CN105826630A

CN105826630A - Method for recycling manganese and lithium from lithium ion battery anode material lithium manganese oxide waste

Info

Publication number: CN105826630A
Application number: CN201610322562.7A
Authority: CN
Inventors: 王亚莉
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-05-16
Filing date: 2016-05-16
Publication date: 2016-08-03

Abstract

Disclosed is a method for recycling manganese and lithium from lithium ion battery anode material lithium manganese oxide waste. The method comprises the steps that a waste lithium ion battery is discharged and disassembled to obtain a waste anode piece, the waste anode piece is subjected to calcination, water dissolution and filtering to obtain a waste lithium manganese oxide; the waste lithium manganese oxide and sodium sulfate are mixed and then subjected to ball milling, and a product obtained after ball milling is placed into an absorption device; tail gas from acid production is converted and then led into the absorption device, gas exhausted from the absorption device meets the emission standard and is exhausted to the atmosphere, a mixture in the absorption device is taken out and leached with water, a sodium carbonate solution is added into the solution to be filtered, lithium carbonate is supplemented into filter residues, then, ball milling, compression and calcination are performed, and the lithium manganese oxide anode material with the good electrochemical performance is obtained again. A filtrate is subjected to crystallization treatment to obtain sodium sulfate.

Description

The method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material

Technical field

The method that the present invention relates to reclaim manganese lithium in lithium cell anode material lithium manganate waste material.

Background technology

Sulphuric acid is widely used in chemical fertilizer industry, metallurgical industry, petroleum industry, mechanical industry, medical industry, the production of detergent, war industry, atomic energy industry and aerospace industry etc..But sulfuric acid industry is also the chemical industry of high pollution, containing sulfur dioxide, sulfuric acid mist in the tail gas produced in sulphuric acid process.The antacid tail gas of sulfuric acid industry every year to gas pollutants such as the substantial amounts of sulfur dioxide of airborne release, severe contamination environment.China has issued " sulfuric acid industry pollutant emission standard " (GB26132-2010) on 30th in December in 2010, discharge to antacid tail gas clearly requires, it may be assumed that after 2013, the content of the antacid sulfur dioxide in tail gas of all newly-built and existing sulphuric acid production enterprises discharge have to be lower than 350mg/m³, sulfuric acid mist have to be lower than 30mg/m³.And current sulfuric acid industry SO in the tail gas that double-absorption production procedure is discharged₂Content typically at 600 ~ 1400mg/m³Left and right, it is impossible to directly to airborne release.

Antacid tail gas through removing sulfuric acid mist and to make SO₂Content reach standard after could be vented.The disclosed method reporting for work antacid treating tail gas has: sodium carbonate absorption process, sodium hydroxide absorption process, lime absorption, magnesium oxide absorption process, ammonia absorption process, ammonia ammonium sulphate process, ammonia-ammonium sulfite, ammonia-ammonium hydrogen sulfate method, sulfurous acid-Potassium acid sulfite method, peroxy-disulfuric acid conversion method, basic aluminum sulfate solution absorption method, Citrate Buffer, Exchange Resin by Adsorption, activated carbon adsorption conversion method etc..Wherein, sodium carbonate absorption process is to SO in antacid tail gas₂Absorbance higher and obtain sodium sulfite product, but sodium sulfite market is limited, and also needs to be continuously added antioxidant in absorption process and stop sodium sulfite to be oxidized to sodium sulfate, and when the price of sodium carbonate is higher than sodium sulfite, this method is the most uneconomical.Calx absorption process uses lime water or lime cream washing antacid tail gas, the method technology maturation, and production cost is low, but SO₂Absorption rate is slow, absorbability is little, the CaSO of generation₃And CaSO₄Easily blocking pipeline and equipment, this method produces substantial amounts of waste residue in addition, and these waste residues cause serious secondary pollution to environment.Ammonia absorption process uses liquefied ammonia or ammonia as absorbent, and absorption efficiency is high, desulfurization is thorough, but ammonia is volatile, and the consumption of absorbent is big, and additionally the source of ammonia is limited by regions bigger.Sodium hydroxide absorption process is to use sodium hydroxide to administer antacid tail gas, SO₂Absorbability is big, absorption rate is fast, efficiency is high, but the problem of maximum is that feed hydrogen sodium oxide is more expensive, and the cost of antacid treating tail gas is high.Additionally, the problem that other antacid method for treating tail gas the most generally exists several general character: 1) raw materials used price height, investment is relatively big, and Operation and Maintenance is relatively costly；2) the side-product added value obtained after antacid treating tail gas is low.

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.LiMn2O4 (LiMn₂O₄) price is low, current potential is high, environmental friendliness, security performance advantages of higher owing to having for positive electrode, part replacement cobalt acid lithium is widely used at compact lithium cell positive electrode and lithium-ion-power cell field.Owing to the service life of lithium ion battery is generally 2-3, therefore, scrap lithium ion battery is brought environmental pollution and resource reutilization problem are increasingly subject to pay attention to.

Have about the recovery method of valuable metal in lithium cell anode material lithium manganate waste material at present: patent [CN201410280343] discloses a kind of method utilizing waste lithium manganese oxide battery to prepare nickel ion doped, by useless LiMn2O4 being carried out leaching process with sulphuric acid and mixed solution of hydrogen peroxide, obtain containing lithium ion, the solution of manganese ion, then adding nickel salt, lithium salts and precipitant in solution, precipitate obtains nickel ion doped (LiNi again after calcining_0.5Mn_1.5O₄).Patent [CN201410246379] reports a kind of recovery manganese and method of copper resource from manganese systems waste and old lithium ion battery, continues with acid pasting, alkali solution technique, the sedimentation method, Vibration Screen point-score, flotation partition method or sonic oscillation method and obtains containing Cu²⁺、Mn²⁺Solution, then carry out electrolysis procedure, it is thus achieved that MnO₂And Cu.Patent [CN201310646706] discloses a kind of method being prepared nickel manganese hydroxide by useless electrokinetic cell.Nickeliferous, the mixed solution of manganese is obtained by dissolving useless nickel lithium manganate cathode material by least one in hydrochloric acid, sulphuric acid and nitric acid, nickel acetate or Nickel dichloride. or nickel 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, the most respectively with sodium hydroxide and the pH value of ammonia regulation solution, then 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, citric acid solution, hydrogenperoxide steam generator is successively used to dissolve the LiMn2O4 obtained from waste and old lithium ion battery, then in solution, lithium nitrate or lithium acetate or lithium sulfate are added, manganese nitrate or manganese acetate or manganese sulfate regulate the mol ratio of Li Yu Mn in solution, obtain gel with the pH value of ammonia regulation solution, then obtain 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 use malic acid solution and hydrogenperoxide steam generator to dissolve the manganate cathode material for lithium obtained from waste and old lithium ion battery, i.e. complete the course of dissolution of useless manganate cathode material for lithium.Patent [CN201210017163] disclose a kind of use pyrometallurgy technology utilize LiMn2O4 waste and old lithium ion battery and scrap iron for raw material manufacture manganeisen method.Patent [CN201010141128] discloses a kind of method reclaiming valuable metal in waste lithium manganese oxide battery.After refuse battery is broken, with N, one or more mixed solvents in dinethylformamide, N-Methyl pyrrolidone, oxolane soak battery core and obtain useless LiMn2O4, with with the addition of hydrogen peroxide mineral acid (hydrochloric acid of 36wt%, the nitric acid of 68wt%, 98wt% sulphuric acid in one or more mixed acid solutions) mixed solution dissolves useless LiMn2O4, solution ph is adjusted twice, it is thus achieved that MnO with NaOH and ammonia₂, add sodium carbonate liquor after precipitation operation, obtain lithium carbonate.Patent [CN200910116656] reports a kind of recovery MnO in anode material of wasted lithium manganate battery₂Method and application, obtain λ-MnO with sulphuric acid, hydrochloric acid, nitric acid or the normal pressure acidleach manganate cathode material for lithium that gives up₂, or the hydro-thermal acidleach manganate cathode material for lithium that gives up obtains α-/β-/γ-MnO₂.An Hongli etc., at " Peking University's journal (natural science edition) " Vol.42, report the recovery research of LiMn2O4 waste and old power lithium-ion battery main chemical elements, with the HNO of 2mol/L in SpecialIssue, Dec.2006,83-86₃The H of+1mol/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, reports based on waste lithium ion cell anode material LiMn in No.1, November2011,3276-3281₂O₄Preparation MnO₂And the achievement in research of chemical property, at normal temperatures and pressures, use the H of 0.5mol/L₂SO₄Acidleach is given up LiMn₂O₄3h prepares λ-MnO₂Nano-particle；Under 140 DEG C of hydrothermal conditions, use the H of 2mol/L₂SO₄Acidleach is given up LiMn₂O₄24h prepares β-MnO₂Nanometer rods.Peng Shantang etc. are at " Wuhan University of Technology's journal " Vol.24, and No.12, Dec.2002,27-29 report secondary oxidation-sedimentation method separation LiMn2O4 (LiMn₂O₄Lithium in) and the achievement in research of manganese, dissolve LiMn2O4 with the mixed solution of the nitric acid or hydrochloric acid or sulphuric acid that add hydrogen peroxide, then be separately added into a certain amount of (NH₄)₂S₂O₈(NH₄)₂CO₃, use secondary oxidation-sedimentation method to prepare MnO₂And lithium carbonate.

It has been reported that the method reclaiming valuable metal from useless LiMn2O4, recovery technology still has to use related chemistry reagent in a large number, such as sulphuric acid, hydrogen peroxide, citric acid, malic acid, hydrochloric acid, nitric acid, sodium bisulfate, sodium pyrosulfate etc., this makes the technology cost recovery currently reclaiming valuable metal from useless LiMn2O4 be difficult to reduce.

Summary of the invention

It is an object of the invention to provide a kind of method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material, the steps include:

Step (1): collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 1-3h in the sodium hydrate aqueous solution that concentration is 0.1-1.0mol/L；After discharge process, the lithium ion battery scrapped 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, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, sieved by the screen cloth of the mixture 10-20 mesh in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；

Step (2): mixed with sodium sulfate by useless LiMn2O4, then ball milling in ball mill, Ball-milling Time is 0.1-1.0h, and rotating speed is 200-500r/min, is loaded in absorption plant by the mixture after ball milling；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the sodium sulfate obtained in the sodium sulfate chemical products or step (5) being to buy of originating of sodium sulfate or the two mixture being mixed to form with arbitrary proportion；

Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.3-0.6m³S108 type vanadium catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation described in step (2), the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas₂Content whether less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, as reached requirement, it is emitted in air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas₂Content reach 350mg/m³Or the content of sulfuric acid mist reaches 30mg/m³, the most no longer it is passed through from conversion system gas out in this absorption plant, carries out SO in the absorption operation under the same terms and exit gas by being passed through in the standby absorption plant described in step (2) from conversion system gas out simultaneously₂Content, the monitoring of content of sulfuric acid mist；Taking out the mixture in the absorption plant being no longer passed through conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；

Step (4): being leached with the water of 20-50 DEG C under conditions of stirring by the mixture being no longer passed through in the absorption plant of conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, the sodium carbonate liquor that concentration is 1.0-3.0mol/L is slowly added to leachate, then filter, washing filtering residue is also dried, analyze Li in filtering residue, the content of Mn, lithium carbonate is supplemented toward filtering residue according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then ball milling in ball mill, again it is being used pressure compaction, Ball-milling Time is 0.5-2h, rotating speed is 200-500r/min, the pressure compressed is 0.1-100MPa, put in clean 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 again at 800 DEG C be incubated 20h, sample comminution after firing, grind, cross 400 mesh sieves, obtain the manganate cathode material for lithium that chemical property is good；

Step (5): the solution that step (4) is filtrated to get is crystallized in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dried under 50-80 DEG C and 0.2-3h and obtains sodium sulfate, it is thus achieved that sodium sulfate return in step (2) and use.

The present invention compared with prior art has easily operation, the low cost of the effective low cost of antacid tail gas clean-up, manganese lithium recovery, the advantage of purification process non-secondary pollution produce life.

Detailed description of the invention

The present invention is the method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material, the steps include:

Step (1): collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 1-3h in sodium hydrate aqueous solution；After discharge process, the lithium ion battery scrapped 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, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, sieved by the mixture screen cloth in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；

Step (2): mixed with sodium sulfate by useless LiMn2O4, then ball milling in ball mill, load the mixture after ball milling in absorption plant；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the sodium sulfate obtained in the sodium sulfate chemical products or step (5) being to buy of originating of sodium sulfate or the two mixture being mixed to form with arbitrary proportion；

Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through equipped with the conversion system of vanadium catalyst carries out conversion operation again, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of vanadium catalyst is rated for: 0.3-0.6m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation described in step (2), the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas₂Content whether less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, as reached requirement, it is emitted in air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas₂Content reach 350mg/m³Or the content of sulfuric acid mist reaches 30mg/m³, the most no longer it is passed through from conversion system gas out in this absorption plant, carries out SO in the absorption operation under the same terms and exit gas by being passed through in the standby absorption plant described in step (2) from conversion system gas out simultaneously₂Content, the monitoring of content of sulfuric acid mist；Taking out the mixture in the absorption plant being no longer passed through conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；

Step (4): being leached with the water of 20-50 DEG C under conditions of stirring by the mixture being no longer passed through in the absorption plant of conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, sodium carbonate liquor is slowly added to leachate, then filter, washing filtering residue is also dried, analyze Li in filtering residue, the content of Mn, lithium carbonate is supplemented toward filtering residue according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then ball milling in ball mill, again it is being used pressure compaction, put in clean 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 again at 800 DEG C be incubated 20h, sample comminution after firing, grind, cross 400 mesh sieves, obtain the manganate cathode material for lithium that chemical property is good；

The concentration of the sodium hydrate aqueous solution in the step (1) of approach described above is 0.1-1.0mol/L.

The positive plate of acquisition is 1:10-1:15 in ratio g/mL of the quality of positive plate Yu the volume of ceramic crucible by the step (1) of approach described above.

The step (1) of approach described above is 1:40-1:70 according to ratio g/mL of the volume of quality and the water of positive plate, positive plate is put into equipped with filling in the container of water and stirring 5-30min with motor stirrer, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min.

The screen cloth that screen cloth is 10-20 mesh in the step (1) of approach described above.

Being mixed with the ratio that sodium sulfate g/g in mass ratio is 1:0.01-2.0 by the useless LiMn2O4 obtained in the step (2) of approach described above, then ball milling in ball mill, Ball-milling Time is 0.1-1.0h, and rotating speed is 200-500r/min.

In the step (4) of approach described above, the concentration of sodium carbonate liquor is 1.0-3.0mol/L.

Ball-milling Time in the step (4) of approach described above is 0.5-2h, and rotating speed is 200-500r/min, and the pressure of compression is 0.1-100MPa.

Vanadium catalyst in the step (3) of method illustrated above is S108 type vanadium catalyst.

The present invention is further spread out below by embodiment.It it is only the better embodiment to the present invention described in embodiment, not the present invention is made any pro forma restriction, the every any simple modification embodiment of embodiment done according to the technical spirit of the present invention, equivalent variations and modification, belong in the range of technical solution of the present invention.

Embodiment 1:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.05 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 2:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.2 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 410 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 3:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.3 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 390 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 4:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.4 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 5:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.5 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 415 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 6:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.6 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 395 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 7:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.7 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 420 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 8:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.8 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 415 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 9:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:0.9 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 380 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 10:

Collect the scrap lithium ion battery doing positive electrode with LiMn2O4, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that ratio (g/mL) is 1:10 of the quality of positive plate Yu the volume of ceramic crucible by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:1.0 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 420 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 11:

Collect and make, with LiMn2O4, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；In the ratio that ratio (g/mL) is 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:1.1 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 410 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 12:

Collect and make, with LiMn2O4, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；In the ratio that ratio (g/mL) is 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:1.2 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 405 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 13:

Collect and make, with LiMn2O4, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；In the ratio that ratio (g/mL) is 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:1.3 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 395 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 14:

Collect and make, with LiMn2O4, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；In the ratio that ratio (g/mL) is 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:1.4 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 430 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Embodiment 15:

Collect and make, with LiMn2O4, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；In the ratio that ratio (g/mL) is 1:10 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 10 DEG C/min furnace temperature be raised to 600 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, it is that positive plate is put into equipped with filling in the container of water and stirring 20min with motor stirrer by 1:50 according to the ratio (g/mL) of the volume of quality and the water of positive plate, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 mesh of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated 1h with the heating rate of 10 DEG C/min, it is thus achieved that useless LiMn2O4；Being mixed with the ratio that sodium sulfate (g/g) in mass ratio is 1:1.5 by useless LiMn2O4, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, it is passed through again in the conversion system equipped with S108 type vanadium catalyst and carries out conversion operation, the condition of conversion operation is: gasinlet temperature 405 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m³Catalyst/(1000m³Antacid tail gas h)；Being passed through from conversion system gas out and have been charged into after ball milling carrying out the absorption plant of mixture absorption operation, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected₂Content less than 350mg/m³And whether the content of sulfuric acid mist is less than 30mg/m³, it is emitted in air after the gas cooling that absorption plant is exported；It is 1:20 leaching 30min with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the mixture in the absorption plant being no longer passed through conversion system exit gas under conditions of stirring；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitate, gained precipitate is through filtering, washing, after drying, analyze Li in precipitate, the content of Mn, a certain amount of lithium carbonate is supplemented toward precipitate according to the requirement that mol ratio is 0.525:1 of lithium Yu manganese, then with the speed abundant ball milling 2h of 400r/min in planetary ball mill, again it is compressed under the pressure of 5MPa, put in clean ceramic crucible, in 450 DEG C of constant temperature 6h in air atmosphere, it is slowly cooled to room temperature after being warming up to 800 DEG C of insulation 20h again, sample comminution after firing, grind, cross 400 mesh sieves, obtain manganate cathode material for lithium；Being crystallized in crystallizing evaporator by the solution being filtrated to get in above-mentioned steps, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium sulfate.

Above content is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the thought of the present invention, the most all will change, and this specification content should not be construed as limitation of the present invention.

Claims

1. the method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material, it is characterised in that the steps include:

The method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material the most according to claim 1, it is characterised in that: the positive plate of acquisition is 1:10-1:15 in ratio g/mL of the quality of positive plate Yu the volume of ceramic crucible by step (1).

The method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material the most according to claim 2, it is characterized in that: step (1) is 1:40-1:70 according to ratio g/mL of the volume of quality and the water of positive plate, positive plate is put into equipped with filling in the container of water and stirring 5-30min with motor stirrer, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min.

The method reclaiming manganese lithium in lithium cell anode material lithium manganate waste material the most according to claim 3, it is characterized in that: the useless LiMn2O4 obtained is mixed by step (2) with the ratio that sodium sulfate g/g in mass ratio is 1:0.01-2.0, then ball milling in ball mill.