CN104466292B - The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material - Google Patents

The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material Download PDF

Info

Publication number
CN104466292B
CN104466292B CN201410833979.0A CN201410833979A CN104466292B CN 104466292 B CN104466292 B CN 104466292B CN 201410833979 A CN201410833979 A CN 201410833979A CN 104466292 B CN104466292 B CN 104466292B
Authority
CN
China
Prior art keywords
lithium
positive plate
ratio
temperature
positive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410833979.0A
Other languages
Chinese (zh)
Other versions
CN104466292A (en
Inventor
陈怀敬
王大辉
文豪
赵午祥
曹胜强
黄允文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanzhou University of Technology
Original Assignee
Lanzhou University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanzhou University of Technology filed Critical Lanzhou University of Technology
Priority to CN201410833979.0A priority Critical patent/CN104466292B/en
Publication of CN104466292A publication Critical patent/CN104466292A/en
Application granted granted Critical
Publication of CN104466292B publication Critical patent/CN104466292B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, the steps include: to carry out used Li ion cell discharging, disassembling the useless positive plate of acquisition, and useless positive plate roasting, water dissolution, filtration obtain useless cobalt acid lithium powder；Roasting after useless cobalt acid lithium powder is mixed by a certain percentage with sodium bisulfate, product of roasting water logging goes out, then filter after adding sodium carbonate liquor in solution, filtering residue supplements its ball milling after a certain amount of lithium carbonate, compress, put into resistance kiln roasting, regain the lithium cobaltate cathode material that chemical property is good.Filtrate can be used again with sulphuric acid adjusting component the sodium bisulfate that obtains after carrying out crystallization treatment.

