CN104577104B

CN104577104B - Regeneration method of positive material lithium manganate waste of lithium ion battery

Info

Publication number: CN104577104B
Application number: CN201510019006.8A
Authority: CN
Inventors: 王大辉; 文豪; 陈怀敬
Original assignee: Lanzhou University of Technology
Current assignee: Lanzhou University of Technology
Priority date: 2015-01-15
Filing date: 2015-01-15
Publication date: 2017-01-11
Anticipated expiration: 2035-01-15
Also published as: CN104577104A

Abstract

The invention relates to a regeneration method of positive material lithium manganate waste of a lithium ion battery. The method comprises the steps: discharging the waste lithium ion battery, disintegrating or collecting positive electrode leftovers and positive electrode plates to obtain waste positive electrode plates, roasting the waste positive electrode plates, dissolving the waste positive electrode plates into water to obtain a solution, and filtering the solution to obtain waste lithium managanate powder; and mixing the waste lithium manganate powder and sodium hydrogen sulfate according to a given ratio to obtain a mixture, roasting the mixture to obtain a roast product, lixiviating the roast product by utilizing the water to obtain a solution I, adding a sodium carbonate solution into the solution I to obtain a mixed solution, filtering the mixed solution to obtain filter slag, adding lithium carbonate of a given amount into the filter slag to obtain a mixture I, ball milling the mixture I, pressing the mixture I after ball milling, and roasting the mixture I after pressing in a resistor furnace to obtain the lithium managanate positive material again. After sulfuric acid is used for adjusting components of filter liquid so as to obtain a solution II, the solution II is crystallized to obtain the sodium hydrogen sulfate, and the obtained sodium hydrogen sulfate can be reutilized.

Description

The renovation process of lithium cell anode material lithium manganate waste material

Technical field

The present invention relates to the regeneration techniques of lithium cell anode material lithium manganate waste material.

Background technology

Lithium ion battery is the secondary cell of new generation developed rapidly the nineties in 20th century, is widely used in miniature portable Formula telecommunications product and electric vehicle.According to statistics, within 2009, China's lithium ion battery yield reaches 18.7 hundred million, 2010 The yield of China's lithium ion battery reaches 26.8 hundred million.Owing to the service life of lithium ion battery is generally 2-3, therefore, report Environmental pollution and problem of resource waste that used Li ion cell brings also become increasingly conspicuous, and the most rationally dispose waste lithium ion Problem can not be ignored.Recycling to resources such as Co, Ni, Mn, Li, Al and Cu in used Li ion cell, both gram Take discarding method and disposed scrap lithium ion battery pollution on the environment, the most also made limited resource be circulated profit With, not only there is great economic benefit, be also significant in terms of environmental conservation.

The positive electrode that lithium ion battery uses is one of critical material manufacturing lithium ion battery, in lithium ion battery Occupy core status.Current most anode material for lithium-ion batteries is Co based material, but owing to Co is a kind of dilute Have a metal, amount less and valency is expensive, constrain lithium ion battery extensive development.The aboundresources of manganese, low price, low toxicity, easily return Receiving, the lithium manganese oxide of various embedding lithiums has become the anode material for lithium-ion batteries received much concern.LiMn2O4 (LiMn₂O₄) positive pole Material has great potentiality in lithium ion anode material, as battery in lithium-ion-power cell and large-scale energy-storage battery Positive active material be applied.

Renovation process about lithium cell anode material lithium manganate waste material has at present: patent [CN201410280343] Disclose a kind of method utilizing waste lithium manganese oxide battery to prepare nickel ion doped, by with sulphuric acid and mixed solution of hydrogen peroxide pair Useless LiMn2O4 carries out leaching process, obtains containing lithium ion, the solution of manganese ion, then adds nickel salt, lithium salts in solution and sinks Shallow lake agent, precipitate obtains nickel ion doped (LiNi again after calcining_0.5Mn_1.5O₄).Patent [CN201410246379] reports one Plant manganese and the method for copper resource of reclaiming from manganese systems waste and old lithium ion battery, continue with acid pasting, alkali solution technique, the sedimentation method, shake Dynamic sieve sieve method, flotation partition method or sonic oscillation method obtain containing Cu²⁺、Mn²⁺Solution, then carry out electrolysis procedure, it is thus achieved that MnO₂ And Cu.Patent [CN201310646706] discloses a kind of method being prepared nickel manganese hydroxide by useless electrokinetic cell.By with At least one in hydrochloric acid, sulphuric acid and nitric acid is dissolved useless nickel lithium manganate cathode material and is obtained nickeliferous, the mixed solution of manganese, toward dissolving After solution in add nickel acetate or Nickel dichloride. or nickel sulfate, manganese chloride or manganese sulfate or manganese acetate, glycerol or ethylene glycol or BT or 1,2-PD or 1,3-PD, the most respectively with sodium hydroxide and the pH value of ammonia regulation solution, Again through heating for dissolving-microwave reaction cooling-filter-wash-obtain nickel manganese hydroxide after drying.Patent [CN201310630619] discloses a kind of method preparing manganate cathode material for lithium for raw material with waste and old lithium ion battery, successively Use citric acid solution, hydrogenperoxide steam generator to dissolve the LiMn2O4 obtained from waste and old lithium ion battery, then add in solution In lithium nitrate or lithium acetate or lithium sulfate, manganese nitrate or manganese acetate or manganese sulfate regulation solution, the mol ratio of Li Yu Mn, uses ammonia The pH value of regulation solution obtains gel, then obtains manganate cathode material for lithium after ageing-dry-pre-burning-calcining.Patent [CN201310630768] reports a kind of method dissolving waste lithium ion cell anode material, successively uses malic acid solution Dissolve, with hydrogenperoxide steam generator, the manganate cathode material for lithium obtained from waste and old lithium ion battery, i.e. complete useless lithium manganate cathode The course of dissolution of material.Patent [CN201210017163] discloses a kind of employing pyrometallurgy technology and utilizes the waste and old lithium of LiMn2O4 Ion battery and scrap iron are the method that raw material manufactures manganeisen.Patent [CN201010141128] discloses a kind of from waste and old manganese The method reclaiming valuable metal in acid lithium battery.After refuse battery is broken, with DMF, N-Methyl pyrrolidone, One or more mixed solvents in oxolane soak battery core and obtain useless LiMn2O4, with the mineral acid that with the addition of hydrogen peroxide (hydrochloric acid of 36wt%, the nitric acid of 68wt%, 98wt% sulphuric acid in one or more mixed acid solutions) mixed solution is molten Solve useless LiMn2O4, adjust solution ph twice with NaOH and ammonia, it is thus achieved that MnO₂, add sodium carbonate liquor and obtain after precipitation operation Obtain lithium carbonate.Patent [CN200910116656] reports a kind of recovery MnO in anode material of wasted lithium manganate battery₂Side Method and application thereof, obtain λ-MnO with sulphuric acid, hydrochloric acid, nitric acid or the normal pressure acidleach manganate cathode material for lithium that gives up₂, or hydro-thermal acidleach is useless Manganate cathode material for lithium obtains α-/β-/γ-MnO₂.An Hongli etc. at " Peking University's journal (natural science edition) " Vol.42, Special Issue, Dec. 2006,83-86 reports LiMn2O4 waste and old power lithium-ion battery main chemical elements Reclaim research, with the HNO of 2mol/L₃The H of+1 mol/L₂O₂The mixed solution molten process LiMn2O4 (LiMn of acid₂O₄) best results, The dissolution rate of LiMn2O4 is 100%.Yang Ze is identical at " Journal of Chemical Industry and Engineering " Vol.62, No.1, November 2011,3276-3281 In report based on waste lithium ion cell anode material LiMn₂O₄Preparation MnO₂And the achievement in research of chemical property, often Under normal temperature and pressure, use the H of 0.5mol/L₂SO₄Acidleach is given up LiMn₂O₄3h prepares λ-MnO₂Nano-particle；At 140 DEG C of hydro-thermal bars Under part, use the H of 2 mol/L₂SO₄Acidleach is given up LiMn₂O₄24h prepares β-MnO₂Nanometer rods.Peng Shantang etc. are " Wuhan science and engineering is big Learn journal " Vol.24, No.12, Dec.2002,27-29 report secondary oxidation-sedimentation method separation LiMn2O4 (LiMn₂O₄) In lithium and the achievement in research of manganese, dissolve LiMn2O4 with the mixed solution adding the nitric acid of hydrogen peroxide or hydrochloric acid or sulphuric acid, then It is separately added into a certain amount of (NH₄)₂S₂O₈(NH₄)₂CO₃, use secondary oxidation-sedimentation method to prepare MnO₂And lithium carbonate.

At present it has been reported that lithium cell anode material lithium manganate waste material renovation process in use sulphuric acid, nitric acid, Citric acid, malic acid dissolve useless LiMn2O4, are inevitably generated containing acid gas, NO in removal process_xWaste gas and mineral acid contain Amount, the waste water that organic acid content is the highest, this causes serious secondary pollution to atmospheric environment, water environment；Course of dissolution is adopted again With higher acid concentration and addition hydrogen peroxide or Ammonium persulfate., this is the highest to the requirement of reclaimer Corrosion Protection；Dissolve After subsequent treatment operation long, the cost making the regeneration of useless LiMn2O4 is high.Use pyrometallurgy technology LiMn2O4 applying waste lithium ionic 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

It is an object of the invention to provide the renovation process of a kind of lithium cell anode material lithium manganate waste material.

The present invention is the renovation process of lithium cell anode material lithium manganate waste material, the steps include:

Step (1): by collect come do the scrap lithium ion battery of positive electrode with LiMn2O4 and be at room temperature positioned over The sodium hydrate aqueous solution of 0.1-1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium-ion electric that will scrap Pond is disassembled, it is thus achieved that positive plate；Collect and do, with LiMn2O4, the positive pole limit that the lithium ion battery manufacture process of positive electrode produces Corner material, positive pole relic, it is thus achieved that positive plate；

Step (2): by the positive plate that obtains in step (1) by the ratio of the quality of positive plate and the volume of ceramic crucible- G/mL is that positive plate is loaded in ceramic crucible by the ratio of 1:10-1:15, be subsequently placed in resistance furnace from room temperature start with 5 DEG C/ The heating rate of min makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h, then makes resistance furnace power-off, naturally cools to room temperature；Take out warp Cross the positive plate of roasting, be that positive plate is put into dress by 1:40-1:70 according to the ratio-g/mL of the volume of quality and the water of positive plate Having in the container of water and stir 5-30min, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min； After stopping stirring, being sieved by the screen cloth of the mixture 10-20 mesh in container, oversize is aluminium foil, and siftage is for containing The solution of positive active material；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying；Siftage carries out sucking filtration, thing in filter Clean 1-3 time with water, it is thus achieved that positive active material；

Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in resistance furnace Furnace temperature is made to be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless LiMn2O4 powder；

Step (4): useless LiMn2O4 powder step (3) obtained and sodium bisulfate-g/g in mass ratio are 1:0.2-1: Putting into after the ratio mixing of 1.2 and be fully ground mix homogeneously in ceramic mortar, the mixture after grinding loads ceramic crucible also Add on ceramic cap lid, be then placed in resistance kiln roasting, make furnace temperature be raised to 400-650 DEG C also with the heating rate of 3-10 DEG C/min Insulation 10-60min；

Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, 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, by 1.0- The sodium carbonate liquor of 3.0mol/L is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes Li, Mn in filtering residue Content, supplements lithium carbonate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese toward filtering residue, then abundant ball in ball mill Mill, then it is compressed under the pressure of 0.1-100MPa, put in ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, It is slowly cooled to room temperature after being warming up to 750 DEG C of insulation 20h again, the sample comminution after firing, grinding, crosses 400 mesh sieves, it is thus achieved that mangaic acid Lithium anode material；

Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, Then crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystallization Thing is dried under 50-80 DEG C and 0.2-3h and obtains sodium bisulfate, it is thus achieved that sodium bisulfate return in step (4) and use.

The operation low, easy of present invention regeneration cost compared with the prior art, to equipment anticorrosion require low, regeneration LiMn2O4 just Pole material property is excellent, do not produce secondary pollution in regenerative process.

Detailed description of the invention

Renovation process in accordance with the above, the sodium bisulfate described in step (4) is: sodium bisulfate chemical products or step Suddenly the sodium bisulfate obtained in (6) or the two mixture being mixed to form with arbitrary proportion.

The mixing ratio of renovation process in accordance with the above, the useless LiMn2O4 powder described in step (4) and sodium bisulfate Example is: mass ratio-g/g is 1:0.2-1:1.2.

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

Renovation process in accordance with the above, 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 hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.76 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Porcelain crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 650 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 2

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.76 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Porcelain crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 3

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.76 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Porcelain crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 500 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 20min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 4

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.76 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Porcelain crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 450 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 20min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 5

Collect and do, with LiMn2O4, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 20min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By useless LiMn2O4 powder and acquisition in step of the present invention (6) Sodium bisulfate (g/g) in mass ratio is that the ratio of 1:1 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 450 DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 40 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:30 leaches 30min；Then leachate is warmed up to 95 DEG C, is slowly added to the sodium carbonate liquor of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to lithium and manganese The requirement that mol ratio is 0.525:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant ball milling 2h of min, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, at air atmosphere In in 450 DEG C of constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made solution PH value is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystallization Thing is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Embodiment 6

Collect and do, with LiMn2O4, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 20min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By useless LiMn2O4 powder and acquisition in step of the present invention (6) Sodium bisulfate (g/g) in mass ratio is that the ratio of 1:1 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 500 DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 40 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:30 leaches 30min；Then leachate is warmed up to 95 DEG C, is slowly added to the sodium carbonate liquor of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to lithium and manganese The requirement that mol ratio is 0.525:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant ball milling 2h of min, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, at air atmosphere In in 450 DEG C of constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made solution PH value is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystallization Thing is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Embodiment 7

Collect and do, with LiMn2O4, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 20min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By useless LiMn2O4 powder and acquisition in step of the present invention (6) Sodium bisulfate (g/g) in mass ratio is that the ratio of 1:1 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 550 DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 40 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:30 leaches 30min；Then leachate is warmed up to 98 DEG C, is slowly added to the sodium carbonate liquor of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to lithium and manganese The requirement that mol ratio is 0.525:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant ball milling 2h of min, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, at air atmosphere In in 450 DEG C of constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made solution PH value is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystallization Thing is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Embodiment 8

Collect and do, with LiMn2O4, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 20min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By useless LiMn2O4 powder and acquisition in step of the present invention (6) Sodium bisulfate (g/g) in mass ratio is that the ratio of 1:1 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 650 DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 40 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:30 leaches 30min；Then leachate is warmed up to 98 DEG C, is slowly added to the sodium carbonate liquor of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to lithium and manganese The requirement that mol ratio is 0.525:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant ball milling 2h of min, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, at air atmosphere In in 450 DEG C of constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made solution PH value is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystallization Thing is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Embodiment 9

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.25 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Porcelain crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 10

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:1.2 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated with the heating rate of 5 DEG C/min 20min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 11

Collect and do, with LiMn2O4, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 20min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By useless LiMn2O4 powder and acquisition in step of the present invention (6) Sodium bisulfate (g/g) in mass ratio is that the ratio of 1:0.5 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture load ceramic crucible and add to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature liter with the heating rate of 5 DEG C/min To 600 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/mL) it is that 1:20 leaches 20min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leaching Go out liquid and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to lithium with The mol ratio of manganese is that the requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant ball milling 2h of 400r/min, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, at air In 450 DEG C of constant temperature 6h in atmosphere, then it is slowly cooled to room temperature after being warming up to 750 DEG C of insulation 20h, sample comminution after firing, grinds Mill, crosses 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made The pH value of solution is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Embodiment 12

Collect and do, with LiMn2O4, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 20min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By useless LiMn2O4 powder and acquisition in step of the present invention (6) Sodium bisulfate (g/g) in mass ratio is that the ratio of 1:0.5 is put into and is fully ground mix homogeneously in ceramic mortar, after then grinding Mixture load ceramic crucible and add to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature liter with the heating rate of 5 DEG C/min To 600 DEG C and be incubated 10min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/mL) it is that 1:20 leaches 20min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leaching Go out liquid and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to lithium with The mol ratio of manganese is that the requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant ball milling 2h of 400r/min, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, at air In 450 DEG C of constant temperature 6h in atmosphere, then it is slowly cooled to room temperature after being warming up to 750 DEG C of insulation 20h, sample comminution after firing, grinds Mill, crosses 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made The pH value of solution is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Embodiment 13

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.9 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:30 soaks with the water of 45 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 14

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.9 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 650 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:30 soaks with the water of 45 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Embodiment 15

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless LiMn2O4 powder；By the sodium bisulfate chemical products of useless LiMn2O4 powder and purchase in mass ratio (g/g) being that the ratio of 1:0.9 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:30 soaks with the water of 45 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Mn in precipitate, according to the mol ratio of lithium with manganese be The requirement of 0.525:1 supplements a certain amount of lithium carbonate toward precipitate, then with the speed of 400r/min in planetary ball mill Fully ball milling 2h, then it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C in air atmosphere Constant temperature 6h, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, Obtain manganate cathode material for lithium；By the pH value that the solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps makes solution it is 1.0, then crystallize in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is 80 DEG C and 2h under be dried obtain sodium bisulfate.

Claims

1. the renovation process of lithium cell anode material lithium manganate waste material, it is characterised in that the steps include:

Step (1): by collect come do the scrap lithium ion battery of positive electrode with LiMn2O4 and be at room temperature positioned over 0.1- The sodium hydrate aqueous solution of 1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium ion battery scrapped is entered Row is disassembled, it is thus achieved that positive plate；Collect and make, with LiMn2O4, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；

Step (2): by the positive plate of acquisition in step (1) in the ratio-g/mL of the quality of positive plate Yu the volume of ceramic crucible Positive plate is loaded in ceramic crucible by the ratio for 1:10-1:15, is subsequently placed in resistance furnace and starts with 5 DEG C/min's from room temperature Heating rate makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h, then makes resistance furnace power-off, naturally cools to room temperature；Take out through roasting The positive plate burnt, is that positive plate is put into equipped with water by 1:40-1:70 according to the ratio-g/mL of the volume of quality and the water of positive plate Container in and stir 5-30min, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min；Stop After stirring, being sieved by the screen cloth of the mixture 10-20 mesh in container, oversize is aluminium foil, and siftage is containing positive pole The solution of active substance；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying；Siftage carries out sucking filtration, thing water in filter Clean 1-3 time, it is thus achieved that positive active material；

Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in resistance furnace with 5 DEG C/heating rate of min makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h, it is thus achieved that useless LiMn2O4 powder；

Step (4): useless LiMn2O4 powder step (3) obtained and sodium bisulfate-g/g in mass ratio are 1:0.2-1:1.2's Putting into after ratio mixing and be fully ground mix homogeneously in ceramic mortar, the mixture after grinding loads ceramic crucible and adds pottery Lid covers, and is then placed in resistance kiln roasting, makes furnace temperature be raised to 400-650 DEG C and be incubated with the heating rate of 3-10 DEG C/min 10-60min；

Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, leaches Time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, by 1.0-3.0mol/L's Sodium carbonate liquor is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes the content of Li, Mn in filtering residue, according to lithium The requirement that mol ratio is 0.525:1 with manganese supplements lithium carbonate toward filtering residue, then abundant ball milling in ball mill, then by its Compress under the pressure of 0.1-100MPa, put in ceramic crucible, in 450 DEG C of constant temperature 4-7h in air atmosphere, then be warming up to 750 DEG C insulation 20h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 400 mesh sieves, it is thus achieved that manganate cathode material for lithium；

Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, then Crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, and crystal exists Be dried under 50-80 DEG C and 0.2-3h and obtain sodium bisulfate, it is thus achieved that sodium bisulfate return in step (4) and use.

The renovation process of lithium cell anode material lithium manganate waste material the most according to claim 1, it is characterised in that step Suddenly the sodium bisulfate described in (4) is: the sodium bisulfate that obtains in sodium bisulfate chemical products or step (6) or the two is with arbitrarily The mixture that ratio is mixed to form.

The renovation process of lithium cell anode material lithium manganate waste material the most according to claim 1, it is characterised in that step Suddenly the Ball-milling Time in (5) is 0.5-2h, and rotating speed is 200-500r/min.