CN105742747B - Utilize the method for useless cobalt acid lithium purification relieving haperacidity tail gas and Call Provision lithium - Google Patents

Utilize the method for useless cobalt acid lithium purification relieving haperacidity tail gas and Call Provision lithium Download PDF

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CN105742747B
CN105742747B CN201610315842.5A CN201610315842A CN105742747B CN 105742747 B CN105742747 B CN 105742747B CN 201610315842 A CN201610315842 A CN 201610315842A CN 105742747 B CN105742747 B CN 105742747B
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lithium
cobalt acid
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positive plate
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陈怀敬
王大辉
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Lanzhou University of Technology
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

Using the method for useless cobalt acid lithium purification relieving haperacidity tail gas and Call Provision lithium, step is：Used Li ion cell is discharged, disassembles the useless positive plate of acquisition, the fired positive plate that gives up, water dissolution, filtering obtain useless cobalt acid lithium；Ball milling after useless cobalt acid lithium is mixed with sodium sulphate, ball milling product are packed into absorption plant；Relieving haperacidity tail gas is passed through absorption plant again after first passing through conversion, the gas for meeting discharge standard of absorption plant out drains into air, mixture taking-up in absorption plant is gone out with water logging, it is filtered after adding in sodium carbonate liquor into solution again, ball milling, compression, roasting after supplement lithium carbonate, regain the good lithium cobaltate cathode material of chemical property in filter residue.Sodium sulphate is obtained after the crystallized processing of filtrate.

Description

Utilize the method for useless cobalt acid lithium purification relieving haperacidity tail gas and Call Provision lithium
Technical field
The present invention relates to the technologies that relieving haperacidity tail gas and Call Provision lithium are purified with useless cobalt acid lithium.
Background technology
Sulfuric acid is widely used in chemical fertilizer industry, metallurgical industry, the life of petroleum industry, mechanical industry, medical industry, detergent Production, war industry, atomic energy industry and aerospace industry etc..But sulfuric acid industry is also the chemical industry of high pollution, gas washing in SA production Contain sulfur dioxide, sulfuric acid mist in the tail gas generated in the process.The relieving haperacidity tail gas of sulfuric acid industry discharges a large amount of to air every year The gas pollutants such as sulfur dioxide, have seriously polluted the environment.It is issued on December 30th, 2010 in China《Sulfuric acid industry pollutant Discharge standard》(GB26132-2010), the discharge of relieving haperacidity tail gas is clearly required, i.e.,：After 2013 it is all newly-built and The content of the relieving haperacidity sulfur dioxide in tail gas of existing sulphuric acid production enterprises discharge has to be lower than 400mg/m3, sulfuric acid mist must be low In 30 mg/m3.And SO in the tail gas that current sulfuric acid industry is discharged through double-absorption production procedure2Content generally 600 ~ 1400 mg/m3Left and right, it is impossible to be discharged directly to the atmosphere.
Relieving haperacidity tail gas will pass through removing sulfuric acid mist and make SO2Content reach standard after could be vented.The disclosed system of reporting for work The method of sour treating tail gas has：Sodium carbonate absorption process, sodium hydroxide absorption process, lime absorption, magnesia absorption process, ammonia absorb Method, ammonia ammonium sulphate process, ammonia-ammonium sulfite, ammonia-ammonium hydrogen sulfate method, sulfurous acid-potassium bisulfite method, peroxy-disulfuric acid conversion Method, basic aluminum sulfate solution absorption method, Citrate Buffer, Exchange Resin by Adsorption, activated carbon adsorption and conversion method etc..Its In, sodium carbonate absorption process is to SO in relieving haperacidity tail gas2Absorptivity it is higher and obtain sodium sulfite product, but sodium sulfite market It is limited, and also need to be continuously added antioxidant in absorption process and sodium sulfite is prevented to be oxidized to sodium sulphate, when the valency of sodium carbonate When lattice are higher than sodium sulfite, this method is with regard to uneconomical.Lime absorption process is using limewash or milk of lime washing relieving haperacidity tail gas, the party Law technology is ripe, and production cost is low, but SO2Absorption rate is slow, absorbability is small, the CaSO of generation3And CaSO4Easily block pipe Road and equipment, a large amount of waste residue of method generation, these waste residues cause serious secondary pollution to environment in addition.Ammonia absorption process uses Liquefied ammonia or ammonium hydroxide are as absorbent, absorption efficiency is high, desulfurization is thorough, but ammonia is volatile, and the consumption of absorbent is big, in addition ammonia Source is limited by regions larger.Sodium hydroxide absorption process is to administer relieving haperacidity tail gas, SO using sodium hydroxide2Absorbability is big, The problem of absorption rate is fast, efficient, but maximum is that raw material sodium hydroxide is more expensive, relieving haperacidity treating tail gas it is of high cost.In addition, its The problem of its relieving haperacidity method for treating tail gas all generally existing several general character:1) raw materials used price is high, invests larger, Operation and Maintenance Cost is higher；2) the byproduct added value obtained after relieving haperacidity treating tail gas is low.
