CN105742748A

CN105742748A - Method for recovering cobalt and lithium from lithium cobalt oxide waste of lithium ion battery positive material

Info

Publication number: CN105742748A
Application number: CN201610322563.1A
Authority: CN
Inventors: 郭菲
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-05-16
Filing date: 2016-05-16
Publication date: 2016-07-06

Abstract

The invention relates to a method for recovering cobalt and lithium from lithium cobalt oxide waste of a lithium ion battery positive material. The method comprises the following steps: discharging and dismantling a waste lithium ion battery to obtain a waste positive plate, and roasting, water-dissolving and filtering the waste positive plate to obtain waste lithium cobalt oxide; mixing the waste lithium cobalt oxide and potassium sulfate to obtain a mixture, ball-milling the mixture, and loading a ball-milling product into an absorption device; converting acid preparation exhaust, then introducing the converted acid preparation exhaust into the absorption device, discharging gas going out from the absorption device and satisfying the emission standard to the atmosphere, taking out the mixture in the absorption device, leaching the mixture by water, adding a potassium carbonate solution into the solution, filtering, supplementing lithium carbonate to filter residues, and then ball-milling, compressing and roasting, therbey obtaining the lithium cobalt oxide positive material with excellent electrochemical performance again. The filtrate is crystallized to obtain potassium sulfate.

Description

The method of Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material

Technical field

The present invention relates to the method for Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material.

Background technology

Sulphuric acid is widely used in chemical fertilizer industry, metallurgical industry, petroleum industry, mechanical industry, medical industry, the production of detergent, war industry, atomic energy industry and aerospace industry etc..But sulfuric acid industry is also the chemical industry of high pollution, the antacid tail gas of sulfuric acid industry every year to gas pollutants such as the substantial amounts of sulfur dioxide of airborne release, severe contamination environment.China has issued " sulfuric acid industry pollutant emission standard " (GB26132-2010) on 30th in December in 2010, the discharge of antacid tail gas is clearly required, it may be assumed that after 2013, the content of the antacid sulfur dioxide in tail gas of all newly-built and existing sulphuric acid production enterprises discharge have to be lower than 400mg/m³, sulfuric acid mist have to be lower than 30mg/m³.And current sulfuric acid industry SO in the tail gas that double-absorption production procedure is discharged₂Content be typically in 600 ~ 1400mg/m³Left and right, it is impossible to directly to airborne release.

Antacid tail gas to pass through and removes sulfuric acid mist and make SO₂Content reach could emptying after standard.The disclosed method reporting for work antacid treating tail gas has: potassium carbonate absorption process, sodium hydroxide absorption process, lime absorption, magnesium oxide absorption process, ammonia absorption process, ammonia ammonium sulphate process, ammonia-ammonium sulfite, ammonia-ammonium hydrogen sulfate method, sulfurous acid-Potassium acid sulfite method, peroxy-disulfuric acid conversion method, basic aluminum sulfate solution absorption method, Citrate Buffer, Exchange Resin by Adsorption, activated carbon adsorption conversion method etc..Wherein, potassium carbonate absorption process is to SO in antacid tail gas₂Absorbance higher and obtain potassium sulfite product, but potassium sulfite market is limited, and also needs to be continuously added antioxidant in absorption process and stop potassium sulfite to be oxidized to potassium sulfate, and when the price of potassium carbonate is higher than potassium sulfite, this method is just uneconomical.Calx absorption process adopts lime water or lime cream washing antacid tail gas, the method technology maturation, and production cost is low, but SO₂Absorption rate is slow, absorbability is little, the CaSO of generation₃And CaSO₄Easily blocking pipeline and equipment, this method produces substantial amounts of waste residue in addition, and these waste residues cause serious secondary pollution to environment.Ammonia absorption process adopts liquefied ammonia or ammonia as absorbent, and absorption efficiency is high, desulfurization is thorough, but ammonia is volatile, and the consumption of absorbent is big, and additionally the source of ammonia is limited by regions bigger.Sodium hydroxide absorption process is to use sodium hydroxide to administer antacid tail gas, SO₂Absorbability is big, absorption rate is fast, efficiency is high, but maximum problem is that feed hydrogen sodium oxide is more expensive, and the cost of antacid treating tail gas is high.Additionally, the problem of other antacid method for treating tail gas several general character of all ubiquities: (1) raw materials used price is high, and investment is relatively big, and Operation and Maintenance is relatively costly；2) the side-product added value obtained after antacid treating tail gas is low.

