CN104466292A - Method for recovering cobalt lithium metal from waste lithium ion battery of lithium cobalt oxide positive material - Google Patents

Method for recovering cobalt lithium metal from waste lithium ion battery of lithium cobalt oxide positive material Download PDF

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Publication number
CN104466292A
CN104466292A CN201410833979.0A CN201410833979A CN104466292A CN 104466292 A CN104466292 A CN 104466292A CN 201410833979 A CN201410833979 A CN 201410833979A CN 104466292 A CN104466292 A CN 104466292A
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lithium
positive plate
temperature
ratio
water
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CN104466292B (en
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陈怀敬
王大辉
文豪
赵午祥
曹胜强
黄允文
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Lanzhou University of Technology
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Lanzhou University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention discloses a method for recovering cobalt lithium metal from a waste lithium ion battery of a lithium cobalt oxide positive material. The method comprises the following steps: discharging and disassembling the waste lithium ion battery to obtain a waste positive plate, roasting the waste positive plate, dissolving with water and filtering to obtain waste lithium cobalt oxide powder; mixing the waste lithium cobalt oxide powder and sodium hydrogen sulfate according to a certain proportion and then roasting; leaching the roasting product with water; adding sodium carbonate solution into the solution and then filtering; supplementing a certain quantity of lithium carbonate into filter residue and then performing ball milling, pressing and placing in a resistance furnace to roast to newly obtain the lithium cobalt oxide positive material with good electrochemical performance, wherein the ingredients of the filter liquor are adjusted by using sulfuric acid and the sodium hydrogen sulfate obtained after the crystallization treatment is performed can be reutilized.

Description

The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material
Technical field
The present invention relates to the technology of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material.
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 output reaches 18.7 hundred million, and the output of China's lithium ion battery in 2010 reaches 26.8 hundred million.Because the useful life of lithium ion battery is generally 2-3, therefore, the environmental pollution that scrap lithium ion battery is brought and problem of resource waste also become increasingly conspicuous, and the problem how rationally disposing waste lithium ion can not be ignored.To the recycling of the 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 protection.
The positive electrode that lithium ion battery adopts is one of critical material manufacturing lithium ion battery, in lithium ion battery, occupy core status.The positive electrode of commercial application mainly contains cobalt acid lithium (LiCoO at present 2), LiMn2O4 (LiMn 2o 4), nickle cobalt lithium manganate (LiNi 1/3co 1/3mn 1/3o 2) ternary material and LiFePO4 (LiFePO 4), wherein, cobalt acid lithium is still the positive electrode that main flow uses, and is applied to the small-sized lithium ion battery with high energy density field of high-end electronic product.
That has openly reported mainly contains from employing cobalt acid lithium as the method reclaiming valuable metal the used Li ion cell of positive electrode, Zhang P W etc. are at " Hydrometallurgy " Vol.47 No.2-3,1998, report in 259-271 and adopt Leaching in Hydrochloric Acid lithium ion cell anode waste, then obtain cobaltous sulfate and lithium carbonate through operations such as extraction, precipitations.Wu Fang is at " China YouSe Acta Metallurgica Sinica " Vol.14 No.4,2004, report the anode waste employing obtained in used Li ion cell in 697-701 and at high temperature use sulfuric acid and hydrogen peroxide Ore Leaching, then obtain cobaltous sulfate and lithium carbonate through extraction, precipitation operation.Myoung J etc., at " Journal of Power Sources " Vol.112, reporting the anode waste with obtaining in hot nitric acid dissolve used Li ion cell, then after electro-deposition operation, low temperature calcination, obtaining Co in 2002,639-642 3o 4.Patent [CN201210491084] reports one and produce Co from waste and old lithium ion battery 3o 4method, by scrap lithium ion battery positive pole dipping in organic solvent, positive pole