CN104485494B

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

Info

Publication number: CN104485494B
Application number: CN201410834047.8A
Authority: CN
Inventors: 王大辉; 文豪; 陈怀敬; 黄允文; 曹胜强; 赵午祥
Original assignee: Lanzhou University of Technology
Current assignee: Lanzhou University of Technology
Priority date: 2014-12-30
Filing date: 2014-12-30
Publication date: 2016-07-06
Anticipated expiration: 2034-12-30
Also published as: CN104485494A

Abstract

The renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell, the steps include: to be undertaken 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 sodium pyrosulfate, product of roasting water logging goes out, then filter after adding sodium carbonate liquor 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.Filtrate obtains sodium bisulfate with carrying out crystallization treatment after sulphuric acid adjusting component.

Description

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

Technical field

The present invention relates to the regeneration techniques of positive electrode active materials in cobalt acid lithium used Li ion cell.

Background technology

Lithium ion battery is the secondary cell of new generation developed rapidly the nineties in 20th century, is widely used in small-sized portable electronic communication product and electric vehicle.According to statistics, within 2009, China's lithium ion battery yield reaches 18.7 hundred million, and the yield of China's lithium ion battery in 2010 reaches 26.8 hundred million.Owing to the service life of lithium ion battery is generally 2-3, therefore, environmental pollution and problem of resource waste that scrap lithium ion battery is brought also become increasingly conspicuous, and the problem how rationally disposing waste lithium ion can not be ignored.Recycling to resources such as Co, Ni, Mn, Li, Al and Cu in used Li ion cell; both overcome discarding method and dispose scrap lithium ion battery pollution on the environment; also make limited resource be recycled simultaneously; not only there is great economic benefit, be also significant in environmental conservation.

The positive electrode that lithium ion battery adopts is one of critical material manufacturing lithium ion battery, occupies core status in lithium ion battery.At present the positive electrode of commercial application mainly has cobalt acid lithium, LiMn2O4, cobalt nickel lithium manganate ternary material and LiFePO4, and wherein, cobalt acid lithium is still mainstay material, is mainly used in high-end electronic product with small-sized lithium ion battery with high energy density field.

Open report mainly has from employing cobalt acid lithium as the method reclaiming valuable metal the used Li ion cell of positive electrode, ZhangPW etc. are at " Hydrometallurgy " Vol.47No.2-3,1998,259-271 reports employing Leaching in Hydrochloric Acid lithium ion cell anode waste, obtains cobaltous sulfate and lithium carbonate then through operations such as extraction, precipitations.Wu Fang reports the anode waste obtained in used Li ion cell in " China YouSe Acta Metallurgica Sinica " Vol.14No.4,2004,697-701 and adopts at high temperature with sulphuric acid and hydrogen peroxide Ore Leaching, obtains cobaltous sulfate and lithium carbonate then through extraction, precipitation operation.MyoungJ etc. report in " JournalofPowerSources " Vol.112,2002,639-642 and dissolve, with hot nitric acid, the anode waste obtained in used Li ion cell, obtain Co after being then passed through electro-deposition operation, low temperature calcination₃O₄.Patent [CN201210491084] reports one and produces Co from waste and old lithium ion battery₃O₄Method, scrap lithium ion battery positive pole is impregnated in organic solvent, makes positive pole powder material and aluminum foil current collector separate, then in positive pole powder material, add roasting after organic fluorocompound, obtain Co₃O₄Material.Patent [CN201210167969] reports a kind of method of metal in efficient Strengthen education waste lithium ion, by adding cobalt acid lithium powder in dilute acid soln, control solid-to-liquid ratio and add ferrous sulfate, logical DC voltage, improve the leaching efficiency of cobalt acid lithium.Patent [CN201180048492] reports a kind of method for reclaiming Li ion, by introducing one or more cyclosiloxane, so that lithium ion forms one or more cyclosiloxane-Li ionic complex, then by the organic facies containing cyclosiloxane-Li ionic complex and aqueous phase separation.Patent [CN201010523257] reports a kind of method reclaiming lithium from waste and old lithium ion battery and waste pole piece, by being leached with acid and reducing agent, and the impurity such as the ferrum in leachate, copper, aluminum are removed with chemical method, then precipitate the lithium in leachate with villiaumite, obtain lithium fluoride product.Patent [CN200910117702] reports by by useless LiCoO₂Powder mix with the salt of alkali metallic sodium and potassium after in higher roasting temperature, product of roasting is going out with water logging, and leachate obtains cobalt oxalate and lithium carbonate through heavy cobalt and sinker operation.Patent [CN200910093727] reports a kind of method utilizing waste and old lithium ion battery recovery to prepare cobalt acid lithium, by by waste and old lithium ion battery electric eliminating, fractionation, pulverizing, NMP process, calcining, obtaining waste and old LiCoO₂Material, then by LiCoO₂Material mix with natural organic acids and hydrogen peroxide after ball milling, and obtain Li⁺、Co²⁺Solution, dropping ammonia prepares xerogel and secondary clacining obtains cobalt acid lithium electrode material in the solution.Patent [CN200910039217] discloses recovery and the regeneration method of a kind of waste lithium ion battery cathode material, by being undertaken used Li ion cell cathode waste crushing, grinding, except aluminum, acidleach, extraction copper, chemical subtraction, precipitation, addition lithium source secondary high-temperature baking operation, it is achieved cathode material regenerates.Patent [CN200810028730] discloses a kind of method reclaiming from waste and old lithium ion battery, preparing cobalt acid lithium.After lithium ion battery positive plate being pulverized, sieves, it is thus achieved that useless cobalt acid lithium；Constant temperature resistance furnace removes binding agent, conductive 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.Waste lithium ion cell anode material is at high temperature removed binding agent PVDF, at high temperature calcining cobalt acid lithium, make inefficacy cobalt acid lithium produce crystallization reaction, again possess layer structure.Patent [CN200510018601] reports a kind of method of separating and recovering cobalt from the positive pole material of lithium cobalt acid of waste and old lithium ion battery.Waste and old lithium ion battery carries out after physics is disassembled, calcined, organic solvent soaks, obtaining useless cobalt acid lithium, being placed in useless cobalt acid lithium under acid condition and using H₂O₂Or Na₂S₂O₃As reducing agent, dissolve and obtain containing Co²⁺And Li⁺Solution, then with NaOH solution for 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.Used Li ion cell positive electrode it is cut into fractionlet and is immersed in METHYLPYRROLIDONE liquid, separating and obtain active substance Li_xCoO₂Black powder, then black powder is scattered in salpeter solution or hydrochloric acid solution, then through filtration, precipitation operation, obtaining blue precipitate, precipitate is roasting at high temperature, obtains Li_xCoO₂Powder body.

At present it have been reported that cobalt acid lithium used Li ion cell in positive electrode active materials renovation process in adopt sulphuric acid to add hydrogen peroxide, sodium thiosulfate, hydrochloric acid, nitric acid dissolve useless LiCoO₂, leaching process is inevitably generated containing acid gas, Cl₂Or NO_xWaste gas, environment is caused serious secondary pollution by removal process.Additionally, the subsequent treatment operation of leachate is many, long flow path causes that cost recovery is high；Leaching process all have employed again higher acid concentration and extraction temperature to improve metal recovery rate and shortening extraction time, and leaching equipment antiseptical is required significantly high by this.Positive active material under peeling off from used Li ion cell positive plate at high temperature calcines cobalt acid lithium electrochemical performance prepared by the method regaining cobalt acid lithium can not meet performance of lithium ion battery requirement.Adopt useless LiCoO₂Powder mix with the salt of alkali metallic sodium and potassium after the method for roasting, the salt consumption that there is alkali metallic sodium and potassium in roasting process is big, precipitant oxalates consumption is many in removal process, causes the shortcoming that cost recovery is high；Adopt useless LiCoO₂Material mix with natural organic acids and hydrogen peroxide after ball grinding technique, there is removal process and easily make ball-grinding machine be corroded and produce the shortcoming containing organic wastewater.