The lithium ion batteries of positive electrode active materials has been done since the 1990s commercial applications with cobalt acid lithium, it is wide It is general to be applied to the fields such as mobile phone, laptop, video camera, digital camera.However, the use of the type lithium ion battery Service life is typically about 3 ~ 5 years, and the type lithium ion battery quantity currently scrapped is more than 10,000,000,000.The discarded lithium of rationally disposition The problem of ion battery, can not be ignored.
Lithium cobalt valuable metal is recycled in the positive pole material of lithium cobalt acid obtained from scrap lithium ion battery widely to be closed Note.The method of recycling valuable metal from the used Li ion cell that positive electrode is done using cobalt acid lithium for having disclosed report is main Have, Zhang P W etc. exist《Hydrometallurgy》It is reported in Vol.47 No.2-3,1998,259-271 using hydrochloric acid Lithium ion cell anode waste is leached, then cobaltous sulfate and lithium carbonate are obtained through the operations such as extracting, precipitating.Wu Fang exists《China YouSe Acta Metallurgica Sinica》The anode waste obtained in used Li ion cell is reported in Vol.14 No.4,2004,697-701 to use With sulfuric acid and hydrogen peroxide Ore Leaching under high temperature, cobaltous sulfate and lithium carbonate are obtained using extraction, precipitation operation.Myoung J etc. exist 《Journal of Power Sources》It is reported in Vol.112,2002,639-642 and dissolves used Li ion with hot nitric acid Then the anode waste obtained in battery obtains Co after electro-deposition operation, low temperature calcination3O4.Patent [CN201210491084] reports one kind and Co is produced from waste and old lithium ion battery3O4Method, by scrap lithium ion battery just Pole impregnates in organic solvent, separates positive pole powder material and aluminum foil current collector, then add and contain into positive pole powder material It is roasted after fluorine organic, obtains Co3O4Material.Patent [CN201210167969] reports a kind of efficient enhanced leaching and discards lithium The method of metal in ion battery, by adding in cobalt acid lithium powder in dilute acid soln, controlling solid-to-liquid ratio and adding in ferrous sulfate, Logical DC voltage improves the leaching efficiency of cobalt acid lithium.Patent [CN201180048492] report it is a kind of for recycle Li from The method of son, by introducing one or more cyclosiloxane, so that lithium ion forms one or more cyclosiloxane-Li ions and matches Object is closed, then the organic phase containing cyclosiloxane-Li ionic complexs is separated from the water.Patent [CN201010523257] is reported A kind of method that lithium is recycled from the waste and old lithium ion battery and waste pole piece, is leached by using acid and reducing agent, is used in combination Chemical method removes the impurity such as iron, copper, the aluminium in leachate, then precipitates the lithium in leachate with villiaumite, obtains lithium fluoride product.Patent [CN200910117702] is reported by by useless LiCoO2Powder is mixed with the salt of alkali metallic sodium and potassium after higher temperature Lower roasting, product of roasting are gone out with water logging, and leachate obtains cobalt oxalate and lithium carbonate through heavy cobalt and sinker operation.Patent [CN200910093727] reports a kind of method for being recycled using waste and old lithium ion battery and preparing cobalt acid lithium, by by waste and old lithium Ion battery electric eliminating, fractionation, crushing, NMP processing, calcining, obtain waste and old LiCoO2Material, then by LiCoO2Material with it is natural Ball milling after organic acid and hydrogen peroxide mixing, and obtain Li+、Co2+Solution, ammonium hydroxide is added dropwise in the solution and prepares xerogel and secondary Calcining obtains cobalt acid lithium electrode material.Patent [CN200910039217] discloses a kind of waste lithium ion battery cathode material Recycling and regeneration method, by being crushed, being ground, except aluminium, acidleach, extraction copper, chemistry by used Li ion cell cathode waste Removal of impurities, adds in lithium source secondary high-temperature baking operation at precipitation, realizes cathode material regeneration.Patent [CN200810028730] is open A kind of method for being recycled from waste and old lithium ion battery, preparing cobalt acid lithium.By the way that lithium ion battery positive plate is crushed, After screening, useless cobalt acid lithium is obtained；Except no-bonder, conductive agent acetylene black in constant temperature resistance furnace, it is incorporated the carbonic acid of proper proportion Lithium synthesizes active cobalt acid lithium battery material in the sintering of Muffle furnace high temperature.Patent [CN200710057623] discloses A kind of waste lithium ion cell anode material lithium cobaltate activating process.Waste lithium ion cell anode material is removed at high temperature Binding agent PVDF, calcines cobalt acid lithium at high temperature, and failure cobalt acid lithium is made to generate crystallization reaction, has layer structure again.Patent The method that [CN200510018601] reports separating and recovering cobalt in a kind of positive pole material of lithium cobalt acid from waste and old lithium ion battery. Waste and old lithium ion battery carries out physics and disassembles, calcines, after organic solvent immersion, obtains useless cobalt acid lithium, useless cobalt acid lithium is placed in acid H is used under the conditions of property2O2Or Na2S2O3As reducing agent, dissolving is obtained containing Co2+And Li+Solution, then using NaOH solution as precipitation Agent, by the Co in solution2+Ion conversion is into Co (OH)2Precipitation.Patent [CN200510015078] discloses a kind of from scrapping Recycling prepares Li in lithium ion battery x CoO2Method.Used Li ion cell positive electrode is cut into fractionlet and is immersed in N- first In base -2-Pyrrolidone liquid, separation obtains active material LixCoO2Black powder, then black powder is scattered in salpeter solution Or in hydrochloric acid solution, using filter, precipitation operation, blue precipitate is obtained, sediment roasts at high temperature, obtains LixCoO2Powder Body.
