CN104485494A - Method for regenerating anode active materials in lithium cobalt oxide spent lithium-ion batteries - Google Patents

Method for regenerating anode active materials in lithium cobalt oxide spent lithium-ion batteries Download PDF

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CN104485494A
CN104485494A CN201410834047.8A CN201410834047A CN104485494A CN 104485494 A CN104485494 A CN 104485494A CN 201410834047 A CN201410834047 A CN 201410834047A CN 104485494 A CN104485494 A CN 104485494A
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lithium
temperature
ratio
positive plate
positive
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CN201410834047.8A
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CN104485494B (en
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王大辉
文豪
陈怀敬
黄允文
曹胜强
赵午祥
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兰州理工大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The invention discloses a method for regenerating anode active materials in lithium cobalt oxide spent lithium-ion batteries. The method comprises the following steps: discharging and dismantling a spent lithium-ion battery to obtain a waste anode plate; carrying out roasting, water dissolution and filtration on the waste anode plate to obtain waste lithium cobalt oxide powder; mixing the waste lithium cobalt oxide powder with sodium purosulfate according to a certain proportion and roasting; leaching the roasted product by water; adding a sodium carbonate solution into the solution and filtering; supplementing a certain amount of lithium carbonate into the filter residue and carrying out ball milling and compaction; putting into a resistance furnace to roast so as to re-obtain the lithium cobalt oxide anode material which is favorable in electrochemical property; adjusting the ingredients of the filtrate by sulfuric acid and carrying out crystallization treatment to obtain sodium hydrogen sulfate.

Description

The renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell
Technical field
The present invention relates to the regeneration techniques of positive electrode active materials in cobalt acid lithium used Li ion cell.
Background technology
Lithium ion battery is the secondary cell of new generation developed rapidly the nineties in 20th century, is widely used in small-sized portable electronic communication product and electric vehicle.According to statistics, within 2009, China's lithium ion battery 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, LiMn2O4, cobalt nickel lithium manganate ternary material and LiFePO4 at present, and wherein, cobalt acid lithium is still mainstay material, is mainly used in 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 is going out with water logging, and leachate obtains cobalt oxalate and lithium carbonate through heavy cobalt and sinker operation.Patent [CN200910093727] reports a kind of method utilizing waste and old lithium ion battery recovery to prepare cobalt acid lithium, by by waste and old lithium ion battery electric eliminating, fractionation, pulverizing, NMP process, calcining, 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, by useless cobalt acid lithium be placed in acid condition under 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.
In the cobalt acid lithium used Li ion cell reported at present positive electrode active materials renovation process in adopt that 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.At high temperature calcine cobalt acid lithium electrochemical performance prepared by the method that regains cobalt acid lithium from the positive active material under used Li ion cell positive plate is peeled off and can not meet performance of lithium ion battery requirement.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 produce the shortcoming containing organic wastewater 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 the renovation process of positive electrode active materials in a kind of cobalt acid lithium used Li ion cell.
The present invention is the renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell, the steps include:
Step (1): 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 sodium pyrosulfate in mass ratio-g/g are that to put into the abundant ground and mixed of ceramic mortar after 1:0.3-1:1.7 ratio 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; In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical products bought;
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 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,
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, and crystal is dry under 50-80 DEG C and 0.2-3h obtains niter cake.
The present invention has that technological process is short, cost recovery is low compared with the prior art, do not produce the advantage of secondary pollution in the lithium cobaltate cathode material function admirable of easy to operate, low to equipment anticorrosion requirement, regeneration, processing procedure.
Embodiment
The present invention is the renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell, the steps include:
Step (1): 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 sodium pyrosulfate in mass ratio-g/g are that to put into the abundant ground and mixed of ceramic mortar after 1:0.3-1:1.7 ratio 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; In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical products bought;
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 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,
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, and crystal is dry under 50-80 DEG C and 0.2-3h obtains niter cake.
According to above-described renovation process, the mixed proportion of the useless cobalt acid lithium powder described in step (4) and sodium pyrosulfate is: mass ratio-g/g is 1:0.3-1:1.7.
According to above-described renovation process, the process conditions of resistance kiln roasting in step (4): heating rate is 3-10 DEG C/min, and sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.
According to above-described renovation process, 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:0.68 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:0.68 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:0.68 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:0.68 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.7 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 1:30 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:0.3 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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, the useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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; The useless cobalt acid lithium powder and the sodium pyrosulfate ratio that (g/g) is 1:1.14 in mass ratio that recycling are obtained are put into ceramic mortar fully ground and mixed are even, then the mixture loading ceramic crucible after grinding are added ceramic cap and cover 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 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.

Claims (4)

1. the renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell, 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 sodium pyrosulfate in mass ratio-g/g are that to put into the abundant ground and mixed of ceramic mortar after 1:0.3-1:1.7 ratio 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; In this step, the source of sodium pyrosulfate is the sodium pyrosulfate chemical products bought;
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 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,
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, and crystal is dry under 50-80 DEG C and 0.2-3h obtains niter cake.
2. the renovation process of positive electrode active materials in cobalt according to claim 1 acid lithium used Li ion cell, is characterized in that the mixed proportion of the useless cobalt acid lithium powder described in step (4) and sodium pyrosulfate is: mass ratio-g/g is 1:0.3-1:1.7.
3. the renovation process of positive electrode active materials in cobalt according to claim 1 acid lithium used Li ion cell, it is characterized in that the process conditions of resistance kiln roasting in step (4): heating rate is 3-10 DEG C/min, sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.
4. the renovation process of positive electrode active materials in cobalt according to claim 1 acid lithium used Li ion cell, 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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105886777A (en) * 2016-05-16 2016-08-24 兰州理工大学 Method for synergistically treating acid-making exhaust gas and wasted lithium cobalt oxide and recovering cobalt lithium
CN106684486A (en) * 2016-12-28 2017-05-17 天津先众新能源科技股份有限公司 Method for extracting lithium from waste lithium iron phosphate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110065157A (en) * 2009-12-09 2011-06-15 부산대학교 산학협력단 Recycling method of used lithium ion secondary battery
CN102101701A (en) * 2010-12-31 2011-06-22 湖南邦普循环科技有限公司 Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite
CN103985920A (en) * 2014-06-05 2014-08-13 兰州理工大学 Method for separating lithium cobalt oxide and aluminum foil on scrapped lithium ion battery positive pole piece
CN104103870A (en) * 2014-07-30 2014-10-15 兰州理工大学 Method for recovering cobalt lithium aluminum from positive pole plate of scrap lithium ion battery
JP2014203567A (en) * 2013-04-02 2014-10-27 トヨタ自動車株式会社 Method of recovering positive electrode active material particle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110065157A (en) * 2009-12-09 2011-06-15 부산대학교 산학협력단 Recycling method of used lithium ion secondary battery
CN102101701A (en) * 2010-12-31 2011-06-22 湖南邦普循环科技有限公司 Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite
JP2014203567A (en) * 2013-04-02 2014-10-27 トヨタ自動車株式会社 Method of recovering positive electrode active material particle
CN103985920A (en) * 2014-06-05 2014-08-13 兰州理工大学 Method for separating lithium cobalt oxide and aluminum foil on scrapped lithium ion battery positive pole piece
CN104103870A (en) * 2014-07-30 2014-10-15 兰州理工大学 Method for recovering cobalt lithium aluminum from positive pole plate of scrap lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105886777A (en) * 2016-05-16 2016-08-24 兰州理工大学 Method for synergistically treating acid-making exhaust gas and wasted lithium cobalt oxide and recovering cobalt lithium
CN106684486A (en) * 2016-12-28 2017-05-17 天津先众新能源科技股份有限公司 Method for extracting lithium from waste lithium iron phosphate

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