CN104466295A - Method for regenerating positive electrode active material in LiNi1/3Co1/3Mn1/3O2 waste lithium ion battery - Google Patents

Method for regenerating positive electrode active material in LiNi1/3Co1/3Mn1/3O2 waste lithium ion battery Download PDF

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CN104466295A
CN104466295A CN201510007555.3A CN201510007555A CN104466295A CN 104466295 A CN104466295 A CN 104466295A CN 201510007555 A CN201510007555 A CN 201510007555A CN 104466295 A CN104466295 A CN 104466295A
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filter residue
ratio
positive
positive plate
lithium manganate
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CN104466295B (en
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王大辉
文豪
陈怀敬
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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
    • 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
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    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention discloses a method for regenerating a positive electrode active material in a LiNi1/3Co1/3Mn1/3O2 waste lithium ion battery. The method includes the steps that the waste lithium ion battery is subjected to discharging and dismantling or positive pole leftover materials and positive electrode fragments are collected to obtain waste positive plates, and the waste positive plates are subjected to roasting, water dissolving and filtering to obtain waste LiNi1/3Co1/3Mn1/3O2 powder; the waste LiNi1/3Co1/3Mn1/3O2 powder and sodium pyrosulfate are roasted after being mixed according to a certain proportion, roasted products are leached by water, then a sodium carbonate solution is added into liquor, filtering is conducted, after the proportion of Li, Ni, Co and Mn in carbonate modulation filter residues is supplemented, the Li, Ni, Co and Mn are subjected to ball milling, compressing and roasting, and accordingly the LiNi1/3Co1/3Mn1/3O2 positive electrode material is obtained again. Components of filter liquor are adjusted through sulfuric acid, crystallization processing is carried out, and then sodium hydrogen sulfate is obtained.

Description

The renovation process of positive electrode active materials in nickle cobalt lithium manganate used Li ion cell
Technical field
The present invention relates to the regeneration techniques of positive electrode active materials in nickle cobalt lithium manganate 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, nickle cobalt lithium manganate (LiNi at present 1/3co 1/3mn 1/3o 2) ternary material and LiFePO4.Nickle cobalt lithium manganate has the advantages such as electrochemistry capacitance is high, good cycle, synthesis is easy, cost is low, fail safe is good, instead of part cobalt acid lithium in recent years gradually, has entered compact lithium cell positive electrode market.In addition, nickle cobalt lithium manganate specific capacity is high, tap density is comparatively large, energy density is large, is conducive to the volume controlling power lithium-ion battery, is also applied in middle-size and small-size lithium-ion-power cell field.
In the nickle cobalt lithium manganate used Li ion cell reported at present, the renovation process of positive electrode active materials has, and patent [CN201310736549] reports a kind of with the addition of Na 2sO 3sulfuric acid solution dissolve the method for useless nickel-cobalt lithium manganate material.Patent [CN201310736528] reports the method for the useless nickel-cobalt lithium manganate material of mixed solution dissolving of a kind of nitric acid and sulfuric acid.Patent [CN201310736522] reports the useless nickle cobalt lithium manganate lithium ion battery plus-negative plate material of mixed solution dissolving of a kind of nitric acid and sulfuric acid and the method for pasture powder.Patent [CN201310736539] reports the useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material of mixed solution dissolving of a kind of nitric acid and sulfuric acid and the method for corn stalk powder.Patent [CN201310736623] reports the useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material of mixed solution dissolving of a kind of nitric acid and sulfuric acid and the method for levigate pyrolusite.The mixed solution that patent [CN201310736485] reports a kind of nitric acid and sulfuric acid dissolves useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material and does not contain the method for high concentrated organic wastewater of benzene ring substance.Patent [CN201310736513] reports the useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material of mixed solution dissolving of a kind of nitric acid and sulfuric acid and the method for napier grass powder.It take waste and old lithium ion battery as the method that nickel-cobalt lithium manganate cathode material prepared by raw material that patent [CN201310630608] discloses a kind of, organic acid citric acid is adopted to be leaching agent and gel, by collosol and gel-hydrothermal reaction coupling legal system for nickel-cobalt lithium manganate cathode material.Patent [CN201310123337] reports a kind of method of waste and old ter-polymers dynamic lithium battery resource, waste and old ter-polymers dynamic lithium battery carries out discharging, disassembling, and battery pole piece NaOH solution is soaked, acetic acid soaks, acetone soaks, filtering drying obtains nickle cobalt lithium manganate tertiary cathode material and carbon negative pole material.Patent [CN201210421198] discloses a kind of method being prepared nickle cobalt lithium manganate by waste and old electrokinetic cell, the positive plate of old and useless battery is pulverized, sieves, acid dissolve, nickel salt, cobalt salt, manganese salt and ammoniacal liquor is added in filtrate, filtration, drying, obtain nickel cobalt manganese hydroxide powder, in nickel cobalt manganese hydroxide powder, add lithium carbonate, after calcining, obtain nickle cobalt lithium manganate.Patent [CN201210230857] reports a kind of waste lithium ion cell anode material full constituent resource recycle method, adopt the active material in fluorine-containing aqueous solutions of organic acids separating waste, worn anode material for lithium-ion batteries and aluminium foil, high-temperature roasting is carried out respectively containing lithium active material, alkali lye removal of impurities process, nickel cobalt manganese carbonate ternary precursor is prepared in the co-precipitation of leachate ammonium carbonate, active material after process and the regulation and control of nickel cobalt manganese carbonate ternary precursor component of mixture, after allocating a certain proportion of lithium carbonate into, high temperature solid-phase sintering prepares nickle cobalt lithium manganate ternary composite cathode material again.Patent [CN201110243034] provides a kind of waste and old electrokinetic cell ternary system anode material processing method, comprises the steps: alkali leaching, Ore Leaching nickel lithium and manganese cobalt, separating nickel lithium and manganese cobalt, reclaims nickel, reclaims lithium, Call Provision, recovery manganese.Patent [CN201010209830] reports a kind of method of Call Provision, nickel and manganese from waste lithium cell, by the positive pole black powder obtained in useless ion battery, first adopts dilute sulfuric acid to carry out low acid dissolve, then adopts Na 2sO 5or Na 2sO 3or Fe powder adds the concentrated sulfuric acid and carries out reduction of dissolved, high-concentration sulfuric acid is finally adopted to carry out acid dissolve.Patent [CN200910059700] describes a kind of leaching method of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, to be added by anode and cathode mixed materials isolated from waste LiCoxNiyMnzO 2 battery in nitric acid and to pass into the leaching that industrial pure oxygen carries out anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery.It take waste and old lithium ion battery as the method that nickle cobalt lithium manganate prepared by raw material that patent [CN200810198972] discloses a kind of.Sulfuric acid and hydrogen peroxide system is adopted to leach the positive electrode obtained in used Li ion cell, nickel, cobalt, the adjustment of manganese element mol ratio, ammonium carbonate adjust ph in abstraction impurity removal, solution again, the nickel cobalt manganese carbonate precursor obtained allocates appropriate lithium carbonate into, the activated nickle cobalt lithium manganate battery material of high temperature sintering synthesis tool.
In the nickle cobalt lithium manganate used Li ion cell reported at present positive electrode active materials renovation process in adopt sulfuric acid, nitric acid, citric acid, fluorine-containing organic acid dissolves useless nickle cobalt lithium manganate, inevitably produce containing acid gas, NO in removal process x waste gas and acid content, the waste water that content of organics is very high, this causes serious pollution to atmospheric environment, water environment.In addition, course of dissolution have employed again higher acid concentration and add hydrogen peroxide, and this is very high and add the cost of recovery to the requirement of leaching equipment Corrosion Protection.Subsequent treatment operation after useless nickle cobalt lithium manganate dissolves is longer, also causes the cost of recovery high.
Summary of the invention
The object of this invention is to provide the renovation process of positive electrode active materials in a kind of nickle cobalt lithium manganate used Li ion cell.The present invention is the renovation process of positive electrode active materials in nickle cobalt lithium manganate 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 nickle cobalt lithium manganate 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 nickle cobalt lithium manganate, 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 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 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 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 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 nickle cobalt lithium manganate powder;
Step (4): useless nickle cobalt lithium manganate powder step (3) obtained and sodium pyrosulfate in mass ratio-g/g are put into ceramic mortar fully ground and mixed is even after the ratio of 1:0.3-1:2 mixes, mixture after grinding is loaded ceramic crucible and adds ceramic cap and covers, then put into resistance kiln roasting, make furnace temperature be raised to 400-700 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, filter, washing filter residue is also dry, analyze Ni in filter residue, Co, the content of Mn, then nickelous carbonate is supplemented toward filter residue, cobalt carbonate, one or both in manganese carbonate, make the Ni in filter residue after supplementing, Co, Mn mol ratio meets the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements lithium carbonate toward filter residue, then by its abundant ball milling in ball mill, again that it is tight at the pressure of 0.1-100MPa, put into ceramic crucible, in 400-500 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 850 DEG C again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material,
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 regeneration cost is low, easy to operate, low to equipment anticorrosion requirement compared with the prior art, the nickel-cobalt lithium manganate cathode material function admirable of regeneration, do not produce the advantage of secondary pollution in processing procedure.
Embodiment
The present invention is the renovation process of positive electrode active materials in nickle cobalt lithium manganate 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 nickle cobalt lithium manganate 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 nickle cobalt lithium manganate, 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 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 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 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 nickle cobalt lithium manganate powder;
Step (4): useless nickle cobalt lithium manganate powder step (3) obtained and sodium pyrosulfate in mass ratio-g/g are put into ceramic mortar fully ground and mixed is even after the ratio of 1:0.3-1:2 mixes, mixture after grinding is loaded ceramic crucible and adds ceramic cap and covers, then put into resistance kiln roasting, make furnace temperature be raised to 400-700 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, filter, wash filter residue and drying, analyze the content of Ni, Co, Mn in filter residue, then supplement nickelous carbonate (NiCO toward filter residue 3), cobalt carbonate (CoCO 3), manganese carbonate (MnCO 3) in one or both, make the Ni in filter residue after supplementing, Co, Mn mol ratio meets the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements lithium carbonate toward filter residue, then by its abundant ball milling in ball mill, again that it is tight at the pressure of 0.1-100MPa, put into ceramic crucible, in 400-500 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 850 DEG C again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material,
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 Ball-milling Time of the step (5) of the above method is 0.5-2h, and rotating speed is 200-500r/min.
Embodiment 1:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.15 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 650 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, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.15 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.15 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.15 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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 20min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.5 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 450 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 1:30 leaching 30min, then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.5 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 500 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 1:30 leaching 30min, then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.5 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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 40 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, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.5 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 650 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 1:30 leaching 30min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:0.35 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:2 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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 20min, then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:0.7 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:0.7 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 10min 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, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, in filter residue, supplement appropriate manganese carbonate make Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.8 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 700 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 45 DEG C with solid-to-liquid ratio (g/mL) for 1:30 leaching 30min, then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.8 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to cover and put into chamber type electric resistance furnace and make furnace temperature be raised to 650 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 45 DEG C with solid-to-liquid ratio (g/mL) for 1:30 leaching 30min, then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with nickle cobalt lithium manganate, 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, 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 nickle cobalt lithium manganate powder, fully ground and mixed is even give up nickle cobalt lithium manganate powder and the sodium pyrosulfate ratio that (g/g) is 1:1.8 in mass ratio to be put into ceramic mortar, then the mixture after grinding is loaded ceramic crucible and add ceramic cap to 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 45 DEG C with solid-to-liquid ratio (g/mL) for 1:30 leaching 30min, then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added leachate, filter residue after filtration, washing, after drying, analyze Ni in filter residue, Co, the content of Mn, appropriate nickelous carbonate is supplemented in filter residue, manganese carbonate makes Ni in filter residue, Co, Mn mol ratio reaches the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filter residue, then in planetary ball mill with the abundant ball milling 2h of the speed of 400r/min, again that it is tight at the pressure of 5MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4h in air atmosphere, room temperature is slowly cooled to after being warming up to 850 DEG C of insulation 10h again, sample after firing is through pulverizing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material, 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 (2)