It has been reported that the method that valuable metal lithium cobalt is recycled from useless cobalt acid lithium, recovery technology still has to largely use phase Chemical reagent, such as sulfuric acid, hydrogen peroxide, sodium thiosulfate, hydrochloric acid, nitric acid, niter cake, potassium acid sulfate, sodium pyrosulfate are closed, this So that the technology cost recovery that valuable metal lithium cobalt is currently recycled from useless cobalt acid lithium is difficult to reduce.
Invention content
The object of the present invention is to provide a kind of methods for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium.
The present invention is that the present invention is the method for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, and step is：
Step（1）：Collect the scrap lithium ion battery that positive electrode is done with cobalt acid lithium, the hydroxide being positioned at room temperature The discharge treatment of 1-3h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains anode Piece；The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain positive plate；It will obtain The positive plate obtained is fitted into ceramic crucible, and be subsequently placed in resistance furnace makes furnace temperature since room temperature with the heating rate of 5 DEG C/min 550 DEG C of heat preservation 0.5-1h are raised to, then naturally cool to room temperature；The positive plate by roasting is taken out, positive plate is put into and is equipped with It fills in the container of water and stirs 5-30min, the mixture in container is sieved with sieve, oversize is aluminium foil, under sieve Object is the solution containing positive active material；Screenings is filtered, and object washes with water 1-3 times in filter, obtains positive electrode active material Matter；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in resistance furnace makes stove with the heating rate of 5 DEG C/min Temperature is raised to 500-700 DEG C and keeps the temperature 0.5-3h, obtains useless cobalt acid lithium；
Step（2）：Useless cobalt acid lithium with sodium sulphate is mixed, then ball milling in the ball mill, the mixture after ball milling is filled Enter in absorption plant；The mixture after ball milling is packed into another identical absorption plant as spare absorption plant In step（3）Middle use；In this step, the source of sodium sulphate is the sodium sulphate chemical products or step of purchase（5）Middle acquisition Sodium sulphate or the mixture that is mixed to form with arbitrary proportion of the two；
Step（3）：The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, after first passing through heat treatment, then is passed through Conversion operation is carried out in conversion system equipped with vanadium catalyst, the condition of conversion operation is：400-405 DEG C of gasinlet temperature, Flow velocity 0.23-1.2m/s, in conversion system the filling of vanadium catalyst be rated for：0.3-0.6m3Catalyst/(1000m3Relieving haperacidity tail Gas h)；The gas come out from conversion system is passed through step（2）Described in have been charged into after ball milling in the absorption plant of mixture Absorption operation is carried out, the condition of absorption operation is：300-450 DEG C of temperature, inlet gas flow velocity 0.2-1.2m/s；Monitoring absorbs dress Put SO in exit gas2Content whether be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, such as reach requirement, It will be emitted into air after the gas cooling of absorption plant outlet；Such as monitor SO in absorption plant exit gas2Content reach To 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then the gas come out from conversion system is no longer passed through into the absorption plant Body, while the gas come out from conversion system is passed through step（2）It is carried out under the same terms in the spare absorption plant SO in absorption operation and exit gas2Content, the content of sulfuric acid mist monitoring；It takes out and conversion system is no longer passed through in this step Mixture in the absorption plant of exit gas, the absorption plant then return to step（2）In be again loaded into the mixing after ball milling Object uses in this step as spare absorption plant；
Step（4）：By step（3）In the mixture that is no longer passed through in the absorption plant of conversion system exit gas stirring Under conditions of leached with 20-50 DEG C of water, extraction time 5-30min, solid-to-liquid ratio g/mL be 1:10-1:50；Then leaching Go out liquid and be warming up to 95-98 DEG C, sodium carbonate liquor is slowly added to leachate, is then filtered, wash filter residue and drying, analyze filter residue The content of middle Li, Co are 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements lithium carbonate toward filter residue, then in the ball mill Ball milling, then it is put into clean ceramic crucible, using pressure compaction in 650-700 DEG C of constant temperature 2- in air atmosphere 6h, then be warming up at 900 DEG C and be slowly cooled to room temperature after heat preservation 10h, sample comminution, grinding after firing are crossed 500 mesh sieve, are obtained Obtain the good lithium cobaltate cathode material of chemical property；
Step（5）：By step（4）The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.012-0.015MPa, 120-140 DEG C of temperature are spent, crystal is dry under 50-80 DEG C and 0.2-3h to obtain sodium sulphate, acquisition Sodium sulphate return to step（2）Middle use.