powder material and aluminum foil current collector are separated, then in positive pole powder material, add roasting after organic fluorocompound, obtain Co 3o 4material.Patent [CN201210167969] reports the method for metal in a kind of 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 direct 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, to make lithium ion form one or more cyclosiloxane-Li ionic complex, then by the organic phase 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 remove the impurity such as iron, copper, aluminium in leachate with chemical method, again with the lithium in villiaumite precipitation leachate, obtain lithium fluoride product.Patent [CN200910117702] reports by the LiCoO that will give up 2in higher roasting temperature after the salt of powder and alkali metallic sodium and potassium mixes, 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, obtains waste and old LiCoO 2material, then by LiCoO 2ball milling after material mixes with natural organic acids and hydrogen peroxide, and obtain Li +, Co 2+solution, drip ammoniacal liquor in the solution and prepare xerogel and secondary clacining obtains cobalt acid lithium electrode material.Patent [CN200910039217] discloses a kind of recovery of waste lithium ion battery cathode material and the method for regeneration, by used Li ion cell cathode waste being carried out fragmentation, grinding, except aluminium, acidleach, extraction copper, chemical subtraction, precipitating, add lithium source secondary high-temperature baking operation, realize cathode material regeneration.Patent [CN200810028730] discloses a kind of method reclaiming from waste and old lithium ion battery, prepare cobalt acid lithium.After lithium ion battery positive plate being pulverized, sieving, obtain useless cobalt acid lithium; Except no-bonder, conductive agent acetylene black in constant temperature resistance furnace, allocate the lithium carbonate of proper proportion into, the activated cobalt acid lithium battery material of high temperature sintering synthesis tool 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 calcines 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.After waste and old lithium ion battery carries out that physics is disassembled, calcined, organic solvent soaks, obtain useless cobalt acid lithium, under useless cobalt acid lithium is placed in acid condition, use H 2o 2or Na 2s 2o 3as reducing agent, dissolve and obtain containing Co 2+and Li +solution, then be precipitation reagent with NaOH solution, by the Co in solution 2+ion conversion becomes Co (OH) 2precipitation.Patent [CN200510015078] discloses a kind of lithium ion battery from scrapping and reclaims preparation Li x coO 2method.Used Li ion cell positive electrode be cut into fractionlet and be immersed in METHYLPYRROLIDONE liquid, being separated and obtaining active material Li xcoO 2black powder, then black powder is scattered in salpeter solution or hydrochloric acid solution, more after filtration, precipitation operation, obtain blue precipitate, sediment is roasting at high temperature, obtains Li xcoO 2powder.
Reported at present from cobalt acid lithium, as adopting in the method reclaiming valuable metal the used Li ion cell of positive electrode, sulfuric acid adds hydrogen peroxide, sodium thiosulfate, hydrochloric acid, nitric acid dissolve give up LiCoO 2, inevitably produce containing acid gas, Cl in leaching process 2or NO x waste gas, removal process causes serious secondary pollution to environment.In addition, many, the long flow path of the subsequent treatment operation of leachate causes cost recovery high; Leaching process all have employed higher acid concentration and extraction temperature again to improve metal recovery rate and shortening extraction time, and this requires very high to leaching equipment corrosion-resistant.Adopt useless LiCoO 2the method of roasting after the salt of powder and alkali metallic sodium and potassium mixes, the salt consumption that there is alkali metallic sodium and potassium in roasting process is large, precipitation reagent oxalates consumption is many in removal process, causes the shortcoming that cost recovery is high; Adopt useless LiCoO 2, there is removal process and easily make ball-grinding machine be corroded and introduce the shortcoming of impurity in ball grinding technique after material mixes with natural organic acids and hydrogen peroxide.
Summary of the invention
The object of this invention is to provide a kind of method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material.