1. the renovation process of positive electrode active materials in nickle cobalt lithium manganate used Li ion cell, is characterized in that, 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 nickle cobalt lithium manganate 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 nickle cobalt lithium manganate, 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 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 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 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 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 nickle cobalt lithium manganate powder;
Step (4): useless nickle cobalt lithium manganate powder step (3) obtained and sodium pyrosulfate in mass ratio-g/g are put into ceramic mortar fully ground and mixed is even after the ratio of 1:0.3-1:2 mixes, mixture after grinding is loaded ceramic crucible and adds ceramic cap and covers, then put into resistance kiln roasting, make furnace temperature be raised to 400-700 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, filter, washing filter residue is also dry, analyze Ni in filter residue, Co, the content of Mn, then nickelous carbonate is supplemented toward filter residue, cobalt carbonate, one or both in manganese carbonate, make the Ni in filter residue after supplementing, Co, Mn mol ratio meets the requirement of 1:1:1, analyze Li in filter residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the mol ratio of Mn is that the requirement of 1.05:0.33:0.33:0.33 supplements lithium carbonate toward filter residue, then by its abundant ball milling in ball mill, again that it is tight at the pressure of 0.1-100MPa, put into ceramic crucible, in 400-500 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 850 DEG C again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain nickel-cobalt lithium manganate cathode material,
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 nickle cobalt lithium manganate used Li ion cell according to claim 1, it is characterized in that, the Ball-milling Time of step (5) is 0.5-2h, and rotating speed is 200-500r/min.
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