The present invention compared with prior art have it is easy to operate, relieving haperacidity good tail gas purification effect is at low cost, cobalt lithium recycling into The advantages of this low, governance process non-secondary pollution object generates.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
As shown in Figure 1, the present invention is the method for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, step is：
Step（1）：Collect the scrap lithium ion battery that positive electrode is done with cobalt acid lithium, the hydroxide being positioned at room temperature The discharge treatment of 1-3h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains anode Piece；The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain positive plate；It will obtain The positive plate obtained is fitted into ceramic crucible, and be subsequently placed in resistance furnace makes furnace temperature since room temperature with the heating rate of 5 DEG C/min 550 DEG C of heat preservation 0.5-1h are raised to, then naturally cool to room temperature；The positive plate by roasting is taken out, positive plate is put into and is equipped with It fills in the container of water and stirs 5-30min, the mixture in container is sieved with sieve, oversize is aluminium foil, under sieve Object is the solution containing positive active material；Screenings is filtered, and object washes with water 1-3 times in filter, obtains positive electrode active material Matter；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in resistance furnace makes stove with the heating rate of 5 DEG C/min Temperature is raised to 500-700 DEG C and keeps the temperature 0.5-3h, obtains useless cobalt acid lithium；
Step（2）：Useless cobalt acid lithium with sodium sulphate is mixed, then ball milling in the ball mill, the mixture after ball milling is filled Enter in absorption plant；The mixture after ball milling is packed into another identical absorption plant as spare absorption plant In step（3）Middle use；In this step, the source of sodium sulphate is the sodium sulphate chemical products or step of purchase（5）Middle acquisition Sodium sulphate or the mixture that is mixed to form with arbitrary proportion of the two；
Step（3）：The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, after first passing through heat treatment, then is passed through Conversion operation is carried out in conversion system equipped with vanadium catalyst, the condition of conversion operation is：400-405 DEG C of gasinlet temperature, Flow velocity 0.23-1.2m/s, in conversion system the filling of vanadium catalyst be rated for：0.3-0.6m3Catalyst/(1000m3Relieving haperacidity tail Gas h)；The gas come out from conversion system is passed through step（2）Described in have been charged into after ball milling in the absorption plant of mixture Absorption operation is carried out, the condition of absorption operation is：300-450 DEG C of temperature, inlet gas flow velocity 0.2-1.2m/s；Monitoring absorbs dress Put SO in exit gas2Content whether be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, such as reach requirement, It will be emitted into air after the gas cooling of absorption plant outlet；Such as monitor SO in absorption plant exit gas2Content reach To 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then the gas come out from conversion system is no longer passed through into the absorption plant Body, while the gas come out from conversion system is passed through step（2）It is carried out under the same terms in the spare absorption plant SO in absorption operation and exit gas2Content, the content of sulfuric acid mist monitoring；It takes out and conversion system is no longer passed through in this step Mixture in the absorption plant of exit gas, the absorption plant then return to step（2）In be again loaded into the mixing after ball milling Object uses in this step as spare absorption plant；
Step（4）：By step（3）In the mixture that is no longer passed through in the absorption plant of conversion system exit gas stirring Under conditions of leached with 20-50 DEG C of water, extraction time 5-30min, solid-to-liquid ratio g/mL be 1:10-1:50；Then leaching Go out liquid and be warming up to 95-98 DEG C, sodium carbonate liquor is slowly added to leachate, is then filtered, wash filter residue and drying, analyze filter residue The content of middle Li, Co are 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements lithium carbonate toward filter residue, then in the ball mill Ball milling, then it is put into clean ceramic crucible, using pressure compaction in 650-700 DEG C of constant temperature 2- in air atmosphere 6h, then be warming up at 900 DEG C and be slowly cooled to room temperature after heat preservation 10h, sample comminution, grinding after firing are crossed 500 mesh sieve, are obtained Obtain the good lithium cobaltate cathode material of chemical property；
Step（5）：By step（4）The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.012-0.015MPa, 120-140 DEG C of temperature are spent, crystal is dry under 50-80 DEG C and 0.2-3h to obtain sodium sulphate, acquisition Sodium sulphate return to step（2）Middle use.
The step of approach described above（1）In sodium hydrate aqueous solution a concentration of 0.1-1.0mol/L.
The step of approach described above（1）The middle positive plate by acquisition is by the quality of positive plate and the volume of ceramic crucible Ratio g/mL is 1:10-1:15.
The step of approach described above（1）According to positive plate quality and water volume ratio g/mL be 1:40-1: 70, positive plate is put into equipped with filling in the container of water and stir 5-30min with electric mixer, the temperature of water in whipping process It is 20-50 DEG C, mixing speed 10-200r/min.
The step of approach described above（1）In sieve be 10-20 mesh sieve.
The step of approach described above（2）Middle by obtained useless cobalt acid lithium and sodium sulphate g/g is in mass ratio 1:0.01- 2.2 ratio mixing, then ball milling, Ball-milling Time are 0.1-1.0 h in the ball mill, and rotating speed is 200-500 r/min.
The step of approach described above（4）A concentration of 1.0-3.0mol/L of middle sodium carbonate liquor.
The step of approach described above（4）In Ball-milling Time for 0.5-2h, rotating speed 200-500r/min, the pressure of compression Power is 0.1-100MPa.
The step of approach described above（3）In vanadium catalyst be S108 type vanadium catalysts.
Below the present invention is further spread out with embodiment.Only be described in embodiment to the present invention better embodiment and , not make limitation in any form to the present invention, every technical spirit according to the present invention is to the embodiment of embodiment Any simple modification made, equivalent variations and modification, belong in the range of technical solution of the present invention.