The present invention is the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, the steps include:
Step (1): be at room temperature positioned over the discharge process of carrying out 1-3h in the sodium hydrate aqueous solution of 0.1-1.0mol/L by collecting the scrap lithium ion battery doing positive electrode with cobalt acid lithium come; After discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate; Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate;
Step (2): positive plate is loaded in ceramic crucible in the ratio that the ratio-g/mL of the quality of positive plate and the volume of ceramic crucible is 1:10-1:15 by the positive plate obtained in step (1), then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature; Take out the positive plate through roasting, be that positive plate to be put into container that water is housed and stirs 5-30min with electric mixer by 1:40-1:70 according to the ratio-g/mL of the quality of positive plate and the volume of water, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min; After stopping stirring, sieved by the mixture 10-20 object screen cloth in container, oversize is aluminium foil, and screenings is the solution containing positive active material; Aluminium foil use water cleaning 1-3 time, obtains aluminium foil through natural drying; Screenings carries out suction filtration, and in filter, thing use water cleaning 1-3 time, obtains positive active material;
Step (3): loaded in ceramic crucible by the positive active material obtained in step (2), be then placed in chamber type electric resistance furnace and make furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, obtains useless cobalt acid lithium powder;
Step (4): useless cobalt acid lithium powder step (3) obtained and niter cake in mass ratio-g/g are that to put into the abundant ground and mixed of ceramic mortar after the ratio of 1:0.4-1:2 mixes even, mixture after grinding is loaded ceramic crucible and adds ceramic cap and covers, then put into chamber type electric resistance furnace roasting, make furnace temperature be raised to 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min;
Step (5): after roasting terminates, leached with the water of 20-50 DEG C under the condition stirred by the material in crucible, extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50, then leachate is warmed up to 95-98 DEG C, the sodium carbonate liquor of 1.0-3.0mol/L is slowly added leachate, then filter, washing filter residue is also dry, analyze Li in filter residue, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward filter residue, 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 into clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, room temperature is slowly cooled to after being incubated 10h at being warming up to 900 DEG C again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good,
Step (6): step (5) is filtered the solution concentrated sulfuric acid adjusting component obtained and makes the pH value of solution be 0.5-1.0, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains niter cake, and the niter cake of acquisition returns in step (4) and uses.
The present invention has that technological process is short, cost recovery is low compared with the prior art, easy to operate, low to equipment anticorrosion requirement, metallic cobalt and the lithium rate of recovery is high, do not produce the advantage of secondary pollution in processing procedure.
Embodiment
The present invention is the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, the steps include:
Step (1): be at room temperature positioned over the discharge process of carrying out 1-3h in the sodium hydrate aqueous solution of 0.1-1.0mol/L by collecting the scrap lithium ion battery doing positive electrode with cobalt acid lithium come; After discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate; Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate;
Step (2): positive plate is loaded in ceramic crucible in the ratio that the ratio-g/mL of the quality of positive plate and the volume of ceramic crucible is 1:10-1:15 by the positive plate obtained in step (1), then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature; Take out the positive plate through roasting, be that positive plate to be put into container that water is housed and stirs 5-30min with electric mixer by 1:40-1:70 according to the ratio-g/mL of the quality of positive plate and the volume of water, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min; After stopping stirring, sieved by the mixture 10-20 object screen cloth in container, oversize is aluminium foil, and screenings is the solution containing positive active material; Aluminium foil use water cleaning 1-3 time, obtains aluminium foil through natural drying; Screenings carries out suction filtration, and in filter, thing use water cleaning 1-3 time, obtains positive active material;
Step (3): loaded in ceramic crucible by the positive active material obtained in step (2), be then placed in chamber type electric resistance furnace and make furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, obtains useless cobalt acid lithium powder;
Step (4): useless cobalt acid lithium powder step (3) obtained and niter cake in mass ratio-g/g are that to put into the abundant ground and mixed of ceramic mortar after the ratio of 1:0.4-1:2 mixes even, mixture after grinding is loaded ceramic crucible and adds ceramic cap and covers, then put into chamber type electric resistance furnace roasting, make furnace temperature be raised to 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min;
Step (5): after roasting terminates, leached with the water of 20-50 DEG C under the condition stirred by the material in crucible, extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50, then leachate is warmed up to 95-98 DEG C, the sodium carbonate liquor of 1.0-3.0mol/L is slowly added leachate, then filter, washing filter residue is also dry, analyze Li in filter residue, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward filter residue, 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 into clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, room temperature is slowly cooled to after being incubated 10h at being warming up to 900 DEG C again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good,
Step (6): step (5) is filtered the solution concentrated sulfuric acid adjusting component obtained and makes the pH value of solution be 0.5-1.0, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains niter cake, and the niter cake of acquisition returns in step (4) and uses.