Do the lithium ion battery of positive electrode active materials since the nineties in 20th century commercial applications with cobalt acid lithium, be widely used in the fields such as mobile phone, notebook computer, video camera, digital camera.But, it being typically about the service life of the type lithium ion battery 3 ~ 5 years, the type lithium ion battery quantity currently scrapped is more than 10,000,000,000.The problem rationally disposing waste lithium ion can not be ignored.

The method reclaiming valuable metal from the used Li ion cell adopting cobalt acid lithium to do positive electrode of open report mainly has, 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 water logging goes out, 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 under acid condition and use H by useless cobalt acid lithium₂O₂Or 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.

It has been reported that from useless cobalt acid lithium reclaim valuable metal lithium cobalt method, recovery technology still has to use related chemistry reagent in a large number, such as sulphuric acid, hydrogen peroxide, Potassium hyposulfite., hydrochloric acid, nitric acid, potassium acid sulfate, potassium pyrosulfate etc., this makes the current technology cost recovery reclaiming valuable metal lithium cobalt from useless cobalt acid lithium be difficult to.

Summary of the invention

It is an object of the invention to provide a kind of method of Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material, the steps include:

Step (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 1-3h in the sodium hydrate aqueous solution that concentration is 0.1-1.0mol/L；After discharge process, the lithium ion battery scrapped 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, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, 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；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；

Step (2): being mixed with potassium sulfate by useless cobalt acid lithium, then ball milling in ball mill, Ball-milling Time is 0.1-1.0h, and rotating speed is 200-500r/min, loads the mixture after ball milling in absorption plant；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the source of potassium sulfate is the potassium sulfate or the two mixture being mixed to form with arbitrary proportion that obtain in the potassium sulfate chemical products or step (5) bought；

Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.3-0.6m³S108 type vanadium catalyst/(1000m³Antacid tail gas h)；From conversion system gas out pass into described in step (2) have been charged into ball milling after mixture absorption plant carry out absorption operation, the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas₂Content whether lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, as reached requirement, discharge to air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas₂Content reach 350mg/m³Or the content of sulfuric acid mist reaches 30mg/m³, then no longer pass into from conversion system gas out in this absorption plant, by passing into from conversion system gas out, the standby absorption plant described in step (2) carry out the absorption operation under the same terms and SO in exit gas simultaneously₂Content, sulfuric acid mist the monitoring of content；Taking out the mixture in the absorption plant no longer passing into conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；

Step (4): being leached with the water of 20-50 DEG C when stirring by the mixture in the absorption plant no longer passing into conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, the solution of potassium carbonate that concentration is 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, lithium carbonate is supplemented toward filtering residue according to the requirement that mol ratio is 0.525:1 of lithium with cobalt, then ball milling in ball mill, again it is being adopted pressure compaction, Ball-milling Time is 0.5-2h, rotating speed is 200-500r/min, the pressure compressed is 0.1-100MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, it is warming up at 800 DEG C again to be incubated after 20h and is slowly cooled to room temperature, sample comminution after firing, grind, cross 400 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；

Step (5): solution crystallization in crystallizing evaporator that step (4) is filtrated to get, 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 potassium sulfate, it is thus achieved that potassium sulfate return in step (2) and use.

The present invention compared with prior art has the advantage that cost is low, purification process non-secondary pollution produce are raw that effective cost is low, cobalt lithium reclaims of easy operation, antacid tail gas clean-up.

Detailed description of the invention

The present invention is the method for Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material, the steps include:

Step (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 1-3h in sodium hydrate aqueous solution；After discharge process, the lithium ion battery scrapped 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, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, sieved by the mixture screen cloth in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；

Step (2): mixed with potassium sulfate by useless cobalt acid lithium, then ball milling in ball mill, loads the mixture after ball milling in absorption plant；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the source of potassium sulfate is the potassium sulfate or the two mixture being mixed to form with arbitrary proportion that obtain in the potassium sulfate chemical products or step (5) bought；

Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into equipped with the conversion system of vanadium catalyst carries out conversion operation again, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of vanadium catalyst is rated for: 0.3-0.6m³Catalyst/(1000m³Antacid tail gas h)；From conversion system gas out pass into described in step (2) have been charged into ball milling after mixture absorption plant carry out absorption operation, the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas₂Content whether lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, as reached requirement, discharge to air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas₂Content reach 350mg/m³Or the content of sulfuric acid mist reaches 30mg/m³, then no longer pass into from conversion system gas out in this absorption plant, by passing into from conversion system gas out, the standby absorption plant described in step (2) carry out the absorption operation under the same terms and SO in exit gas simultaneously₂Content, sulfuric acid mist the monitoring of content；Taking out the mixture in the absorption plant no longer passing into conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；

Step (4): being leached with the water of 20-50 DEG C when stirring by the mixture in the absorption plant no longer passing into conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, solution of potassium carbonate is slowly added to leachate, then filter, washing filtering residue also dries, analyze Li in filtering residue, the content of Co, lithium carbonate is supplemented toward filtering residue according to the requirement that mol ratio is 0.525:1 of lithium with cobalt, then ball milling in ball mill, again it is being adopted pressure compaction, put in clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, it is warming up at 800 DEG C again to be incubated after 20h and is slowly cooled to room temperature, sample comminution after firing, grind, cross 400 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good；

The concentration of the sodium hydrate aqueous solution in the step (1) of approach described above is 0.1-1.0mol/L.

The positive plate of acquisition is 1:10-1:15 in the ratio g/mL of the quality of positive plate Yu the volume of ceramic crucible by the step (1) of approach described above.

The step (1) of approach described above is 1:40-1:70 according to the ratio g/mL of the quality of positive plate Yu the volume of water, positive plate is put into equipped with filling in the container of water and stirring 5-30min with motor stirrer, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min.

The screen cloth that screen cloth is 10-20 order in the step (1) of approach described above.

Being mixed with the ratio that potassium sulfate g/g in mass ratio is 1:0.01-2.0 by the useless cobalt acid lithium obtained in the step (2) of approach described above, then ball milling in ball mill, Ball-milling Time is 0.1-1.0h, and rotating speed is 200-500r/min.

In the step (4) of approach described above, the concentration of solution of potassium carbonate is 1.0-3.0mol/L.

Ball-milling Time in the step (4) of approach described above is 0.5-2h, and rotating speed is 200-500r/min, and the pressure of compression is 0.1-100MPa.

Vanadium catalyst in the step (3) of method illustrated above is S108 type vanadium catalyst.

The present invention is further spread out below by embodiment.It it is only the better embodiment to the present invention described in embodiment, not the present invention is done any pro forma restriction, the every any simple modification embodiment of embodiment done according to the technical spirit of the present invention, equivalent variations and modification, belong in the scope of technical solution of the present invention.

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.05 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.2 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 410 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 3:

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.3 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 390 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 4:

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.4 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 5:

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.5 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 415 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 6:

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.6 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 395 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.7 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 420 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.8 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 415 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:0.9 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 380 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

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 0.5mol/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 in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:1.0 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 420 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 11:

Collect and make, with cobalt acid lithium, the positive pole leftover pieces 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 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:1.1 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 410 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 12:

Collect and make, with cobalt acid lithium, the positive pole leftover pieces 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 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:1.2 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 405 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 13:

Collect and make, with cobalt acid lithium, the positive pole leftover pieces 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 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:1.3 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 395 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 14:

Collect and make, with cobalt acid lithium, the positive pole leftover pieces 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 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:1.4 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 430 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Embodiment 15:

Collect and make, with cobalt acid lithium, the positive pole leftover pieces 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 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；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；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 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless cobalt acid lithium；The useless cobalt acid lithium ratio that (g/g) is 1:1.5 in mass ratio with potassium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 405 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content lower than 350mg/m³And whether the content of sulfuric acid mist is lower than 30mg/m³, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas 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 solution of potassium carbonate 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 0.525:1 of lithium Yu cobalt, then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, again that it is tight at the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain lithium cobaltate cathode material；The solution crystallization in crystallizing evaporator being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains potassium sulfate.

Above content is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the thought of the present invention, all will change in specific embodiments and applications, and this specification content should not be construed as limitation of the present invention.

Claims

1. the method for Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material, it is characterised in that the steps include:

2. the method for Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material according to claim 1, it is characterised in that: the positive plate of acquisition is 1:10-1:15 in the ratio g/mL of the quality of positive plate Yu the volume of ceramic crucible by step (1).

3. the method for Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material according to claim 2, it is characterized in that: step (1) is 1:40-1:70 according to the ratio g/mL of the quality of positive plate Yu the volume of water, positive plate is put into equipped with filling in the container of water and stirring 5-30min with motor stirrer, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min.

4. the method for Call Provision lithium in lithium ion cell anode material lithium cobaltate waste material according to claim 3, it is characterized in that: the useless cobalt acid lithium obtained is mixed by step (2) with the ratio that potassium sulfate g/g in mass ratio is 1:0.01-2.0, then ball milling in ball mill.