Embodiment 1：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:0.05 ratio mixing, then the ball milling in planetary ball mill, Ball-milling Time are 0.5 h, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；It is come out from gas washing in SA production double-absorption system Relieving haperacidity tail gas, after first passing through heat treatment, then be passed through in the conversion system equipped with S108 type vanadium catalysts and carry out conversion operation, The condition of conversion operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling of S108 type vanadium catalysts in conversion system It is rated for：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；It is passed through after having been charged into ball milling and mixes from the gas of conversion system out It closes in the absorption plant of object and carries out absorption operation, the condition of absorption operation is：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；Inspection Measure SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, will inhale It is emitted into air after the gas cooling of receiving apparatus outlet；It is mixed in the absorption plant of conversion system exit gas by being no longer passed through It closes object to be leached with 25 DEG C of water under conditions of stirring, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then Leachate is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and does It is dry, the content of Li, Co in filter residue are analyzed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of toward sediment Lithium carbonate then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then its pressure in 10MPa is pushed Tightly, it is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to after 900 DEG C of heat preservation 10h slowly It is cooled to room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property Material；The solution being obtained by filtration is crystallized in crystallizing evaporator, cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, Crystal is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 2：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:0.3 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：410 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 3：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:0.5 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：390 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 4：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:0.7 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 5：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:0.9 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：415 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 6：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:1.1 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 7：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:1.3 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：420 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 8：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:1.5 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：415 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 9：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:1.7 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：380 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 10：
The scrap lithium ion battery that positive electrode is done with cobalt acid lithium is collected, is positioned over the hydroxide of 0.5mol/L at room temperature The discharge treatment of 2h is carried out in sodium water solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate； In the quality of positive plate and the ratio of the volume of ceramic crucible (g/mL) it is 1 by the positive plate of acquisition:10 ratio is by positive plate It is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 since room temperature with the heating rate of 5 DEG C/min DEG C heat preservation 0.5h, naturally cool to room temperature after power-off；The positive plate by roasting is taken out, according to the quality of positive plate and the body of water Long-pending ratio (g/mL) is 1:50 are put into positive plate equipped with 20min is stirred in the container for filling water and with electric mixer, stir The temperature of water is 25 DEG C during mixing, mixing speed 100r/min；After stopping stirring, by 10 purposes of the mixture in container Sieve is sieved, and oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, in filter Object washes with water 3 times, obtains positive active material；The positive active material of acquisition is fitted into ceramic crucible, is subsequently placed in case Furnace temperature is made to be raised to 550 DEG C with the heating rate of 5 DEG C/min in formula resistance furnace and keep the temperature 1h, obtain useless cobalt acid lithium；By useless cobalt acid lithium It is 1 with sodium sulphate (g/g) in mass ratio:1.9 ratio mixes, then the ball milling in planetary ball mill, Ball-milling Time 0.5 H, rotating speed are 300 r/min；Mixture after ball milling is fitted into absorption plant；The system come out from gas washing in SA production double-absorption system Sour tail gas after first passing through heat treatment, then is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, conversion The condition of operation is：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, the filling quota of S108 type vanadium catalysts in conversion system For：0.5m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system, which is passed through, has been charged into mixture after ball milling Absorption plant in carry out absorption operation, the condition of absorption operation is：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；It detects SO in absorption plant exit gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, filled absorbing It is emitted into air after putting the gas cooling of outlet；The mixture in the absorption plant of conversion system exit gas will be no longer passed through It is leached under conditions of stirring with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leaching Liquid is warming up to 97 DEG C, and the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, and washs filter residue and drying, point The content of Li, Co in filter residue are analysed, is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of carbonic acid toward sediment Lithium then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it is compressed under the pressure of 10MPa, It is put into clean ceramic crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then is warming up to Slow cooling after 900 DEG C of heat preservation 10h To room temperature, sample comminution, grinding after firing cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It will The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 0.015MPa, 120 DEG C of temperature, crystallization Object is dry under 80 DEG C and 2h to obtain sodium sulphate.
Embodiment 11：
The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain anode Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is packed into ceramic crucible by 10 ratio In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of heat preservation 0.5h since room temperature with the heating rate of 5 DEG C/min, Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate ML it is) 1:50 are put into positive plate equipped with filling in the container of water and stir 20min with electric mixer, water in whipping process Temperature is 25 DEG C, mixing speed 100r/min；After stopping stirring, the mixture in container is sieved with the sieve of 10 mesh Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, and object washes with water 3 in filter It is secondary, obtain positive active material；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and keeps the temperature 1h, obtains useless cobalt acid lithium；Useless cobalt acid lithium and sodium sulphate are pressed into matter Amount is 1 than (g/g):2.1 ratio mixing, the then ball milling in planetary ball mill, Ball-milling Time are 0.5 h, rotating speed 300 r/min；Mixture after ball milling is fitted into absorption plant；The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, first passes through After crossing heat treatment, then it is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, the condition of conversion operation For：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, in conversion system the filling of S108 type vanadium catalysts be rated for：0.5m3It urges Agent/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system is passed through the absorption plant for having been charged into mixture after ball milling Middle carry out absorption operation, the condition of absorption operation are：410 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect that absorption plant goes out SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, by the gas of absorption plant outlet It is emitted into air after body cooling；By the mixture being no longer passed through in the absorption plant of conversion system exit gas stirring item It is leached under part with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leachate is warming up to 97 DEG C, the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, washs filter residue and drying, analyze Li in filter residue, The content of Co is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of lithium carbonate toward sediment, is then expert at With the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it under the pressure of 10MPa is compressed, be put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is slowly cooled to room temperature, fires after being warming up to 900 DEG C of heat preservation 10h Sample comminution afterwards, grinding cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It is molten by what is be obtained by filtration Liquid crystallizes in crystallizing evaporator, cerium sulphate crystal condition for vacuum degree 0.015MPa, 120 DEG C of temperature, crystal at 80 DEG C and It is dry under 2h to obtain sodium sulphate.
Embodiment 12：
The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain anode Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is packed into ceramic crucible by 10 ratio In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of heat preservation 0.5h since room temperature with the heating rate of 5 DEG C/min, Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate ML it is) 1:50 are put into positive plate equipped with filling in the container of water and stir 20min with electric mixer, water in whipping process Temperature is 25 DEG C, mixing speed 100r/min；After stopping stirring, the mixture in container is sieved with the sieve of 10 mesh Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, and object washes with water 3 in filter It is secondary, obtain positive active material；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and keeps the temperature 1h, obtains useless cobalt acid lithium；Useless cobalt acid lithium and sodium sulphate are pressed into matter Amount is 1 than (g/g):1.0 ratio mixing, the then ball milling in planetary ball mill, Ball-milling Time are 0.5 h, rotating speed 300 r/min；Mixture after ball milling is fitted into absorption plant；The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, first passes through After crossing heat treatment, then it is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, the condition of conversion operation For：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, in conversion system the filling of S108 type vanadium catalysts be rated for：0.5m3It urges Agent/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system is passed through the absorption plant for having been charged into mixture after ball milling Middle carry out absorption operation, the condition of absorption operation are：405 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect that absorption plant goes out SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, by the gas of absorption plant outlet It is emitted into air after body cooling；By the mixture being no longer passed through in the absorption plant of conversion system exit gas stirring item It is leached under part with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leachate is warming up to 97 DEG C, the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, washs filter residue and drying, analyze Li in filter residue, The content of Co is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of lithium carbonate toward sediment, is then expert at With the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it under the pressure of 10MPa is compressed, be put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is slowly cooled to room temperature, fires after being warming up to 900 DEG C of heat preservation 10h Sample comminution afterwards, grinding cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It is molten by what is be obtained by filtration Liquid crystallizes in crystallizing evaporator, cerium sulphate crystal condition for vacuum degree 0.015MPa, 120 DEG C of temperature, crystal at 80 DEG C and It is dry under 2h to obtain sodium sulphate.
Embodiment 13：
The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain anode Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is packed into ceramic crucible by 10 ratio In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of heat preservation 0.5h since room temperature with the heating rate of 5 DEG C/min, Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate ML it is) 1:50 are put into positive plate equipped with filling in the container of water and stir 20min with electric mixer, water in whipping process Temperature is 25 DEG C, mixing speed 100r/min；After stopping stirring, the mixture in container is sieved with the sieve of 10 mesh Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, and object washes with water 3 in filter It is secondary, obtain positive active material；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and keeps the temperature 1h, obtains useless cobalt acid lithium；Useless cobalt acid lithium and sodium sulphate are pressed into matter Amount is 1 than (g/g):0.6 ratio mixing, the then ball milling in planetary ball mill, Ball-milling Time are 0.5 h, rotating speed 300 r/min；Mixture after ball milling is fitted into absorption plant；The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, first passes through After crossing heat treatment, then it is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, the condition of conversion operation For：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, in conversion system the filling of S108 type vanadium catalysts be rated for：0.5m3It urges Agent/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system is passed through the absorption plant for having been charged into mixture after ball milling Middle carry out absorption operation, the condition of absorption operation are：395 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect that absorption plant goes out SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, by the gas of absorption plant outlet It is emitted into air after body cooling；By the mixture being no longer passed through in the absorption plant of conversion system exit gas stirring item It is leached under part with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leachate is warming up to 97 DEG C, the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, washs filter residue and drying, analyze Li in filter residue, The content of Co is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of lithium carbonate toward sediment, is then expert at With the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it under the pressure of 10MPa is compressed, be put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is slowly cooled to room temperature, fires after being warming up to 900 DEG C of heat preservation 10h Sample comminution afterwards, grinding cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It is molten by what is be obtained by filtration Liquid crystallizes in crystallizing evaporator, cerium sulphate crystal condition for vacuum degree 0.015MPa, 120 DEG C of temperature, crystal at 80 DEG C and It is dry under 2h to obtain sodium sulphate.
Embodiment 14：
The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain anode Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is packed into ceramic crucible by 10 ratio In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of heat preservation 0.5h since room temperature with the heating rate of 5 DEG C/min, Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate ML it is) 1:50 are put into positive plate equipped with filling in the container of water and stir 20min with electric mixer, water in whipping process Temperature is 25 DEG C, mixing speed 100r/min；After stopping stirring, the mixture in container is sieved with the sieve of 10 mesh Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, and object washes with water 3 in filter It is secondary, obtain positive active material；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and keeps the temperature 1h, obtains useless cobalt acid lithium；Useless cobalt acid lithium and sodium sulphate are pressed into matter Amount is 1 than (g/g):1.2 ratio mixing, the then ball milling in planetary ball mill, Ball-milling Time are 0.5 h, rotating speed 300 r/min；Mixture after ball milling is fitted into absorption plant；The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, first passes through After crossing heat treatment, then it is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, the condition of conversion operation For：400 DEG C, flow velocity 0.3m/s of gasinlet temperature, in conversion system the filling of S108 type vanadium catalysts be rated for：0.5m3It urges Agent/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system is passed through the absorption plant for having been charged into mixture after ball milling Middle carry out absorption operation, the condition of absorption operation are：425 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect that absorption plant goes out SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, by the gas of absorption plant outlet It is emitted into air after body cooling；By the mixture being no longer passed through in the absorption plant of conversion system exit gas stirring item It is leached under part with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leachate is warming up to 97 DEG C, the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, washs filter residue and drying, analyze Li in filter residue, The content of Co is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of lithium carbonate toward sediment, is then expert at With the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it under the pressure of 10MPa is compressed, be put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is slowly cooled to room temperature, fires after being warming up to 900 DEG C of heat preservation 10h Sample comminution afterwards, grinding cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It is molten by what is be obtained by filtration Liquid crystallizes in crystallizing evaporator, cerium sulphate crystal condition for vacuum degree 0.015MPa, 120 DEG C of temperature, crystal at 80 DEG C and It is dry under 2h to obtain sodium sulphate.
Embodiment 15：
The anode leftover pieces for doing the lithium ion battery manufacturing process of positive electrode with cobalt acid lithium and generating are collected, obtain anode Piece；Ratio (g/mL) in the volume of the quality and ceramic crucible of positive plate is 1:Positive plate is packed into ceramic crucible by 10 ratio In, be subsequently placed in chamber type electric resistance furnace makes furnace temperature be raised to 550 DEG C of heat preservation 0.5h since room temperature with the heating rate of 5 DEG C/min, Room temperature is naturally cooled to after power-off；The positive plate by roasting is taken out, according to the ratio (g/ of the volume of the quality and water of positive plate ML it is) 1:50 are put into positive plate equipped with filling in the container of water and stir 20min with electric mixer, water in whipping process Temperature is 25 DEG C, mixing speed 100r/min；After stopping stirring, the mixture in container is sieved with the sieve of 10 mesh Point, oversize is aluminium foil, and screenings is the solution containing positive active material；Screenings is filtered, and object washes with water 3 in filter It is secondary, obtain positive active material；The positive active material of acquisition is fitted into ceramic crucible, be subsequently placed in chamber type electric resistance furnace with The heating rate of 5 DEG C/min makes furnace temperature be raised to 550 DEG C and keeps the temperature 1h, obtains useless cobalt acid lithium；Useless cobalt acid lithium and sodium sulphate are pressed into matter Amount is 1 than (g/g):1.4 ratio mixing, the then ball milling in planetary ball mill, Ball-milling Time are 0.5 h, rotating speed 300 r/min；Mixture after ball milling is fitted into absorption plant；The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, first passes through After crossing heat treatment, then it is passed through in the conversion system equipped with S108 type vanadium catalysts and carries out conversion operation, the condition of conversion operation For：405 DEG C, flow velocity 0.3m/s of gasinlet temperature, in conversion system the filling of S108 type vanadium catalysts be rated for：0.5m3It urges Agent/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system is passed through the absorption plant for having been charged into mixture after ball milling Middle carry out absorption operation, the condition of absorption operation are：400 DEG C of temperature, inlet gas flow velocity 0.3m/s；Detect that absorption plant goes out SO in gas2Content be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, by the gas of absorption plant outlet It is emitted into air after body cooling；By the mixture being no longer passed through in the absorption plant of conversion system exit gas stirring item It is leached under part with 25 DEG C of water, extraction time 25min, solid-to-liquid ratio (g/mL) is 1:30；Then leachate is warming up to 97 DEG C, the sodium carbonate liquor of 2.0mol/L is slowly added to leachate, is then filtered, washs filter residue and drying, analyze Li in filter residue, The content of Co is 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements a certain amount of lithium carbonate toward sediment, is then expert at With the abundant ball milling 2h of the speed of 400r/min in planetary ball mill, then it under the pressure of 10MPa is compressed, be put into clean pottery In porcelain crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is slowly cooled to room temperature, fires after being warming up to 900 DEG C of heat preservation 10h Sample comminution afterwards, grinding cross 500 mesh sieve, obtain the good lithium cobaltate cathode material of chemical property；It is molten by what is be obtained by filtration Liquid crystallizes in crystallizing evaporator, cerium sulphate crystal condition for vacuum degree 0.015MPa, 120 DEG C of temperature, crystal at 80 DEG C and It is dry under 2h to obtain sodium sulphate.

Claims (9)

1. the method for relieving haperacidity tail gas and Call Provision lithium is purified using useless cobalt acid lithium, which is characterized in that its step is：
Step（1）：Collect the scrap lithium ion battery that positive electrode is done with cobalt acid lithium, the sodium hydroxide water being positioned at room temperature The discharge treatment of 1-3h is carried out in solution；After discharge treatment, the lithium ion battery scrapped is disassembled, obtains positive plate；It receives Collection makees the anode leftover pieces of the lithium ion battery manufacturing process generation of positive electrode with cobalt acid lithium, obtains positive plate；By acquisition Positive plate is fitted into ceramic crucible, and be subsequently placed in resistance furnace is raised to furnace temperature since room temperature with the heating rate of 5 DEG C/min 550 DEG C of heat preservation 0.5-1h, then naturally cool to room temperature；The positive plate by roasting is taken out, positive plate is put into equipped with filling In the container of water and 5-30min is stirred, the mixture in container is sieved with sieve, oversize is aluminium foil, and screenings is Solution containing positive active material；Screenings is filtered, and object washes with water 1-3 times in filter, obtains positive active material；It will The positive active material of acquisition is fitted into ceramic crucible, and be subsequently placed in resistance furnace makes furnace temperature liter with the heating rate of 5 DEG C/min To 500-700 DEG C and 0.5-3h is kept the temperature, obtains useless cobalt acid lithium；
Step（2）：Useless cobalt acid lithium with sodium sulphate is mixed, then ball milling in the ball mill, the mixture after ball milling is packed into and is inhaled In receiving apparatus；The mixture after ball milling is packed into another identical absorption plant as spare absorption plant in step Suddenly（3）Middle use；In this step, the source of sodium sulphate is the sodium sulphate chemical products or step of purchase（5）The sulphur of middle acquisition The mixture that sour sodium or the two are mixed to form with arbitrary proportion；
Step（3）：The relieving haperacidity tail gas come out from gas washing in SA production double-absorption system, after first passing through heat treatment, then is passed through and is equipped with Conversion operation is carried out in the conversion system of vanadium catalyst, the condition of conversion operation is：400-405 DEG C of gasinlet temperature, flow velocity 0.23-1.2m/s, in conversion system the filling of vanadium catalyst be rated for：0.3-0.6m3Catalyst/(1000m3Relieving haperacidity tail gas h)；The gas come out from conversion system is passed through step（2）Described in have been charged into after ball milling and carried out in the absorption plant of mixture Absorption operation, the condition of absorption operation are：300-450 DEG C of temperature, inlet gas flow velocity 0.2-1.2m/s；Monitoring absorption plant goes out SO in gas2Content whether be less than 400mg/m3And whether the content of sulfuric acid mist is less than 30mg/m3, such as reach requirement, will inhale It is emitted into air after the gas cooling of receiving apparatus outlet；Such as monitor SO in absorption plant exit gas2Content reach 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then the gas come out from conversion system is no longer passed through into the absorption plant Body, while the gas come out from conversion system is passed through step（2）It is carried out under the same terms in the spare absorption plant SO in absorption operation and exit gas2Content, the content of sulfuric acid mist monitoring；It takes out and conversion system is no longer passed through in this step Mixture in the absorption plant of exit gas, the absorption plant then return to step（2）In be again loaded into the mixing after ball milling Object uses in this step as spare absorption plant；
Step（4）：By step（3）In be no longer passed through item of the mixture in the absorption plant of conversion system exit gas in stirring It is leached under part with 20-50 DEG C of water, extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate 95-98 DEG C is warming up to, sodium carbonate liquor is slowly added to leachate, is then filtered, washs filter residue and drying, is analyzed in filter residue The content of Li, Co are 1.05 according to the molar ratio of lithium and cobalt:1 requirement supplements lithium carbonate toward filter residue, then ball in the ball mill Mill, then it is put into using pressure compaction in clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, It is warming up to after keeping the temperature 10h at 900 DEG C and is slowly cooled to room temperature again, sample comminution, grinding after firing cross 500 mesh sieve, obtain electricity The good lithium cobaltate cathode material of chemical property；
Step（5）：By step（4）The solution being obtained by filtration crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum degree 120-140 DEG C of 0.012-0.015MPa, temperature, crystal is dry under 50-80 DEG C and 0.2-3h to obtain sodium sulphate, the sulphur of acquisition Sour sodium return to step（2）Middle use.
2. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（1）In sodium hydrate aqueous solution a concentration of 0.1-1.0mol/L.
3. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（1）The middle positive plate by acquisition is 1 in the ratio g/mL of the quality of positive plate and the volume of ceramic crucible:10-1:15.
4. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（1）According to positive plate quality and water volume ratio g/mL be 1:40-1:70, positive plate is put into equipped with filling 5-30min is stirred in the container of water and with electric mixer, the temperature of water is 20-50 DEG C in whipping process, mixing speed 10- 200r/min。
5. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（1）In sieve be 10-20 mesh sieve.
6. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（2）Middle by obtained useless cobalt acid lithium and sodium sulphate g/g is in mass ratio 1:The ratio mixing of 0.01-2.2, then in ball milling Ball milling in machine, Ball-milling Time are 0.1-1.0 h, and rotating speed is 200-500 r/min.
7. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（4）A concentration of 1.0-3.0mol/L of middle sodium carbonate liquor.
8. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（4）In Ball-milling Time for 0.5-2h, rotating speed 200-500r/min, the pressure of compression is 0.1-100MPa.
9. the method according to claim 1 for purifying relieving haperacidity tail gas and Call Provision lithium using useless cobalt acid lithium, it is characterised in that： Step（3）In vanadium catalyst be S108 type vanadium catalysts.
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