CN104600389A - Method for recycling metal from spent lithium ion battery of lithium manganate anode material - Google Patents

Abstract

The invention relates to a method for recycling metal from a spent lithium ion battery of a lithium manganate positive material. The method comprises the following steps of discharging the spent lithium ion battery, disassembling or collecting anode scraps and positive fragments so as to obtain waste positive pieces, and roasting, dissolving and filtering the waste positive pieces so as to obtain waste lithium manganate powder; and roasting after mixing the waste lithium manganate powder with potassium hydrogen sulphate according to a certain proportion, leaching a roasted product by using water, then, filtering after adding potassium carbonate solution into the solution, and carrying out ball milling, replenishing a certain amount of lithium carbonate into filter residues, pressing the filter residues and putting the pressed filter residues into a resistance furnace to roast, so as to obtain the lithium manganate positive material again. Components in the filtrate are adjusted by using sulphuric acid; and crystallized potassium hydrogen sulphate can be recycled.

Description

The method of Footwall drift from the used Li ion cell of manganate cathode material for lithium

Technical field

The present invention relates to the technology from Footwall drift the used Li ion cell doing positive electrode with LiMn2O4.

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.Current most anode material for lithium-ion batteries be Co based material, but due to Co be a kind of rare metal, amount less and valency is expensive, constrains lithium ion battery extensive development.Aboundresources, low price, the low toxicity of manganese, easily reclaim, the lithium manganese oxide of various embedding lithium has become the anode material for lithium-ion batteries received much concern.LiMn2O4 (LiMn ₂o ₄) positive electrode has great potentiality in lithium ion anode material, the positive active material as battery in lithium-ion-power cell and large-scale energy-storage battery is applied.

Method at present about Footwall drift from the used Li ion cell doing positive electrode with LiMn2O4 has: patent [CN201410280343] discloses a kind of method utilizing waste lithium manganese oxide battery to prepare nickel ion doped, by carrying out leaching process with sulfuric acid and mixed solution of hydrogen peroxide to useless LiMn2O4, obtain the solution containing lithium ion, manganese ion, then in solution, add nickel salt, lithium salts and precipitation reagent, sediment obtains nickel ion doped (LiNi again after calcining _0.5mn _1.5o ₄).Patent [CN201410246379] reports a kind of method reclaiming manganese and copper resource from manganese system waste and old lithium ion battery, adopts acid extracting, alkali solution technique, the precipitation method, Vibration Screen point-score, flotation partition method or sonic oscillation method to obtain containing Cu continuously ²⁺, Mn ²⁺solution, then carry out electrolysis procedure, obtain MnO ₂and Cu.Patent [CN201310646706] discloses a kind of method being prepared nickel manganese hydroxide by useless electrokinetic cell.Mixed solution that is nickeliferous, manganese is obtained by dissolving useless nickel lithium manganate cathode material by least one in hydrochloric acid, sulfuric acid and nitric acid, nickel acetate or nickel chloride or nickelous sulfate, manganese chloride or manganese sulfate or manganese acetate, glycerol or ethylene glycol or 1 is added in the solution after dissolving, 2,4-butantriol or 1,2-propylene glycol or 1, ammediol, then regulate the pH value of solution respectively with NaOH and ammoniacal liquor, then obtain nickel manganese hydroxide after heating for dissolving-microwave reaction cooling-filtration-washing-drying.It take waste and old lithium ion battery as the method that manganate cathode material for lithium prepared by raw material that patent [CN201310630619] discloses a kind of, successively citric acid solution, hydrogenperoxide steam generator is used to dissolve the LiMn2O4 obtained from waste and old lithium ion battery, then in solution, add lithium nitrate or lithium acetate or lithium sulfate, manganese nitrate or manganese acetate or manganese sulfate regulate the mol ratio of Li and Mn in solution, regulate the pH value of solution to obtain gel with ammoniacal liquor, then obtain manganate cathode material for lithium after ageing-drying-pre-burning-calcining.Patent [CN201310630768] reports a kind of method of dissolving waste lithium ion cell anode material, successively use malic acid solution and hydrogenperoxide steam generator to dissolve the manganate cathode material for lithium obtained from waste and old lithium ion battery, namely complete the course of dissolution of useless manganate cathode material for lithium.Patent [CN201210017163] discloses a kind of pyrometallurgy technology that adopts and utilizes the method that LiMn2O4 waste and old lithium ion battery and scrap iron are raw material manufacture manganeisen.Patent [CN201010141128] discloses a kind of method reclaiming valuable metal in waste lithium manganese oxide battery.After refuse battery fragmentation, with N, one or more mixed solvents in dinethylformamide, 1-METHYLPYRROLIDONE, oxolane soak battery core and obtain useless LiMn2O4, useless LiMn2O4 is dissolved with inorganic acid (one or more mixed acid solutions in the sulfuric acid of the hydrochloric acid of 36wt%, the nitric acid of 68wt%, the 98wt%) mixed solution that with the addition of hydrogen peroxide, adjust solution ph twice with NaOH and ammoniacal liquor, obtain MnO ₂, add sodium carbonate liquor and obtain lithium carbonate after precipitation operation.Patent [CN200910116656] reports one and reclaim MnO in anode material of wasted lithium manganate battery ₂method and application, obtain λ-MnO with sulfuric acid, hydrochloric acid, nitric acid or the normal pressure acidleach manganate cathode material for lithium that gives up ₂, or the hydro-thermal acidleach manganate cathode material for lithium that gives up obtains α-/β-/γ-MnO ₂.An Hongli etc. report the recovery research of the waste and old power lithium-ion battery main chemical elements of LiMn2O4 in " Peking University's journal (natural science edition) " Vol.42, Special Issue, Dec. 2006,83-86, with the HNO of 2mol/L ₃the H of+1 mol/L ₂o ₂the acid-soluble process LiMn2O4 of mixed solution (LiMn ₂o ₄) best results, the dissolution rate of LiMn2O4 is 100%.Yang Ze is identical to be reported based on waste lithium ion cell anode material LiMn in " Journal of Chemical Industry and Engineering " Vol.62, No.1, November 2011,3276-3281 ₂o ₄preparation MnO ₂and the achievement in research of chemical property, at normal temperatures and pressures, adopt the H of 0.5mol/L ₂sO ₄acidleach is given up LiMn ₂o ₄3h prepares λ-MnO ₂nano particle; Under 140 DEG C of hydrothermal conditions, adopt the H of 2 mol/L ₂sO ₄acidleach is given up LiMn ₂o ₄24h obtains β-MnO ₂nanometer rods.Peng Shantang etc. report secondary oxidation-precipitation method at " Wuhan University of Technology's journal " Vol.24, No.12, Dec.2002,27-29 and are separated LiMn2O4 (LiMn ₂o ₄) in lithium and the achievement in research of manganese, dissolve LiMn2O4 with the mixed solution of the nitric acid or hydrochloric acid or sulfuric acid that add hydrogen peroxide, then add a certain amount of (NH respectively ₄) ₂s ₂o ₈(NH ₄) ₂cO ₃, adopt secondary oxidation-precipitation method to prepare MnO ₂and lithium carbonate.

Adopt from the method for Footwall drift the used Li ion cell doing positive electrode with LiMn2O4 sulfuric acid, nitric acid, citric acid, the malic acid reported at present dissolve useless LiMn2O4, inevitably produce containing acid gas, NO in removal process _x waste gas and mineral acid content, the waste water that organic acid content is very high, this causes serious secondary pollution to atmospheric environment, water environment; Course of dissolution have employed again higher acid concentration and adds hydrogen peroxide or ammonium persulfate, and this is very high to the requirement of reclaimer Corrosion Protection; Subsequent treatment operation after dissolving is long, and the cost that useless LiMn2O4 is regenerated is high.Employing pyrometallurgy technology LiMn2O4 waste and old lithium ion battery is that the method for raw material manufacture manganeisen then also exists the shortcoming that reconstituted product added value is low, regenerative process energy consumption is high.

Summary of the invention

The object of this invention is to provide a kind of method of Footwall drift from the used Li ion cell of manganate cathode material for lithium.

The present invention is the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium, 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 LiMn2O4 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 LiMn2O4, 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 LiMn2O4 powder;

Step (4): useless LiMn2O4 powder step (3) obtained and potassium acid sulfate in mass ratio-g/g are put into ceramic mortar fully ground and mixed is even after the ratio of 1:0.2-1:1.2 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 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min;

Step (5): after roasting terminates, leached with the water of 20-50 DEG C under the condition stirred by the material in crucible, extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50, then leachate is warmed up to 95-98 DEG C, the solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements lithium carbonate toward filter residue, then abundant ball milling in ball mill, again that it is tight at the pressure of 0.1-100MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium,

Step (6): step (5) is filtered the solution concentrated sulfuric acid adjusting component obtained and makes the pH value of solution be 0.5-1.0, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains potassium acid sulfate, and the potassium acid sulfate of acquisition returns in step (4) and uses.

The present invention has that cost recovery is low, easy to operate, low to equipment anticorrosion requirement compared with the prior art, the manganate cathode material for lithium function admirable of regeneration, do not produce secondary pollution in regenerative process.

Embodiment

The present invention is the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium, 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 LiMn2O4 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 LiMn2O4, 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 LiMn2O4 powder;

Step (4): useless LiMn2O4 powder step (3) obtained and potassium acid sulfate in mass ratio-g/g are put into ceramic mortar fully ground and mixed is even after the ratio of 1:0.2-1:1.2 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 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min;

Step (5): after roasting terminates, leached with the water of 20-50 DEG C under the condition stirred by the material in crucible, extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50, then leachate is warmed up to 95-98 DEG C, the solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements lithium carbonate toward filter residue, then abundant ball milling in ball mill, again that it is tight at the pressure of 0.1-100MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium,

Step (6): step (5) is filtered the solution concentrated sulfuric acid adjusting component obtained and makes the pH value of solution be 0.5-1.0, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains potassium acid sulfate, and the potassium acid sulfate of acquisition returns in step (4) and uses.

According to above-described method, the potassium acid sulfate described in step (4) is: the potassium acid sulfate obtained in potassium acid sulfate chemical products or step (6) or the mixture that the two is mixed to form with arbitrary proportion.

According to above-described method, the mixed proportion of the useless LiMn2O4 powder described in step (4) and potassium acid sulfate is: mass ratio-g/g is 1:0.2-1:1.2.

According to above-described method, in step (4), the process conditions of resistance kiln roasting are: heating rate is 3-10 DEG C/min, and sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.

According to above-described method, the Ball-milling Time in step (5) is 0.5-2h, and rotating speed is 200-500r/min.

Embodiment 1:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.75 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 2

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.75 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 3

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.75 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 4

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.75 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 5

Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate ratio that (g/g) is 1:1 in mass ratio obtained in give up LiMn2O4 powder and step of the present invention (6) to be put into ceramic mortar, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into chamber type electric resistance furnace and make furnace temperature be raised to 450 DEG C and be incubated 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 6

Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate ratio that (g/g) is 1:1 in mass ratio obtained in give up LiMn2O4 powder and step of the present invention (6) to be put into ceramic mortar, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into chamber type electric resistance furnace and make furnace temperature be raised to 500 DEG C and be incubated 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 7

Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate ratio that (g/g) is 1:1 in mass ratio obtained in give up LiMn2O4 powder and step of the present invention (6) to be put into ceramic mortar, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into chamber type electric resistance furnace and make furnace temperature be raised to 550 DEG C and be incubated 20min with the heating rate of 5 DEG C/min, after roasting terminates, by the material in crucible under the condition stirred with the water of 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 8

Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate ratio that (g/g) is 1:1 in mass ratio obtained in give up LiMn2O4 powder and step of the present invention (6) to be put into ceramic mortar, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into chamber type electric resistance furnace and make furnace temperature be raised to 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 9

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.25 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 10

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:1.2 in mass ratio of useless LiMn2O4 powder and purchase 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 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 11

Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate ratio that (g/g) is 1:0.5 in mass ratio obtained in give up LiMn2O4 powder and step of the present invention (6) to be put into ceramic mortar, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 30min with the heating rate of 5 DEG C/min, after roasting terminates, by the material in crucible under the condition stirred with the water of 50 DEG C with solid-to-liquid ratio (g/mL) for 1:20 leaching 20min, then leachate is warmed up to 98 DEG C, the solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 12

Collect positive pole leftover pieces, the positive pole relic of the lithium ion battery manufacture process generation doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate ratio that (g/g) is 1:0.5 in mass ratio obtained in give up LiMn2O4 powder and step of the present invention (6) to be put into ceramic mortar, then the mixture loading ceramic crucible after grinding is added ceramic cap and covers and put into chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C and be incubated 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 1:20 leaching 20min, then leachate is warmed up to 98 DEG C, the solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 13

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.9 in mass ratio of useless LiMn2O4 powder and purchase 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 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 14

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.9 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Embodiment 15

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, 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 LiMn2O4 powder, fully ground and mixed is even the potassium acid sulfate chemical products ratio that (g/g) is 1:0.9 in mass ratio of useless LiMn2O4 powder and purchase 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 solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements a certain amount of lithium carbonate toward sediment, 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 6h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium, 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 potassium acid sulfate.

Claims (5)

1. the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium, 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 LiMn2O4 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 LiMn2O4, 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 LiMn2O4 powder;

Step (4): useless LiMn2O4 powder step (3) obtained and potassium acid sulfate in mass ratio-g/g are put into ceramic mortar fully ground and mixed is even after the ratio of 1:0.2-1:1.2 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 400-650 DEG C and be incubated 10-60min with the heating rate of 3-10 DEG C/min;

Step (5): after roasting terminates, leached with the water of 20-50 DEG C under the condition stirred by the material in crucible, extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50, then leachate is warmed up to 95-98 DEG C, the solution of potassium carbonate 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 Mn, the requirement being 0.525:1 according to the mol ratio of lithium and manganese supplements lithium carbonate toward filter residue, then abundant ball milling in ball mill, again that it is tight at the pressure of 0.1-100MPa, put into clean ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, room temperature is slowly cooled to after being warming up to 750 DEG C of insulation 20h again, sample comminution after firing, grinding, cross 400 mesh sieves, obtain manganate cathode material for lithium,

Step (6): step (5) is filtered the solution concentrated sulfuric acid adjusting component obtained and makes the pH value of solution be 0.5-1.0, then crystallization in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains potassium acid sulfate, and the potassium acid sulfate of acquisition returns in step (4) and uses.

2. the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium according to claim 1, is characterized in that the potassium acid sulfate described in step (4) is: the potassium acid sulfate obtained in potassium acid sulfate chemical products or step (6) or the mixture that the two is mixed to form with arbitrary proportion.

3. the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium according to claim 1, is characterized in that the mixed proportion of the useless LiMn2O4 powder described in step (4) and potassium acid sulfate is: mass ratio-g/g is 1:0.2-1:1.2.

4. the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium according to claim 1, it is characterized in that the process conditions of resistance kiln roasting in step (4) are: heating rate is 3-10 DEG C/min, sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.

5. the method for Footwall drift from the used Li ion cell of manganate cathode material for lithium according to claim 1, it is characterized in that the Ball-milling Time in step (5) is 0.5-2h, rotating speed is 200-500r/min.