Summary of the invention

It is an object of the invention to provide the renovation process of positive electrode active materials in a kind of cobalt acid lithium used Li ion cell.

The present invention is the renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell, 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 discharge process carrying out 1-3h in the sodium hydrate aqueous solution of 0.1-1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；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, it is thus achieved that positive plate；

Step (2): positive plate is loaded in ceramic crucible in the ratio that ratio-g/mL is 1:10-1:15 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained in step (1), 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 of insulation 0.5-1h from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with stirring 5-30min in the container of water and with motor stirrer by 1:40-1:70 according to the ratio-g/mL of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min；After stopping stirring, being sieved by the screen cloth of the mixture 10-20 order in container, oversize 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 chamber type electric resistance furnace and makes 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 and the sodium pyrosulfate-g/g in mass ratio step (3) obtained puts into be fully ground in ceramic mortar after the mixing of 1:0.3-1:1.7 ratio to mix homogeneously, mixture after grinding is loaded ceramic crucible and adds on ceramic cap lid, it is then placed in chamber type electric resistance furnace roasting, makes furnace temperature be raised to 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min；In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical products bought；

Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C when stirring, and extraction time 5-30min, solid-to-liquid ratio-g/mL is 1:10-1:50；nullThen leachate is warmed up to 95-98 DEG C，The sodium carbonate liquor of 1.0-3.0mol/L is slowly added to leachate，Then filter，Washing filtering residue also dries，Analyze Li in filtering residue、The content of Co，A certain amount of lithium carbonate is supplemented toward filtering residue according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt，Then abundant spheroidal graphite in planetary ball mill，Ball-milling Time is 0.5-2h，Rotating speed is 200-500r/min，Again that it is tight at the pressure of 0.1-100MPa，Put in clean ceramic crucible，In 650-700 DEG C of constant temperature 2-6h in air atmosphere，It is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again，Sample comminution after firing、Grind，Cross 500 mesh sieves，Obtain the lithium cobaltate cathode material that chemical property is good；

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 crystallization in crystallizing evaporator, cerium sulphate crystal condition be vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains sodium bisulfate.

The present invention has that technological process is short, cost recovery is low compared with the prior art, easy operation, the advantage that do not produce secondary pollution in equipment anticorrosion requirement is low, the lithium cobaltate cathode material function admirable of regeneration, processing procedure.

Detailed description of the invention

The mixed proportion of renovation process in accordance with the above, the useless cobalt acid lithium powder described in step (4) and sodium pyrosulfate is: mass ratio-g/g is 1:0.3-1:1.7.

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, and sintering temperature is 400-650 DEG C, 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, and solid-to-liquid ratio-g/mL is 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 discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 2

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

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, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 500 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

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, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 450 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

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, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:0.68 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

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, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:0.68 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 7

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:0.68 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 500 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 8

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:0.68 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 400 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 9

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.7 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:30 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 10

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:0.3 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；Then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

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, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 20min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

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, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 550 DEG C and be incubated 20min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 13

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 500 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 14

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:40 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Co, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grind, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Embodiment 15

Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate Yu the volume of 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, being put into by positive plate equipped with in the container of water and with the motor stirrer mixing speed stirring 20min with 50r/min for 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, obtains 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；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；Put into ceramic mortar is fully ground by the useless cobalt acid lithium powder ratio that (g/g) is 1:1.14 in mass ratio with sodium pyrosulfate that obtains of recycling and mix homogeneously, then by the mixture loading ceramic crucible after grinding and add ceramic cap lid to be put in chamber type electric resistance furnace and make furnace temperature be raised to 450 DEG C and be incubated 30min with the heating rate of 5 DEG C/min；After roasting terminates, the material in crucible is leached 30min with solid-to-liquid ratio (g/mL) for 1:40 with the water of 50 DEG C when stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt, then with the abundant spheroidal graphite 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is warming up to 900^oC is slowly cooled to room temperature after being incubated 10h, the sample comminution after firing, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Being 1.0 by the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium bisulfate.

Claims

1. the renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell, it is characterised in that the method comprises the following steps: