CN106921000B - A kind of ball milling acidleach method of waste lithium ion cell anode active material - Google Patents

A kind of ball milling acidleach method of waste lithium ion cell anode active material Download PDF

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CN106921000B
CN106921000B CN201710247447.2A CN201710247447A CN106921000B CN 106921000 B CN106921000 B CN 106921000B CN 201710247447 A CN201710247447 A CN 201710247447A CN 106921000 B CN106921000 B CN 106921000B
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lithium ion
ball milling
anode active
cell anode
ion cell
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CN106921000A (en
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张治安
杨声海
杨心慧
赖延清
方静
洪波
张凯
李劼
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Central South University
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    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • C22B7/007—Wet processes by acid 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Secondary Cells (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of ball milling acidleach method of waste lithium ion cell anode active material, waste and old lithium ion battery obtains electrode material powder through short circuit dischange, dismantling, binder removing, crushing and screening；The electrode material powder is put into prefabricated gelatinized corn starch, and the common ball milling of sulfuric acid solution, filtered after flushing positive electrode active materials aqueous solution.The method greatly reduces the cost of business practical application, green non-pollution, simple process, while greatly improving the reaction rate and leaching rate of leaching process, can be mass-produced.

Description

A kind of ball milling acidleach method of waste lithium ion cell anode active material
Technical field
The present invention relates to a kind of reductic acid leaching methods of positive electrode active materials in waste and old lithium ion battery removal process, belong to Field of lithium ion battery.
Background technique
Lithium ion battery since the advent of the world, because voltage itself is high, specific capacity is high, cyclicity is good, memory-less effect, small in size The advantages that, extensive reference has been obtained in fields such as electronic product, electric tool, energy storage device, electric vehicles, has been acknowledged as most Promising secondary cell.Especially along with the rise in domestic electric vehicle market in recent years and increase rapidly, lithium ion battery Monomer scale and whole dosage be all obviously improved.Meanwhile more and more performance degradations and reaching service life Battery faces disposal difficulties.
There are also in the leaching method about active material, such as Publication No. CN103035977A in the prior art State's patent document disclose it is a kind of from waste and old lithium ion battery recycle valuable metal method, mainly using salt water electric discharge → Artificial dismantling → alkali leaching separation (or low-temperature bake) → reduction acidleach (sulfuric acid+hydrogen peroxide) → chemical precipitation, extracts positive electrode In valuable metal.In this process flow, core is that the leaching process of active material, leaching process directly determine valuable Metal recovery rate, effect also can largely influence subsequent dedoping step, and rate influences the rate of overall flow.
The Chinese patent literature of Publication No. CN105322247A discloses one kind and directly prepares cobalt acid with lithium ion battery The method of lithium specifically discloses the acid leaching process using sulfur dioxide or hydrogen as additive.Though mixed processing method is simple easily Row, process is short, but the processing of SO 2 tail gas or the use of hydrogen will bring new environmental and safety problems.
In conclusion this field is badly in need of developing a kind of efficient, quick, inexpensive, free of contamination active material leaching method, To establish a kind of process flow of adaptation waste and old lithium ion battery recycling heavy industrialization operation.
Summary of the invention
It is of the invention to provide in a kind of waste and old lithium ion battery removal process just to overcome the problems, such as that the prior art encounters The ball milling reductic acid leaching method of pole active material, it is intended to reduce production cost, and promote valuable metal leaching rate.
A kind of ball milling acidleach method of waste lithium ion cell anode active material, waste and old lithium ion battery are put through short circuit Electricity, dismantling, binder removing, crushing and screening obtain electrode material powder；Electrode material powder, gelatinized corn starch and the acid solution are mixed Colloidal solution is closed to obtain, the colloidal solution is subjected to ball-milling treatment, obtains slurry；Slurry with water is rinsed, positive work is filtered to obtain The aqueous solution of property material.
In the present invention, electrode material is dispersed in the colloidal dispersion without fluidised form water of gelatinized corn starch and acid solution composition, then lead to The method for crossing ball milling auxiliary realizes the reducing leaching of the valuable element in electrode material.The present invention realizes positive electrode active materials A step leach, while substantially increasing reaction rate, save production cost, in addition, treatment process of the present invention is in room temperature, normal It is carried out under the conditions of pressure, without heating equipment and high press device, is suitable for industrial-scale processing.
It is imitated the inventors discovered that the colloid system without fluidised form water is carried out ball milling and can reach good leaching Fruit.However, ball milling leaching effect is decreased obviously when containing more fluidised form water.
Good colloid sliminess is controlled, can be realized by the starch concentration in regulation colloidal solution.By largely grinding Study carefully discovery, in colloidal solution, the content of starch is 25~50g/L.Under the colloidal dispersion of the preferred concentration, leaching efficiency The leaching of high and ball milling is easier.
Further preferably, in colloidal solution, the content of starch is 30~40g/L.The present inventors have additionally discovered that in the shallow lake Under powder content, leaching effect is more preferable.
The acid solution is the aqueous solution of inorganic acid.
Preferably, the acid solution is aqueous sulfuric acid.
Preferably, sour mass fraction is 10~17.5% in colloidal solution.Under the preferred mass fraction, leaching Effect is more preferable out, and helps to reduce processing cost, reduces the corrosion condition to processing equipment.
Preferably, used gelatinized corn starch solid content is between 50~100g/L.
In the present invention, starch gelatinization process uses common process.The preparation method of the gelatinized corn starch is for example are as follows: presses solid-liquid Than mixing starch with water for the ratio of 50~100g/L, 65~70 DEG C are heated with stirring to, stable paste, as starch are formed Paste.
Further preferably, used gelatinized corn starch solid content is between 60~80g/L.
Preferably, the concentration of dilution heat of sulfuric acid is mass fraction 20~35% in reaction process.
In the present invention, electrode material powder can be dispersed in the gelatinized corn starch and acid solution mixed in equal volume, obtain the glue Liquid solution.In actual process, preferably electrode material powder is dispersed in gelatinized corn starch, after stirring, then is added and starch The acid solution of the isometric mass fraction of paste, ball milling leaches after mixing evenly.
In the present invention, in the colloidal solution, the content of electrode material powder is not specially required, with can be evenly dispersed In the colloidal solution system, for example, in the colloidal solution, the content of electrode material powder is preferably 10~ 50g/L。
Under the starch concentration and sulfuric acid concentration, preferably, in mechanical milling process, drum's speed of rotation 200~ Between 300rpm, the reaction time is between 1~2h.
Ball milling leaching process carries out at room temperature, and the temperature for the treatment of process is less than 50 DEG C.
By the Collaborative Control of the acid wet-milling, it can be obviously shortened extraction time, by the method for the invention, entire ball Can be controlled in mill-leaching total time 2h and within, leaching efficiency is high, and valuable element leaching rate is high.
In the present invention, discharge process, as discharge medium, is disassembled process using negative-pressure sealing and disassembles work using carbon ground-slag end Skill, binder remove low-temperature bake method.
Preferably, during short circuit dischange, by waste and old lithium ion battery in the carbon ground-slag end short circuit dischange, directly It is lower than 1V to final voltage.
Preferably, be heat-treated the material after dismantling in air atmosphere, 350~450 DEG C in removing adhesive process, Remove binder.
In the present invention, a kind of leaching method of waste lithium ion cell anode active material, specifically includes the following steps:
Step a): waste and old lithium ion battery is discharged in the powder of the slag containing waste carbon, blanking voltage 1V；
Step b): battery is disassembled under closed subnormal ambient, separate housing, core, electrolyte；
Step c): by 350~450 DEG C of core roastings, crushing and screenings, electrode material powder is obtained；
Step d): starch and water are mixed in the ratio of 50~100g/L, 70 DEG C is heated with stirring to, forms stable paste Shape；
Step e): 20~35% dilution heat of sulfuric acid is added in gelatinized corn starch obtained by step d), another that electrode material powder is added End is sufficiently stirred；
Step f): being put into ball mill for mixture obtained by step e), runs 1~2h with the revolving speed of 200~300rpm；
Step g): mixture obtained by step e) is added water and stirred, filtrate is taken after filtering.
In step c), the electrode material powder includes positive electrode active materials, conductive agent and cathode graphite etc., substantially not Containing collector, binder.
In step g), the filtrate is the sulfate liquor containing lithium ion and valuable metal ions after leaching；It can be to this Filtrate is handled, and is separated, is purified into each valuable element；It can also recycled in its entirety directly after edulcoration purification.
The invention has the benefit that
(1) electrode material is originally dispersed in the colloidal solution system of Starch formation by the present invention, passes through ball milling institute The gluing system stated, to realize the efficient leaching of the electrode material in old and useless battery；
(2) ball milling for passing through the colloidal solution can unexpectedly reach the high of electrode material valuable element and leach Effect.The study found that under the collaboration of the preferred starch concentration of colloidal solution of the present invention, sour condition and rotational speed of ball-mill, The leaching rate of valuable element is up to 98% or more；
(3) production cost is greatlyd save as reducing agent using starch acid hydrolysate, reduces the corrosion to equipment, and mention High leaching efficiency；
(4) ball-milling method assisted Reduction leaching process is used, the rate and leaching efficiency of reaction are improved；
(5) treatment process of the present invention carries out under room temperature, condition of normal pressure, is not necessarily to press device, can large scale processing.
Detailed description of the invention
Fig. 1 is the process flow chart that positive electrode active materials leach in waste and old lithium ion battery removal process of the present invention.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention, rather than protects to the claims in the present invention The limitation of range.
Embodiment 1:
It takes waste mobile phone cobalt acid lithium battery several, puts it into the powder of the slag containing waste carbon and discharge, until voltage is lower than It is picked up when 1V, takes remaining electrolyte away after cutting open shell, take out core.Core is tentatively broken, it is put into roaster and is heated to 400 DEG C, the binder on burning-off pole piece and most of carbon material used as anode, tail gas are absorbed with lime aqueous solution in air atmosphere.It takes out Sintered solid mixture is sieved, and is copper foil and aluminium foil fragment, the lower predominantly positive electrode active materials containing cobalt acid lithium of sieve on sieve.
Embodiment 2:
Starch 50g is weighed, 1L deionized water is added, keep stirring and is heated to 70 DEG C, until system is in stable paste, life Entitled S1 solution.
Embodiment 3:
Starch 60g is weighed, 1L deionized water is added, keep stirring and is heated to 70 DEG C, until system is in stable paste, life Entitled S2 solution.
Embodiment 4:
Starch 80g is weighed, 1L deionized water is added, keep stirring and is heated to 70 DEG C, until system is in stable paste, life Entitled S3 solution.
Embodiment 5:
Starch 100g is weighed, 1L deionized water is added, keep stirring and is heated to 70 DEG C, until system is in stable paste, It is named as S4 solution.
Embodiment 6:
1 gained undersized product of 20g embodiment is taken, is put into the S1 solution of 500ml, is added 500ml20%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 1h with 200rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 97.2% of former old and useless battery standard amount containing Co.
Embodiment 7:
1 gained undersized product of 20g embodiment is taken, is put into the S1 solution of 500ml, is added 500ml30%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 1h with 200rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 97.9% of former old and useless battery standard amount containing Co.
Embodiment 8:
1 gained undersized product of 20g embodiment is taken, is put into the S1 solution of 500ml, is added 500ml30%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 2h with 300rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 98.2% of former old and useless battery standard amount containing Co.
Embodiment 9:
1 gained undersized product of 20g embodiment is taken, is put into the S2 solution of 500ml, is added 500ml30%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 2h with 300rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 98.5% of former old and useless battery standard amount containing Co.
Embodiment 10:
1 gained undersized product of 20g embodiment is taken, is put into the S3 solution of 500ml, is added 500ml35%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 2h with 300rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 98.6% of former old and useless battery standard amount containing Co.
Embodiment 11:
1 gained undersized product of 20g embodiment is taken, is put into the S4 solution of 500ml, is added 500ml35%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 1h with 200rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 98.5% of former old and useless battery standard amount containing Co.
Embodiment 12:
1 gained undersized product of 20g embodiment is taken, is put into the S4 solution of 500ml, is added 500ml35%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 2h with 300rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 98.3% of former old and useless battery standard amount containing Co.
Embodiment 13:
It takes waste and old automobile-used ternary battery several, puts it into the powder of the slag containing waste carbon and discharge, until when voltage is lower than 1V It picks up, takes remaining electrolyte away after cutting open shell, take out core.Core is tentatively broken, it is put into roaster and is heated to 400 DEG C, The binder on burning-off pole piece and most of carbon material used as anode, tail gas are absorbed with lime aqueous solution in air atmosphere.It takes out and burns Solid mixture after knot is sieved, and is copper foil and aluminium foil fragment, the positive-active of the lower predominantly LiMn2O4 containing nickel-cobalt-of sieve on sieve Material.
20g undersized product is taken, is put into the S3 solution of 500ml, the dilution heat of sulfuric acid of 500ml 35% is added while stirring, 30min is persistently stirred, the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, planetary ball is started Grinding machine takes out after running 2h with 300rpm.Add hot water injection into the ball grinder of taking-up, filters, must clarify after restoring mobility Filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is glucose, sulphur in filtrate Acid, cobaltous sulfate, manganese sulfate, nickel sulfate, lithium sulfate, wherein cobalt element content accounts for the 98.7% of former old and useless battery standard amount containing Co.
Comparative example 1:
Starch 20g is weighed, 1L deionized water is added, keep stirring and is heated to 70 DEG C, until system is in stable paste.It takes 1 gained undersized product of 20g embodiment is put into solution, and the dilution heat of sulfuric acid of 500ml 20% is added while stirring, lasting to stir 30min, system are in non-uniform paste.Mixing paste is transferred in ball grinder, starts planetary ball mill, is run with 200rpm It is taken out after 1h.Add hot water injection into the ball grinder of taking-up, is filtered after restoring mobility, obtain clear filtrate.After sampling is evaporated, It detecting through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is glucose, sulfuric acid, cobaltous sulfate, lithium sulfate in filtrate, Wherein cobalt element content accounts for the 47% of former old and useless battery standard amount containing Co.In this comparative example, though it reacts under identical parameters, But gelatinized corn starch water content is excessively high, ball milling poor effect.
Comparative example 2:
Starch 125g is weighed, 1L deionized water is added, keep stirring and is heated to 70 DEG C, until system is in stable paste. 1 gained undersized product of 20g embodiment is taken, is put into solution, the dilution heat of sulfuric acid of 500ml 20% is added while stirring, persistently stirs 30min is mixed, system is in sticky paste.Mixing paste is transferred in ball grinder, starts planetary ball mill, is run with 300rpm It is taken out after 2h.Add hot water injection into the ball grinder of taking-up, is filtered after restoring mobility, obtain clear filtrate.After sampling is evaporated, It detecting through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is glucose, sulfuric acid, cobaltous sulfate, lithium sulfate in filtrate, Wherein cobalt element content accounts for the 88.6% of former old and useless battery standard amount containing Co.In this comparative example, colloidal solution viscosity is excessive, ball milling Effect is poor.
Comparative example 3:
1 gained undersized product of 20g embodiment is taken, is put into the S3 solution of 500ml, is added 500ml10%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 2h with 200rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 26% of former old and useless battery standard amount containing Co.This comparative example In, since acid solution is too low, the non-complete hydrolysis of starch causes a large amount of cobalt elements not to be reduced.
Comparative example 4:
1 gained undersized product of 20g embodiment is taken, is put into the S3 solution of 500ml, is added 500ml35%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 2h with 100rpm.Add hot water injection into the ball grinder of taking-up, restores mistake after mobility Filter, obtains clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is in filtrate Glucose, sulfuric acid, cobaltous sulfate, lithium sulfate, wherein cobalt element content accounts for the 79.3% of former old and useless battery standard amount containing Co.This comparison In example, since rotational speed of ball-mill is too low, leaching process reaction rate is too slow, is difficult to leach completely in 2h.
Comparative example 5:
1 gained undersized product of 20g embodiment is taken, is put into the S3 solution of 500ml, is added 500ml35%'s while stirring Dilution heat of sulfuric acid persistently stirs 30min, and the system after stablizing still is in sticky paste.Mixing paste is transferred in ball grinder, is opened Dynamic planetary ball mill, takes out after running 4h with 300rpm.Into the ball grinder of taking-up plus hot water injection, colloid mucus wall built-up are tight Weight.In this comparative example, since Ball-milling Time is too long, aqueous colloidal evaporation is excessive, settles after system unstability.
In conclusion the present invention is used as reducing agent using starch acid hydrolysate, to applying waste lithium ionic electricity under ball milling auxiliary Positive electrode active materials are recycled in pond, and the valuable constituent rate of recovery is 97% or more, when solid content and sulfuric acid concentration are in preferred stripe When under part, the rate of recovery more reaches 98.5% or more, greatly reduces the cost of industrial application, green non-pollution, simple process, together When improve the rate and efficiency of reaction.

Claims (8)

1. a kind of ball milling acidleach method of waste lithium ion cell anode active material, which is characterized in that waste and old lithium ion battery Electrode material powder is obtained through short circuit dischange, dismantling, binder removing, crushing and screening；By the electrode material powder, gelatinized corn starch Colloidal solution is mixed to obtain with acid solution, the colloidal solution is subjected to ball-milling treatment, obtains slurry；Slurry with water is rinsed, is filtered Obtain the aqueous solution of positive electrode active materials；
The acid solution is the aqueous solution of inorganic acid.
2. the ball milling acidleach method of waste lithium ion cell anode active material according to claim 1, which is characterized in that In colloidal solution, the content of starch is 25 ~ 50g/L.
3. the ball milling acidleach method of waste lithium ion cell anode active material according to claim 1, which is characterized in that In colloidal solution, the content of starch is 30 ~ 40g/L.
4. the ball milling acidleach method of waste lithium ion cell anode active material according to claim 1, which is characterized in that The acid solution is aqueous sulfuric acid.
5. the ball milling acidleach method of waste lithium ion cell anode active material according to claim 4, which is characterized in that In colloidal solution, sour mass fraction is 10 ~ 17.5%.
6. the ball milling acidleach method of waste lithium ion cell anode active material according to claim 1, which is characterized in that In the gelatinized corn starch, the concentration of starch is 50 ~ 100g/L；Acid solution is dilution heat of sulfuric acid, mass fraction 20 ~ 35%；By electrode Material powder is dispersed in the gelatinized corn starch and acid solution mixed in equal volume, obtains the colloidal solution.
7. the ball milling acidleach method of described in any item waste lithium ion cell anode active materials according to claim 1 ~ 6, It is characterized in that, the revolving speed of mechanical milling process is 200 ~ 300rpm.
8. the ball milling acidleach method of waste lithium ion cell anode active material according to claim 1, which is characterized in that Ball-milling Time is 1 ~ 2h.
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