) obtained and potassium acid sulfate are in mass ratio for 1:0.4 g/g-1:2 g/g Ratio mixing after put into ceramic mortar be fully ground mix homogeneously, the mixture after grinding loads ceramic crucible and adds pottery Porcelain lid covers, and is then placed in roasting in chamber type electric resistance furnace, makes furnace temperature be raised to 400-650 DEG C also with the heating rate of 3-10 DEG C/min Insulation 10-60min；

Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, leaches Time 5-30min, solid-to-liquid ratio is 1:10 g/mL-1:50 g/mL；Then leachate is warmed up to 95-98 DEG C, by 1.0- The solution of potassium carbonate of 3.0mol/L is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes Li, Co in filtering residue Content, supplements a certain amount of lithium carbonate toward filtering residue, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt Abundant ball milling in grinding machine, Ball-milling Time is 0.5-2h, and rotating speed is 200-500r/min, then by it under the pressure of 0.1-100MPa Compress, put in clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, then be warming up to 900 DEG C of insulations It is slowly cooled to room temperature after 10h, the sample comminution after firing, grinding, crosses 500 mesh sieves, it is thus achieved that lithium cobaltate cathode material；

Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, then Crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, and crystal exists Be dried under 50-80 DEG C and 0.2-3h and obtain potassium acid sulfate, it is thus achieved that potassium acid sulfate return in step (4) and use.