According to above-described method, the niter cake described in step (4) is: the niter cake obtained in the chemical products of niter cake or step (6) or the mixture that the two is mixed to form with arbitrary proportion;
According to above-described method, the mixed proportion of the useless cobalt acid lithium powder described in step (4) and niter cake is: mass ratio-g/g is 1:0.4-1:2.
According to above-described method, in step (4), the process conditions of resistance kiln roasting are: heating rate is 3-10 DEG C/min, and sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.
According to above-described method, 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 of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 20min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, useless cobalt acid lithium powder and the niter cake chemical products ratio that (g/g) is 1:1.41 in mass ratio of purchase are put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 2
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, the niter cake chemical products ratio that (g/g) is 1:1.41 in mass ratio recycling the cobalt acid lithium powder and the purchase that obtain is put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 3
Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, the niter cake chemical products ratio that (g/g) is 1:1.41 in mass ratio recycling the cobalt acid lithium powder and the purchase that obtain is put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 4
Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, the niter cake chemical products ratio that (g/g) is 1:1.41 in mass ratio recycling the cobalt acid lithium powder and the purchase that obtain is put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 5
Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate; Positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature; Take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C; After stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material; Aluminium foil water cleans 3 times, obtains aluminium foil through natural drying; Screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material; The positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder; Put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:0.99 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min; Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze the content of Li, Co in sediment, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 oc slowly cools to room temperature, the sample comminution after firing, grinding after being incubated 10h, crosses 500 mesh sieves, obtains the lithium cobaltate cathode material that chemical property is good; The pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 6
Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:0.99 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 7
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:0.99 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 8
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:0.99 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 9
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, the niter cake chemical products ratio that (g/g) is 1:2 in mass ratio recycling the cobalt acid lithium powder and the purchase that obtain is put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 10
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, the niter cake chemical products ratio that (g/g) is 1:0.4 in mass ratio recycling the cobalt acid lithium powder and the purchase that obtain is put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 40 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 11
Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:1.41 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 12
Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, the niter cake chemical products ratio that (g/g) is 1:1.41 in mass ratio recycling the cobalt acid lithium powder and the purchase that obtain is put into ceramic mortar, and fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 13
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:1.41 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 20min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 14
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:1.41 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:40 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.
Embodiment 15
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the discharge process of carrying out 2h in the sodium hydrate aqueous solution of 1.0mol/L, after discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate, positive plate loads in ceramic crucible by the ratio being 1:15 in the ratio (g/mL) of the quality of positive plate and the volume of ceramic crucible, then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C and be incubated 30min with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature, take out the positive plate through roasting, also stir 20min with electric mixer with the mixing speed of 50r/min according to the ratio (g/mL) of the quality of positive plate and the volume of water for positive plate is put into the container that water is housed by 1:50, in whipping process, the temperature of water is 30 DEG C, after stopping stirring, sieved by the 10 object screen clothes of the mixture in container, oversize is aluminium foil, and screenings is the solution containing positive active material, aluminium foil water cleans 3 times, obtains aluminium foil through natural drying, screenings carries out suction filtration, and in filter, thing water cleans 3 times, obtains positive active material, the positive active material obtained is loaded in ceramic crucible, is then 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, obtain useless cobalt acid lithium powder, put into ceramic mortar by recycling the niter cake ratio that (g/g) is 1:1.41 in mass ratio obtained in the cobalt acid lithium powder and the step of the present invention (6) that obtain fully ground and mixed is even, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into 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, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:40 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added leachate and produce sediment, gained sediment after filtration, washing, after drying, analyze Li in sediment, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward sediment, then in planetary ball mill with the abundant spheroidal graphite 2h of the speed of 400r/min, again that it is tight at the pressure of 10MPa, put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 900 DEG C of insulation 10h again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good, the pH value of solution is made to be 1.0 by filtering the solution concentrated sulfuric acid adjusting component obtained in above-mentioned steps, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains niter cake.