Description

The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material
Technical field
The present invention relates to the technology of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material.
Background technology
Lithium ion battery is the secondary cell of new generation developed rapidly the nineties in 20th century, is widely used in miniature portable Formula telecommunications product and electric vehicle.According to statistics, within 2009, China's lithium ion battery yield reaches 18.7 hundred million, 2010 The yield of China's lithium ion battery reaches 26.8 hundred million.Owing to the service life of lithium ion battery is generally 2-3, therefore, report Environmental pollution and problem of resource waste that used Li ion cell brings also become increasingly conspicuous, and the most rationally dispose waste lithium ion Problem can not be ignored.Recycling to resources such as Co, Ni, Mn, Li, Al and Cu in used Li ion cell, both gram Take discarding method and disposed scrap lithium ion battery pollution on the environment, the most also made limited resource be circulated profit With, not only there is great economic benefit, be also significant in terms of environmental conservation.
The positive electrode that lithium ion battery uses is one of critical material manufacturing lithium ion battery, in lithium ion battery Occupy core status.The positive electrode of commercial application the most mainly has cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), nickel Cobalt manganic acid lithium (LiNi1/3Co1/3Mn1/3O2) ternary material and LiFePO4 (LiFePO4), wherein, cobalt acid lithium is still main flow and uses Positive electrode, be applied to high-end electronic product with small-sized lithium ion battery with high energy density field.
Disclose report from using cobalt acid lithium as the used Li ion cell of positive electrode reclaims valuable metal Method mainly has, and Zhang P W etc., at " Hydrometallurgy " Vol.47 No.2-3, reports in 1998,259-271 Use salt Ore Leaching lithium ion cell anode waste, then obtain cobaltous sulfate and lithium carbonate through operations such as extraction, precipitations.Wu Fang exists " China YouSe Acta Metallurgica Sinica " Vol.14 No.4,2004,697-701 reports the positive pole obtained in used Li ion cell Waste material uses at high temperature uses sulphuric acid and hydrogen peroxide Ore Leaching, then obtains cobaltous sulfate and lithium carbonate through extraction, precipitation operation. Myoung J etc. reports in " Journal of Power Sources " Vol.112,2002,639-642 and uses hot nitric acid Dissolve the anode waste obtained in used Li ion cell, after being then passed through electro-deposition operation, low temperature calcination, obtain Co3O4.Patent [CN201210491084] reports one and produces Co from waste and old lithium ion battery3O4Method, by scrap lithium ion battery just Pole impregnates in organic solvent, makes positive pole powder material and aluminum foil current collector separate, then adds in positive pole powder material and contain Roasting after fluorine organic, obtains Co3O4Material.Patent [CN201210167969] reports a kind of efficiently Strengthen education and discards lithium The method of metal in ion battery, by adding cobalt acid lithium powder in dilute acid soln, controls solid-to-liquid ratio and adds ferrous sulfate, Logical DC voltage, improves the leaching efficiency of cobalt acid lithium.Patent [CN201180048492] report a kind of for reclaim Li from The method of son, by introducing one or more cyclosiloxane, so that lithium ion forms one or more cyclosiloxane-Li ion and joins Compound, then by separated from the water for the organic facies containing cyclosiloxane-Li ionic complex.Patent [CN201010523257] is reported A kind of method reclaiming lithium from waste and old lithium ion battery and waste pole piece, by being leached with acid and reducing agent, and uses Chemical method removes the impurity such as the ferrum in leachate, copper, aluminum, then with the lithium in villiaumite precipitation leachate, obtains lithium fluoride product.Patent [CN200910117702] reports by by useless LiCoO2Powder mix with the salt of alkali metallic sodium and potassium after in higher temperature Lower roasting, product of roasting water logging goes out, and leachate obtains cobalt oxalate and lithium carbonate through heavy cobalt and sinker operation.Patent [CN200910093727] reports a kind of method utilizing waste and old lithium ion battery recovery to prepare cobalt acid lithium, by by waste and old lithium Ion battery electric eliminating, split, pulverize, NMP process, calcining, obtain waste and old LiCoO2Material, then by LiCoO2Material is with natural Ball milling after organic acid and hydrogen peroxide mixing, and obtain Li+、Co2+Solution, in the solution dropping ammonia prepare xerogel secondary Calcining obtains cobalt acid lithium electrode material.Patent [CN200910039217] discloses a kind of waste lithium ion battery cathode material Reclaim and regeneration method, crush, grind, except aluminum, acidleach, extraction copper, chemistry by used Li ion cell cathode waste is carried out Remove impurity, precipitate, add lithium source secondary high-temperature baking operation, it is achieved cathode material regenerates.Patent [CN200810028730] is open A kind of method reclaiming from waste and old lithium ion battery, preparing cobalt acid lithium.By lithium ion battery positive plate is pulverized, After screening, it is thus achieved that useless cobalt acid lithium；In constant temperature resistance furnace, remove binding agent, conductive agent acetylene black, allocate the carbonic acid of proper proportion into Lithium, the cobalt acid lithium battery material that high temperature sintering synthesis is active in Muffle furnace.Patent [CN200710057623] discloses A kind of waste lithium ion cell anode material lithium cobaltate activating process.Waste lithium ion cell anode material is at high temperature removed Binding agent PVDF, at high temperature calcining cobalt acid lithium, make inefficacy cobalt acid lithium produce crystallization reaction, again possess layer structure.Patent [CN200510018601] reports a kind of method of separating and recovering cobalt from the positive pole material of lithium cobalt acid of waste and old lithium ion battery. Waste and old lithium ion battery carries out after physics is disassembled, calcined, organic solvent soaks, obtaining useless cobalt acid lithium, useless cobalt acid lithium being placed in acid H is used under the conditions of property2O2Or Na2S2O3As reducing agent, dissolve and obtain containing Co2+And Li+Solution, then with NaOH solution for precipitation Agent, by the Co in solution2+Ion conversion becomes Co (OH)2Precipitation.Patent [CN200510015078] discloses a kind of from scrapping Lithium ion battery reclaims preparation LixCoO2Method.Used Li ion cell positive electrode is cut into fractionlet and is immersed in N-first In base-2-Pyrrolidone liquid, separate and obtain active substance LixCoO2Black powder, then black powder is scattered in salpeter solution Or in hydrochloric acid solution, then through filtration, precipitation operation, obtain blue precipitate, and precipitate at high temperature roasting, obtain LixCoO2Powder Body.
At present it has been reported that from cobalt acid lithium as the side reclaiming valuable metal the used Li ion cell of positive electrode Method use sulphuric acid add hydrogen peroxide, sodium thiosulfate, hydrochloric acid, the useless LiCoO of nitric acid dissolving2, inevitable real estate in leaching process Raw containing acid gas, Cl2Or NOxWaste gas, removal process causes serious secondary pollution to environment.Additionally, the follow-up place of leachate Science and engineering sequence is many, long flow path causes cost recovery high；Leaching process is the most all adopted to improve metal recovery rate and shortening extraction time With higher acid concentration and extraction temperature, leaching equipment antiseptical is required the highest by this.Use useless LiCoO2Powder and alkali gold Belonging to the method for roasting after the salt mixing of sodium and potassium, the salt consumption that there is alkali metallic sodium and potassium in roasting process is big, removal process Middle precipitant oxalates consumption is many, causes the shortcoming that cost recovery is high；Use useless LiCoO2Material and natural organic acids and dioxygen , there is the shortcoming that removal process easily makes ball-grinding machine be corroded and introduce impurity in ball grinding technique after water mixing.
Summary of the invention
It is an object of the invention to provide a kind of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material Method.
The present invention is the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, the steps include:
Step (1): by collect come do the scrap lithium ion battery of positive electrode with cobalt acid lithium and be at room temperature positioned over The sodium hydrate aqueous solution of 0.1-1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium-ion electric that will scrap Pond is disassembled, it is thus achieved that positive plate；Collect and do, with cobalt acid lithium, the positive pole limit that the lithium ion battery manufacture process of positive electrode produces Corner material, positive pole relic, it is thus achieved that positive plate；
Step (2): by the positive plate that obtains in step (1) by the ratio of the quality of positive plate and the volume of ceramic crucible- G/mL is that positive plate is loaded in ceramic crucible by the ratio of 1:10-1:15, is subsequently placed in chamber type electric resistance furnace and starts with 5 from room temperature DEG C/heating rate of min makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h, then make chamber type electric resistance furnace power-off, naturally cool to room Temperature；Take out through the positive plate of roasting, be that 1:40-1:70 will just according to the quality of positive plate with the ratio-g/mL of the volume of water Pole piece is put into equipped with stirring 5-30min in the container of water and with motor stirrer, and in whipping process, the temperature of water is 20-50 DEG C, Mixing speed is 10-200r/min；After stopping stirring, the screen cloth of the mixture 10-20 mesh in container is sieved, on sieve Thing is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying； Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；
Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in box resistance Stove make furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；
Step (4): useless cobalt acid lithium powder step (3) obtained and sodium bisulfate-g/g in mass ratio are 1:0.4-1:2 Ratio mixing after put into ceramic mortar be fully ground mix homogeneously, the mixture after grinding loads ceramic crucible and adds pottery Porcelain lid covers, and is then placed in roasting in chamber type electric resistance furnace, makes furnace temperature be raised to 400-650 DEG C also with the heating rate of 3-10 DEG C/min Insulation 10-60min；
Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, Extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, by 1.0- The sodium carbonate liquor of 3.0mol/L is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes Li, Co in filtering residue Content, supplements a certain amount of lithium carbonate toward filtering residue, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt Abundant spheroidal graphite in grinding machine, Ball-milling Time is 0.5-2h, and rotating speed is 200-500r/min, then by it under the pressure of 0.1-100MPa Compress, put in clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, then be warming up at 900 DEG C insulation It is slowly cooled to room temperature after 10h, the sample comminution after firing, grinding, crosses 500 mesh sieves, it is thus achieved that the cobalt acid that chemical property is good Lithium anode material；
Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, Then crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystallization Thing is dried under 50-80 DEG C and 0.2-3h and obtains sodium bisulfate, it is thus achieved that sodium bisulfate return in step (4) and use.
The present invention has that technological process is short, cost recovery is low compared with the prior art, easy operation, to equipment anticorrosion requirement Low, metallic cobalt and the lithium response rate is high, the advantage that do not produces secondary pollution in processing procedure.
Detailed description of the invention
The present invention is the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, the steps include:
Step (1): by collect come do the scrap lithium ion battery of positive electrode with cobalt acid lithium and be at room temperature positioned over The sodium hydrate aqueous solution of 0.1-1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium-ion electric that will scrap Pond is disassembled, it is thus achieved that positive plate；Collect and do, with cobalt acid lithium, the positive pole limit that the lithium ion battery manufacture process of positive electrode produces Corner material, positive pole relic, it is thus achieved that positive plate；
Step (2): by the positive plate that obtains in step (1) by the ratio of the quality of positive plate and the volume of ceramic crucible- G/mL is that positive plate is loaded in ceramic crucible by the ratio of 1:10-1:15, is subsequently placed in chamber type electric resistance furnace and starts with 5 from room temperature DEG C/heating rate of min makes furnace temperature be raised to 550 DEG C of insulation 0.5-1h, then make chamber type electric resistance furnace power-off, naturally cool to room Temperature；Take out through the positive plate of roasting, be that 1:40-1:70 will just according to the quality of positive plate with the ratio-g/mL of the volume of water Pole piece is put into equipped with stirring 5-30min in the container of water and with motor stirrer, and in whipping process, the temperature of water is 20-50 DEG C, Mixing speed is 10-200r/min；After stopping stirring, the screen cloth of the mixture 10-20 mesh in container is sieved, on sieve Thing is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying； Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；
Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in box resistance Stove make furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；
Step (4): useless cobalt acid lithium powder step (3) obtained and sodium bisulfate-g/g in mass ratio are 1:0.4-1:2 Ratio mixing after put into ceramic mortar be fully ground mix homogeneously, the mixture after grinding loads ceramic crucible and adds pottery Porcelain lid covers, and is then placed in roasting in chamber type electric resistance furnace, makes furnace temperature be raised to 400-650 DEG C also with the heating rate of 3-10 DEG C/min Insulation 10-60min；
Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, Extraction time 5-30min, solid-to-liquid ratio-g/mL are 1:10-1:50；Then leachate is warmed up to 95-98 DEG C, by 1.0- The sodium carbonate liquor of 3.0mol/L is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes Li, Co in filtering residue Content, supplements a certain amount of lithium carbonate toward filtering residue, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt Abundant spheroidal graphite in grinding machine, Ball-milling Time is 0.5-2h, and rotating speed is 200-500r/min, then by it under the pressure of 0.1-100MPa Compress, put in clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, then be warming up at 900 DEG C insulation It is slowly cooled to room temperature after 10h, the sample comminution after firing, grinding, crosses 500 mesh sieves, it is thus achieved that the cobalt acid that chemical property is good Lithium anode material；
Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, Then crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystallization Thing is dried under 50-80 DEG C and 0.2-3h and obtains sodium bisulfate, it is thus achieved that sodium bisulfate return in step (4) and use.
Method in accordance with the above, the sodium bisulfate described in step (4) is: the chemical products of sodium bisulfate or step (6) sodium bisulfate obtained in or the two mixture being mixed to form with arbitrary proportion；
Method in accordance with the above, the useless cobalt acid lithium powder described in step (4) with the mixed proportion of sodium bisulfate is: Mass ratio-g/g is 1:0.4-1:2.
Method in accordance with the above, in step (4), the process conditions of resistance kiln roasting are: heating rate is 3-10 DEG C/min, sintering temperature is 400-650 DEG C, and temperature retention time is 10-60min.
Method in accordance with the above, the extraction temperature described in step (5) is 20-50 DEG C, extraction time 5-30min, Solid-to-liquid ratio-g/mL is 1:10-1:50.
Embodiment 1:
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 20min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；By the sodium bisulfate chemical products of useless cobalt acid lithium powder and purchase in mass ratio (g/g) being that the ratio of 1:1.41 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding loads pottery Porcelain crucible also adds to put on ceramic cap lid in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C and be incubated with the heating rate of 5 DEG C/min 30min；After roasting terminates, it is that 1:20 soaks with the water of 50 DEG C with solid-to-liquid ratio (g/mL) by the material in crucible under conditions of stirring Go out 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces precipitation Thing, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to the mol ratio of lithium with cobalt be The requirement of 1.05:1 supplements a certain amount of lithium carbonate toward precipitate, and then in planetary ball mill, speed with 400r/min is filled Bulb separation ink 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, in 650 DEG C of perseverances in air atmosphere Temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 500 mesh sieves, obtain Obtain the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid adjusting component being filtrated to get in above-mentioned steps is made The pH value of solution is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 2
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Cobalt acid lithium powder recycling obtained produces with the sodium bisulfate chemical industry of purchase Product (g/g) in mass ratio are that the ratio of 1:1.41 is put into and is fully ground mix homogeneously in ceramic mortar, mixed after then grinding Compound loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to the heating rate of 5 DEG C/min 550 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/ ML) it is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, is slowly added to the sodium carbonate liquor of 3.0mol/L leach Liquid produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to lithium and cobalt The requirement that mol ratio is 1.05:1 supplement a certain amount of lithium carbonate toward precipitate, then with 400r/ in planetary ball mill The speed abundant spheroidal graphite 2h of min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at air atmosphere In in 650 DEG C of constant temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, mistake 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps Adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 3
Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and the sulfur of purchase Acid hydrogen sodium chemical product (g/g) in mass ratio is that the ratio of 1:1.41 is put into and is fully ground mix homogeneously in ceramic mortar, then Mixture after grinding loads ceramic crucible adding and puts in chamber type electric resistance furnace the heating rate with 5 DEG C/min on ceramic cap lid Furnace temperature is made to be raised to 500 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C It is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is delayed The slow leachate that adds produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, A certain amount of lithium carbonate is supplemented toward precipitate, then at planetary ball mill according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt In with the speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, puts in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 4
Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and the sulfur of purchase Acid hydrogen sodium chemical product (g/g) in mass ratio is that the ratio of 1:1.41 is put into and is fully ground mix homogeneously in ceramic mortar, then Mixture after grinding loads ceramic crucible adding and puts in chamber type electric resistance furnace the heating rate with 5 DEG C/min on ceramic cap lid Furnace temperature is made to be raised to 450 DEG C and be incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C It is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is delayed The slow leachate that adds produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, A certain amount of lithium carbonate is supplemented toward precipitate, then at planetary ball mill according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt In with the speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, puts in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 5
Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Cobalt acid lithium powder recycling obtained walks with the present invention Suddenly the ratio that sodium bisulfate (g/g) in mass ratio is 1:0.99 obtained in (6) is put into and is fully ground mixing in ceramic mortar all Even, the mixture after then grinding loads ceramic crucible adding and puts on ceramic cap lid in chamber type electric resistance furnace with 5 DEG C/min's Heating rate makes furnace temperature be raised to 600 DEG C and be incubated 30min；After roasting terminates, the material in crucible is used under conditions of stirring The water of 50 DEG C is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, by the carbonic acid of 3.0mol/L Sodium solution is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze Li, Co in precipitate Content, supplement a certain amount of lithium carbonate toward precipitate, then at planet according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt With the speed abundant spheroidal graphite 2h of 400r/min in formula ball mill, then it is compressed under the pressure of 10MPa, put into clean pottery In crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then it is warming up to 900oIt is slowly cooled to room temperature, after firing after C insulation 10h Sample comminution, grinding, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Above-mentioned steps will be filtered The solution concentrated sulphuric acid adjusting component obtained makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, cerium sulphate crystal bar Part is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 6
Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Cobalt acid lithium powder recycling obtained walks with the present invention Suddenly the ratio that sodium bisulfate (g/g) in mass ratio is 1:0.99 obtained in (6) is put into and is fully ground mixing in ceramic mortar all Even, the mixture after then grinding loads ceramic crucible adding and puts on ceramic cap lid in chamber type electric resistance furnace with 5 DEG C/min's Heating rate makes furnace temperature be raised to 550 DEG C and be incubated 30min；After roasting terminates, the material in crucible is used under conditions of stirring The water of 50 DEG C is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, by the carbonic acid of 3.0mol/L Sodium solution is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze Li, Co in precipitate Content, supplement a certain amount of lithium carbonate toward precipitate, then at planet according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt With the speed abundant spheroidal graphite 2h of 400r/min in formula ball mill, then it is compressed under the pressure of 10MPa, put into clean pottery In crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, after firing Sample comminution, grinding, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Above-mentioned steps will be filtered The solution concentrated sulphuric acid adjusting component obtained makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, cerium sulphate crystal bar Part is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 7
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and step of the present invention (6) obtain The ratio that sodium bisulfate (g/g) in mass ratio is 1:0.99 put into ceramic mortar be fully ground mix homogeneously, then will grind Mixture after mill loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make stove with the heating rate of 5 DEG C/min Temperature rise is to 500 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C to consolidate Liquor ratio (g/mL) is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added Enter leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to The requirement that mol ratio is 1.05:1 of lithium and cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at sky In 650 DEG C of constant temperature 6h in gas atmosphere, then it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h, sample comminution after firing, Grind, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution being filtrated to get in above-mentioned steps The pH value making solution with concentrated sulphuric acid adjusting component is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 8
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and step of the present invention (6) obtain The ratio that sodium bisulfate (g/g) in mass ratio is 1:0.99 put into ceramic mortar be fully ground mix homogeneously, then will grind Mixture after mill loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make stove with the heating rate of 5 DEG C/min Temperature rise is to 400 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C to consolidate Liquor ratio (g/mL) is that 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added Enter leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to The requirement that mol ratio is 1.05:1 of lithium and cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at sky In 650 DEG C of constant temperature 6h in gas atmosphere, then it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h, sample comminution after firing, Grind, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution being filtrated to get in above-mentioned steps The pH value making solution with concentrated sulphuric acid adjusting component is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 9
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Cobalt acid lithium powder recycling obtained produces with the sodium bisulfate chemical industry of purchase Product (g/g) in mass ratio are that the ratio of 1:2 is put into and is fully ground mix homogeneously in ceramic mortar, the mixture after then grinding Load ceramic crucible and add to put on ceramic cap lid in chamber type electric resistance furnace and make furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C with solid-to-liquid ratio (g/mL) it is 1:20 leaches 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces Precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to lithium and cobalt mole A certain amount of lithium carbonate is supplemented toward precipitate, then with the speed of 400r/min in planetary ball mill than the requirement for 1.05:1 Spend abundant spheroidal graphite 2h, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, in 650 in air atmosphere DEG C constant temperature 6h, then be slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h, the sample comminution after firing, grinding, cross 500 mesh Sieve, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps is adjusted Composition makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature Spending 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 10
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Cobalt acid lithium powder recycling obtained produces with the sodium bisulfate chemical industry of purchase Product (g/g) in mass ratio are that the ratio of 1:0.4 is put into and is fully ground mix homogeneously in ceramic mortar, the mixing after then grinding Thing loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make furnace temperature be raised to 600 with the heating rate of 5 DEG C/min DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 40 DEG C with solid-to-liquid ratio (g/mL) 30min is leached for 1:20；Then leachate is warmed up to 95 DEG C, the sodium carbonate liquor of 3.0mol/L is slowly added to leachate and produces Raw precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to rubbing of lithium and cobalt You supplement a certain amount of lithium carbonate toward precipitate, then with 400r/min's in planetary ball mill than the requirement for 1.05:1 Speed abundant spheroidal graphite 2h, then it compressed under the pressure of 10MPa, puts in clean ceramic crucible, in air atmosphere in 650 DEG C of constant temperature 6h, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample comminution after firing, grinding, cross 500 Mesh sieve, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution concentrated sulphuric acid being filtrated to get in above-mentioned steps is adjusted Being made into point pH value making solution is 1.0, then in crystallizing evaporator crystallize, cerium sulphate crystal condition be vacuum 0.015MPa, Temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 11
Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；Cobalt acid lithium powder recycling obtained walks with the present invention Suddenly the ratio that sodium bisulfate (g/g) in mass ratio is 1:1.41 obtained in (6) is put into and is fully ground mixing in ceramic mortar all Even, the mixture after then grinding loads ceramic crucible adding and puts on ceramic cap lid in chamber type electric resistance furnace with 5 DEG C/min's Heating rate makes furnace temperature be raised to 600 DEG C and be incubated 20min；After roasting terminates, the material in crucible is used under conditions of stirring The water of 50 DEG C is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, by the carbonic acid of 1.0mol/L Sodium solution is slowly added to leachate and produces precipitate, gained precipitate through filtering, washing, dried, analyze Li, Co in precipitate Content, supplement a certain amount of lithium carbonate toward precipitate, then at planet according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt With the speed abundant spheroidal graphite 2h of 400r/min in formula ball mill, then it is compressed under the pressure of 10MPa, put into clean pottery In crucible, in 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, after firing Sample comminution, grinding, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Above-mentioned steps will be filtered The solution concentrated sulphuric acid adjusting component obtained makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, cerium sulphate crystal bar Part is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 12