Claims (4)

1. the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, it is characterized in that, the method comprises the following steps:
Step (1): be at room temperature positioned over the discharge process of carrying out 1-3h in the sodium hydrate aqueous solution of 0.1-1.0mol/L by collecting the scrap lithium ion battery doing positive electrode with cobalt acid lithium come; After discharge process, the lithium ion battery scrapped is disassembled, obtain positive plate; Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with cobalt acid lithium, obtain positive plate;
Step (2): positive plate is loaded in ceramic crucible in the ratio that the ratio-g/mL of the quality of positive plate and the volume of ceramic crucible is 1:10-1:15 by the positive plate obtained in step (1), then be placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h with the heating rate of 5 DEG C/min from room temperature, then make chamber type electric resistance furnace power-off, naturally cool to room temperature; Take out the positive plate through roasting, be that positive plate to be put into container that water is housed and stirs 5-30min with electric mixer by 1:40-1:70 according to the ratio-g/mL of the quality of positive plate and the volume of water, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min; After stopping stirring, sieved by the mixture 10-20 object screen cloth in container, oversize is aluminium foil, and screenings is the solution containing positive active material; Aluminium foil use water cleaning 1-3 time, obtains aluminium foil through natural drying; Screenings carries out suction filtration, and in filter, thing use water cleaning 1-3 time, obtains positive active material;
Step (3): loaded in ceramic crucible by the positive active material obtained in step (2), be then placed in chamber type electric resistance furnace and make furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, obtains useless cobalt acid lithium powder;
Step (4): useless cobalt acid lithium powder step (3) obtained and niter cake in mass ratio-g/g are that to put into the abundant ground and mixed of ceramic mortar after the ratio of 1:0.4-1:2 mixes even, mixture after grinding is loaded ceramic crucible and adds ceramic cap and covers, then put into chamber type electric resistance furnace roasting, make furnace temperature be raised to 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min;
Step (5): after roasting terminates, leached with the water of 20-50 DEG C under the condition stirred by the material in crucible, extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50, then leachate is warmed up to 95-98 DEG C, the sodium carbonate liquor of 1.0-3.0mol/L is slowly added leachate, then filter, washing filter residue is also dry, analyze Li in filter residue, the content of Co, the requirement being 1.05:1 according to the mol ratio of lithium and cobalt supplements a certain amount of lithium carbonate toward filter residue, 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 into clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, room temperature is slowly cooled to after being incubated 10h at being warming up to 900 DEG C again, sample comminution after firing, grinding, cross 500 mesh sieves, obtain the lithium cobaltate cathode material that chemical property is good,
Step (6): step (5) is filtered the solution concentrated sulfuric acid adjusting component obtained and makes the pH value of solution be 0.5-1.0, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains niter cake, and the niter cake of acquisition returns in step (4) and uses.
2. the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material according to claim 1, is characterized in that the niter cake described in step (4) is: the niter cake obtained in the chemical products of niter cake or step (6) or the mixture that the two is mixed to form with arbitrary proportion;
The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material according to claim 1, is characterized in that the mixed proportion of the useless cobalt acid lithium powder described in step (4) and niter cake is: mass ratio-g/g is 1:0.4-1:2.
3. the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material according to claim 1, it is characterized in that the process conditions of resistance kiln roasting in step (4) are: heating rate is 3-10 DEG C/min, sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.
4. the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material according to claim 1, it is characterized in that the extraction temperature described in step (5) is 20-50 DEG C, extraction time 5-30min, solid-to-liquid ratio-g/mL is 1:10-1:50.
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