Collect and do, with cobalt acid lithium, positive pole leftover pieces, the positive pole relic that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate with the volume of ceramic crucible, positive plate is loaded In ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C also from room temperature Insulation 30min, then makes chamber type electric resistance furnace power-off, naturally cools to room temperature；Take out the positive plate through roasting, according to positive plate The ratio (g/mL) of volume of quality and water be 1:50 positive plate is put into equipped with in the container of water and with motor stirrer with The mixing speed stirring 20min of 50r/min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by the mixing in container The thing screen cloth of 10 mesh sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil water is clear Wash 3 times, obtain aluminium foil through natural drying；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；Will The positive active material obtained loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and the sulfur of purchase Acid hydrogen sodium chemical product (g/g) in mass ratio is that the ratio of 1:1.41 is put into and is fully ground mix homogeneously in ceramic mortar, then Mixture after grinding loads ceramic crucible adding and puts in chamber type electric resistance furnace the heating rate with 5 DEG C/min on ceramic cap lid Furnace temperature is made to be raised to 550 DEG C and be incubated 20min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C It is that 1:20 leaches 30min with solid-to-liquid ratio (g/mL)；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is delayed The slow leachate that adds produces precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, A certain amount of lithium carbonate is supplemented toward precipitate, then at planetary ball mill according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt In with the speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, puts in clean ceramic crucible, In 650 DEG C of constant temperature 6h in air atmosphere, then be warming up to 900 DEG C insulation 10h after be slowly cooled to room temperature, the sample powder after firing Broken, grinding, crosses 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；Molten by what above-mentioned steps was filtrated to get Liquid concentrated sulphuric acid adjusting component makes the pH value of solution be 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum Degree 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 13
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and step of the present invention (6) obtain The ratio that sodium bisulfate (g/g) in mass ratio is 1:1.41 put into ceramic mortar be fully ground mix homogeneously, then will grind Mixture after mill loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make stove with the heating rate of 5 DEG C/min Temperature rise is to 500 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C to consolidate Liquor ratio (g/mL) is that 1:20 leaches 20min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added Enter leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to The requirement that mol ratio is 1.05:1 of lithium and cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at sky In 650 DEG C of constant temperature 6h in gas atmosphere, then it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h, sample comminution after firing, Grind, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution being filtrated to get in above-mentioned steps The pH value making solution with concentrated sulphuric acid adjusting component is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 14
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and step of the present invention (6) obtain The ratio that sodium bisulfate (g/g) in mass ratio is 1:1.41 put into ceramic mortar be fully ground mix homogeneously, then will grind Mixture after mill loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make stove with the heating rate of 5 DEG C/min Temperature rise is to 600 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C to consolidate Liquor ratio (g/mL) is that 1:40 leaches 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added Enter leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to The requirement that mol ratio is 1.05:1 of lithium and cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at sky In 650 DEG C of constant temperature 6h in gas atmosphere, then it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h, sample comminution after firing, Grind, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution being filtrated to get in above-mentioned steps The pH value making solution with concentrated sulphuric acid adjusting component is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.
Embodiment 15
Collect the scrap lithium ion battery doing positive electrode with cobalt acid lithium, be at room temperature positioned over the hydroxide of 1.0mol/L Sodium water solution carries out the discharge process of 2h；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate； In the ratio that ratio (g/mL) is 1:15 of the quality of positive plate Yu the volume of ceramic crucible, positive plate is loaded in ceramic crucible, It is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C and be incubated 30min from room temperature, Then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out the positive plate through roasting, according to quality and the water of positive plate The ratio (g/mL) of volume be that positive plate is put into equipped with in the container of water and with motor stirrer stirring with 50r/min by 1:50 Mixing speed stirring 20min, in whipping process, the temperature of water is 30 DEG C；After stopping stirring, by 10 purposes of the mixture in container Screen cloth sieves, and oversize is aluminium foil, and siftage is the solution containing positive active material；Aluminium foil use water cleans 3 times, through certainly So it is dried and obtains aluminium foil；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive pole that will obtain Active substance loads in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 600 DEG C with the heating rate of 5 DEG C/min And it is incubated 30min, it is thus achieved that useless cobalt acid lithium powder；The cobalt acid lithium powder that recycling is obtained and step of the present invention (6) obtain The ratio that sodium bisulfate (g/g) in mass ratio is 1:1.41 put into ceramic mortar be fully ground mix homogeneously, then will grind Mixture after mill loads ceramic crucible and adds to put in chamber type electric resistance furnace on ceramic cap lid and make stove with the heating rate of 5 DEG C/min Temperature rise is to 450 DEG C and is incubated 30min；After roasting terminates, by the material in crucible under conditions of stirring with the water of 50 DEG C to consolidate Liquor ratio (g/mL) is that 1:40 leaches 30min；Then leachate is warmed up to 98 DEG C, the sodium carbonate liquor of 1.0mol/L is slowly added Enter leachate and produce precipitate, gained precipitate through filtering, washing, dried, analyze the content of Li, Co in precipitate, according to The requirement that mol ratio is 1.05:1 of lithium and cobalt supplements a certain amount of lithium carbonate toward precipitate, then in planetary ball mill with The speed abundant spheroidal graphite 2h of 400r/min, then it is compressed under the pressure of 10MPa, put in clean ceramic crucible, at sky In 650 DEG C of constant temperature 6h in gas atmosphere, then it is slowly cooled to room temperature after being warming up to 900 DEG C of insulation 10h, sample comminution after firing, Grind, cross 500 mesh sieves, it is thus achieved that the lithium cobaltate cathode material that chemical property is good；The solution being filtrated to get in above-mentioned steps The pH value making solution with concentrated sulphuric acid adjusting component is 1.0, then crystallizes in crystallizing evaporator, and cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, crystal is dried under 80 DEG C and 2h and obtains sodium bisulfate.

Claims (1)

1. the method for Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material, it is characterised in that the method bag Include following steps:
Step (1): by collect come do the scrap lithium ion battery of positive electrode with cobalt acid lithium and be at room temperature positioned over 0.1- The sodium hydrate aqueous solution of 1.0mol/L carries out the discharge process of 1-3h；After discharge process, the lithium ion battery scrapped is entered Row is disassembled, it is thus achieved that positive plate；Collect and make, with cobalt acid lithium, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, Obtain positive plate；
Step (2): be 1:10 in the ratio of the quality of positive plate Yu the volume of ceramic crucible by the positive plate that obtains in step (1) Positive plate is loaded in ceramic crucible by g/mL-1:15 g/mL, is subsequently placed in chamber type electric resistance furnace and starts with 5 DEG C/min from room temperature Heating rate make furnace temperature be raised to 550 DEG C insulation 0.5-1h, then make chamber type electric resistance furnace power-off, naturally cool to room temperature；Take out Through the positive plate of roasting, it is that 1:40 g/mL-1:70 g/mL is by positive pole according to the quality of positive plate with the ratio of the volume of water Sheet is put into equipped with stirring 5-30min in the container of water and with motor stirrer, and in whipping process, the temperature of water is 20-50 DEG C, stirs Mixing speed is 10-200r/min；After stopping stirring, the screen cloth of the mixture 10-20 mesh in container is sieved, oversize For aluminium foil, siftage is the solution containing positive active material；Aluminium foil use water cleans 1-3 time, obtains aluminium foil through natural drying；Sieve Lower thing carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；
Step (3): the positive active material obtained in step (2) is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace Furnace temperature is made to be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless cobalt acid lithium powder；
Step (4): useless cobalt acid lithium powder step (3) obtained and sodium bisulfate are in mass ratio for 1:0.4 g/g-1:2 g/g Ratio mixing after put into ceramic mortar be fully ground mix homogeneously, the mixture after grinding loads ceramic crucible and adds pottery Porcelain lid covers, and is then placed in roasting in chamber type electric resistance furnace, makes furnace temperature be raised to 400-650 DEG C also with the heating rate of 3-10 DEG C/min Insulation 10-60min；
Step (5): after roasting terminates, leaches the material in crucible with the water of 20-50 DEG C under conditions of stirring, leaches Time 5-30min, solid-to-liquid ratio is 1:10 g/mL-1:50 g/mL；Then leachate is warmed up to 95-98 DEG C, by 1.0- The sodium carbonate liquor of 3.0mol/L is slowly added to leachate, then filters, and washing filtering residue is also dried, and analyzes Li, Co in filtering residue Content, supplements a certain amount of lithium carbonate toward filtering residue, then at planetary ball according to the requirement that mol ratio is 1.05:1 of lithium Yu cobalt Abundant ball milling in grinding machine, Ball-milling Time is 0.5-2h, and rotating speed is 200-500r/min, then by it under the pressure of 0.1-100MPa Compress, put in clean ceramic crucible, in 650-700 DEG C of constant temperature 2-6h in air atmosphere, then be warming up at 900 DEG C insulation It is slowly cooled to room temperature after 10h, the sample comminution after firing, grinding, crosses 500 mesh sieves, it is thus achieved that lithium cobaltate cathode material；
Step (6): solution concentrated sulphuric acid adjusting component step (5) being filtrated to get makes the pH value of solution be 0.5-1.0, then Crystallizing in crystallizing evaporator, cerium sulphate crystal condition is vacuum 0.012-0.015MPa, temperature 120-140 DEG C, and crystal exists Be dried under 50-80 DEG C and 0.2-3h and obtain sodium bisulfate, it is thus achieved that sodium bisulfate return in step (4) and use.
CN201410833979.0A 2014-12-30 2014-12-30 The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material Active CN104466292B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410833979.0A CN104466292B (en) 2014-12-30 2014-12-30 The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410833979.0A CN104466292B (en) 2014-12-30 2014-12-30 The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material

Publications (2)

Publication Number Publication Date
CN104466292A CN104466292A (en) 2015-03-25
CN104466292B true CN104466292B (en) 2016-08-31

Family

ID=52911956

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410833979.0A Active CN104466292B (en) 2014-12-30 2014-12-30 The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material

Country Status (1)

Country Link
CN (1) CN104466292B (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428747A (en) * 2015-12-30 2016-03-23 深圳先进技术研究院 Restoration and recycling method of lithium cobaltate materials of lithium batteries
CN105886777B (en) * 2016-05-16 2017-08-25 兰州理工大学 Relieving haperacidity tail gas cooperates with the method for administering simultaneously Call Provision lithium with useless cobalt acid lithium
CN105800586B (en) * 2016-05-16 2017-12-08 兰州理工大学 Relieving haperacidity tail gas and the method for reclaiming nickel cobalt manganese lithium are purified using useless nickle cobalt lithium manganate
CN106450549B (en) * 2016-10-24 2019-07-19 中国科学院过程工程研究所 A method of nickel and/or cobalt in cleaning recycling positive electrode
CN106410313A (en) * 2016-11-24 2017-02-15 荆门市格林美新材料有限公司 Method for repairing and regenerating nickel cobalt manganese ternary positive electrode material in waste battery
CN106450555A (en) * 2016-11-24 2017-02-22 荆门市格林美新材料有限公司 Method for reparative regeneration of lithium cobalt oxide anode material in waste batteries
CN106450559A (en) * 2016-12-07 2017-02-22 天津华庆百胜能源有限公司 Method for preparing new electrodes through recovering of waste ion batteries
CN106591584A (en) * 2016-12-23 2017-04-26 江西合纵锂业科技有限公司 Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery
CN106684486A (en) * 2016-12-28 2017-05-17 天津先众新能源科技股份有限公司 Method for extracting lithium from waste lithium iron phosphate
CN109797286B (en) * 2019-02-01 2020-12-25 柯芬 Method for recycling lithium in lithium-containing waste material
CN111834683B (en) * 2019-04-16 2021-08-06 荆门市格林美新材料有限公司 Method for recovering lithium cobaltate waste batteries
CN110512084A (en) * 2019-06-01 2019-11-29 福建华兴达新材料有限公司 A kind of recovery method extracting lithium and cobalt from cobalt acid lithium battery
CN113540605B (en) * 2021-07-16 2022-07-12 南昌航空大学 Harmless treatment method for pyrolysis tail gas of retired old lithium battery

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4202198B2 (en) * 2003-06-19 2008-12-24 カワサキプラントシステムズ株式会社 Method and apparatus for recycling lithium secondary battery electrode material
CN1262042C (en) * 2004-06-09 2006-06-28 南开大学 Method for regenerating anode materials of waste lithium ion secondary battery
CN101383442B (en) * 2008-06-12 2011-04-13 佛山市邦普镍钴技术有限公司 Method for recovering and preparing lithium cobaltate from waste lithium ionic cell
CN101519726B (en) * 2009-04-16 2011-01-05 北京矿冶研究总院 Method for directly roasting and treating waste lithium ion battery and recycling valuable metal
CN103073071A (en) * 2013-01-23 2013-05-01 同济大学 Method for hydrothermally repairing invalid lithium cobalt oxide material in lithium ion battery by ultrasonic field enhancement
CN103151519A (en) * 2013-02-22 2013-06-12 同济大学 Method for oxidizing agent-aided restoration of failed lithium cobalt oxide under reinforcement of ultrasonic field
CN103985920B (en) * 2014-06-05 2016-01-27 兰州理工大学 The separation method of cobalt acid lithium and aluminium foil on scrap lithium ion battery positive plate

Also Published As

Publication number Publication date
CN104466292A (en) 2015-03-25

Similar Documents

Publication Publication Date Title
CN104466292B (en) The method of Call Provision lithium metal from the used Li ion cell of lithium cobaltate cathode material
CN104538696B (en) The method that metal is reclaimed from the used Li ion cell of nickel-cobalt lithium manganate cathode material
CN104466295B (en) The renovation process of positive electrode active materials in nickle cobalt lithium manganate used Li ion cell
CN104485493B (en) The reparative regeneration method of lithium cobaltate cathode active material in used Li ion cell
CN106848470B (en) A method of it recycled from waste and old nickel-cobalt-manganese ternary lithium ion battery, prepare tertiary cathode material
CN104538695B (en) Metal the method for preparing nickle cobalt lithium manganate are reclaimed in useless nickle cobalt lithium manganate battery
CN108550939B (en) A method of selective recovery lithium and lithium carbonate is prepared from waste lithium cell
CN103915661B (en) A kind of direct recovery the method repairing anode material for lithium-ion batteries
CN109449523A (en) A kind of comprehensive recovering process of waste and old lithium ion battery
CN104466294B (en) The method reclaiming metal from waste LiCoxNiyMnzO 2 battery
CN110343864B (en) Method for recovering lithium and cobalt in waste electrode material by microwave roasting assistance
CN102030375A (en) Method for preparing lithium cobaltate by directly using failed lithium ion battery
CN104577104B (en) Regeneration method of positive material lithium manganate waste of lithium ion battery
CN104466293B (en) The renovation process of lithium ion cell anode material lithium cobaltate waste material
CN108963371A (en) A method of recycling valuable metal from waste and old lithium ion battery
CN111600090A (en) Process for recycling waste lithium batteries
CN104600389A (en) Method for recycling metal from spent lithium ion battery of lithium manganate anode material
CN113200574A (en) Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery
CN105244561B (en) The method that high voltage multicomponent material is prepared as raw material using waste and old polynary dynamic lithium battery
Fei et al. Selective lithium extraction of cathode materials from spent lithium-ion batteries via low-valent salt assisted roasting
CN112095000A (en) Method for recovering cobalt and lithium metals from waste lithium cobalt oxide batteries
CN111517340B (en) Method for recycling lithium carbonate from NCM111 positive electrode material of waste ternary lithium ion battery
CN104485494B (en) The renovation process of positive electrode active materials in cobalt acid lithium used Li ion cell
CN104600284B (en) Method for regenerating positive active material in spent lithium manganate lithium ion battery
CN105742747B (en) Utilize the method for useless cobalt acid lithium purification relieving haperacidity tail gas and Call Provision lithium

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant