CN109706320A - A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery - Google Patents
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery Download PDFInfo
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- CN109706320A CN109706320A CN201910084974.5A CN201910084974A CN109706320A CN 109706320 A CN109706320 A CN 109706320A CN 201910084974 A CN201910084974 A CN 201910084974A CN 109706320 A CN109706320 A CN 109706320A
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- 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
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- 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
Abstract
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, belongs to the field of metallurgy that precious metal recycles in waste lithium ion cell anode material.This method are as follows: the solid powder of pretreated cobalt acid lithium is added in the acidleach mixed liquor of dilute sulfuric acid and ethyl alcohol, in 80~90 DEG C of lasting stirrings, acid-leaching reaction solution is filtered, NaOH solution is added into lixivium, Co is precipitated, and obtains Co (OH)2The mixed liquor of precipitating will contain Co (OH)2Residue washing, it is dry, after calcining, obtain Co3O4；To containing Li+Filtrate in, be added dropwise NaOH after, be concentrated by evaporation, be added saturation Na2CO3, it is stirred to react, obtains Li2CO3Sediment is filtered, and is then dried, and Li is obtained2CO3.This method has leaching rate higher, environmental protection, and the benefits such as generation for having the organic matters such as aldehyde, ether and ester.
Description
Technical field
The present invention relates to the field of metallurgy recycled to precious metal in waste lithium ion cell anode material, and in particular to one
A kind of ethyl alcohol of kind is the method for Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery.
Background technique
The modernization of society needs more and more mobile electrons and electric car, these rely primarily on lithium ion battery
(LIBs).With the growth of LIBs demand, the supply of the battery materials such as lithium salts and transition metal is also increasing.In common battery
In material, lithium (Li) and cobalt (Co) are played a crucial role.However, limited Co resource, the uneven distribution of Li mineral
And the uneven concentration that Li is laid in salt water and seawater causes production cost higher.Therefore, Li and Co is considered as tool shadow
Ring the element of power.Compared with natural resources, the concentration of Li and Co wants much higher in useless LIBs, is the resource rich in Li and Co.It examines
Consider environmental problem caused by the useless LIBs of processing, the recycling of LIBs may be a kind of sustainable method, while can expire
The sufficient battery industry demand growing to Li and Co.
Currently, pyrometallurgy and hydrometallurgy route are two kinds of typical methods for recycling useless LIBs.In general, being all first
Refuse battery should be pre-processed, such as discharged, remove etc..Then it is further processed pretreated electrode material.Pyrometallurgy is logical
It crosses pyrometallurgical processes and electrode scrap material is melted to obtain Li's and Co by clinker separation and carbon thermal reduction using high temperature furnace
Oxide separates again later.Pyrometallurgical processes are usually related with noxious gas emission, complex process.Hydrometallurgy is pair
LiCoO2The most important method of recycling because they have high efficiency and beneficial to the low toxicity of atmosphere discharge etc.
Place, and can be with industrialized production.In the hydrometallurgical technology for recycling useless LIB, acidleach is most cost-effectiveness, and
It is simple and environmentally-friendly.
Summary of the invention
It is an object of the present invention to provide a kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, this method
Be in water solution system, ethyl alcohol effect under, redox LiCoO2Co and Li is recycled, is a kind of environmental protection and energy saving low consumption, green
The hydrometallurgical processes of precious metal, pretreated useless anode material of lithium battery powder is pressed in the useless lithium battery of color safe retrieving
Be placed according to certain solid-to-liquid ratio in the mixed solution of dilute sulfuric acid and ethyl alcohol, heated at constant temperature, stir, to Co and Li in useless lithium battery into
Row acidleach recycling, then carries out precipitation and separation.This method has leaching rate higher, environmental protection, and has aldehyde, ether and ester etc. and have
The benefits such as the generation of machine object.
A kind of ethyl alcohol of the invention is the method for Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, comprising the following steps:
Step 1: pretreatment
Useless lithium battery is discharged, is disassembled, positive plate is obtained；
Positive plate is put into sodium hydroxide solution, dissolution removal aluminium obtains cobalt acid lithium black powder mixed liquor；
By cobalt acid lithium black powder mixed liquor, filtering by filter residue and drying, calcining, grinding, obtains the solid powder of cobalt acid lithium
End；
Step 2: acid-leaching reaction
Dilute sulfuric acid and ethyl alcohol are mixed, acidleach mixed liquor is obtained；Wherein, in acidleach mixed liquor, the volume fraction of ethyl alcohol is 5
~20%, surplus is dilute sulfuric acid；The molar concentration of dilute sulfuric acid is 4~6mol/L；
Cobalt acid lithium solid powder is added in acidleach mixed liquor, in 80~90 DEG C of lasting stirrings, and real-time monitoring reaction is molten
The rate of recovery of Co and Li in liquid obtain acid-leaching reaction solution after the rate of recovery of Co and Li no longer changes；Wherein, by solid-liquid
Than cobalt acid lithium solid powder: acidleach mixed liquor=(20~40) g:1L；
Step 3: precipitating
Acid-leaching reaction solution is subjected to first time filtering, obtains lixivium；
NaOH solution is added into lixivium, Co is precipitated, and obtains Co (OH)2The mixed liquor of precipitating carries out second and filters,
It obtains containing Co (OH)2The filter residue of precipitating and contain Li+Filtrate；
Co (OH) will be contained2Residue washing, it is dry, after calcining, obtain Co3O4；
To containing Li+Filtrate in, be added dropwise NaOH, adjust pH value be 9~10, be then concentrated by evaporation, until Li in filtrate+It is dense
Degree is 10g/L or more, and saturation Na is added2CO3, it is stirred to react, obtains Li2CO3Sediment is filtered, and is then dried, and is obtained
Li2CO3；Wherein, it is saturated Na2CO3Additional amount be 1~1.2 times of reaction theory amount.
In the step 1, it is by the method that useless lithium battery discharges, useless lithium battery is put into saturated sodium chloride solution and is soaked
Steep 10~12h.
In the step 1, cobalt acid lithium is attached on aluminium foil on the positive plate, use molar concentration for 2~
The NaOH of 3mol/L, which dissolves aluminium, to be removed, and dosage is that can sufficiently dissolve the amount of aluminium foil.
In the step 1, dry is 50~80 DEG C, and drying time is 8~12h, and calcination temperature is 500~600 DEG C, is forged
The burning time is 6~8h.
In the step 1, the grinding uses agate mortar, and milling time is 30~40min, and the purpose of grinding is
Particle is uniformly dispersed, the particle size of cobalt acid lithium solid powder is 200-300 mesh.
In the step 2, the stirring, stirring rate is 200~400r/min.
In the step 2, in the lasting whipping process, condensing plant is added and flows back to the ethyl alcohol of volatilization.
In the step 2, the method for the rate of recovery of Co and Li in real-time monitoring reaction solution are as follows: to reaction solution into
Row element constituent analysis, and calculate the content of Co and Li.
In the step 3, the molar concentration of the NaOH solution is 2~4mol/L, and Adding Way is first will leaching
The pH value of filtrate is adjusted to 6.0~6.5, current when being settled out, and NaOH is added dropwise until precipitating is not further added by.
The ethyl alcohol is in the useless lithium battery of reducing agent hydrometallurgic recovery in the method for Co and Li, and the water is deionization
Water.
The ethyl alcohol is the Co of generation in the useless lithium battery of reducing agent hydrometallurgic recovery in the method for Co and Li3O4In melting carbon
Electrochemical separation is at Co and oxygen in hydrochlorate.
Use ethyl alcohol of the invention for the method for Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, wherein the rate of recovery of Co
The rate of recovery for 70.9%~90.4%, Li is 94.6%~99.9%.
In the present invention, unless specifically indicated, the water be deionized water, the purity of raw material used be analysis it is pure with
On.
A kind of ethyl alcohol of the invention is the method for Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, and its advantages exist
In:
1, the present invention handles the positive electrode powder of pretreated waste lithium cell, the object of the invention by acid leaching process
It is that the hydrogen peroxide in traditional handicraft is replaced to restore LiCoO using a kind of new reducing agent ethyl alcohol2Obtain Co salt and Li salt.So
Co afterwards2+By addition NaOH solution with Co (OH)2Form collect then in air roasting be translated into Co3O4.Later may be used
By the Co of acquisition3O4Electrochemical separation is at Co and oxygen in fused carbonate.Li with Li2CO3Form collect.
2, Method And Principle of the invention is: using the reproducibility of ethyl alcohol, by the cobalt in cobalt acid lithium under sulfuric acid existence condition
With lithium with Co2+And Li+Form separate out, based on this principle by Co3+It reverts in solution and then cobalt and lithium is recycled.
Both H required for reaction had been provided in acidic environment+, in turn ensure the dissolubility of cobalt and lithium.
3, use method of the invention can by waste lithium cell cobalt and lithium with low cost, environmental-friendly, circulation benefit
Mode recycles and synthesizes the cell positive material with considerable performance again, easy to operate, and leaching rate is high, can be mass-produced.
Detailed description of the invention
Fig. 1 is in the embodiment of the present invention 1, to the XRD analysis figure of battery anode slice calcined product.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
In the embodiment of the present invention, the disused mobile battery used is commercial products.
In the embodiment of the present invention, the ethyl alcohol of use, purity is that analysis is pure.
In the embodiment of the present invention, the sodium hydroxide of use, purity is that analysis is pure.
In the embodiment of the present invention, the sulfuric acid and sodium chloride of use, purity are that analysis is pure.
In the embodiment of the present invention, the water-bath used is heat collecting type heated at constant temperature, stirring rate are as follows: 300r/min.
In the embodiment of the present invention, the bath temperature used is 80 DEG C.
In the embodiment of the present invention, the dry drying box used is new talent DZF-6020 type vacuum oven.
In the embodiment of the present invention, calcine that use be Muffle furnace.
In the embodiment of the present invention, the elemental analyzer used is atomic absorption spectrophotometer, model are as follows: BTS4000.
In the embodiment of the present invention, carrying out heating to reaction unit is that reactor is placed in water-bath to heat.
Embodiment 1
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, comprising the following steps:
Step 1: pretreatment
Disused mobile battery electrode tip is impregnated to 12h to be substantially discharged in saturated sodium chloride solution, later dismantling manually, so
The positive plate after dismantling is sufficiently dissolved with 2.5mol/LNaOH solution afterwards, aluminium is separated, obtains cobalt acid lithium black powder mixed liquor；
By cobalt acid lithium black powder mixed liquor, filtering obtains the filter residue of positive electrode.Then, by the filter residue of positive electrode
60 DEG C of dry 8h in drying box calcine 8h, obtain calcined product, then grind calcined product later 500 DEG C in Muffle furnace
30min is ground, the cobalt acid lithium solid powder that partial size is 200-300 mesh is obtained.XRD analysis is carried out to obtained calcined product, is obtained
XRD diagram see Fig. 1, Cong Tuzhong, it can be determined that, by processing, isolated calcined product is cobalt acid lithium.
Step 2: acidleach
Acid dip solution is made of ethyl alcohol and dilute sulfuric acid, wherein in acid dip solution, dilute sulfuric acid concentration is 5mol/L, ethyl alcohol body
Fraction is 20%, and surplus is dilute sulfuric acid.
1g cobalt acid lithium solid powder is added in 50mL acid dip solution and is reacted, in reaction unit, condensing plant is housed,
In reaction process, speed of agitator 300r/min, bath temperature is 80 DEG C, reaction time 60min, and gained acid-leaching reaction is molten
Liquid carries out elemental analysis, calculates the rate of recovery of Co and Li.
Step 3: separation
(1) precipitate C o
Acid-leaching reaction solution after taking above-mentioned reaction carries out first time filtering, retains filtrate, adds 2mol/L's into filtrate
NaOH solution, adjusting pH value is 6, is then slowly added dropwise from beginning with precipitating and occurs not being further added by stoppings to precipitation capacity, progress the
Secondary filter obtains Co (OH)2The filter residue of precipitating and contain Li+Filtrate, by Co (OH)2The filter residue of precipitating is calcined to obtain Co3O4；
(2) Li: Xiang Hanyou Li is precipitated+Filtrate in, continue plus 2mol/LNaOH solution to pH be 9-10, then pass through water
Heating evaporation concentration is bathed by Li+Concentration is adjusted to 10g/L, and saturation Na is then added2CO3Additional amount is CO3 2-With Li+Reaction obtains
Li2CO31.2 times of theoretical amount, stirring obtains precipitating Li2CO3, filtration drying obtains Li2CO3。
In the present embodiment, the rate of recovery that the rate of recovery of Li is 99.3%, Co is 77.1%.
Embodiment 2
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, in acid dip solution, reaction temperature is 90 DEG C；
Other modes are identical.
In the present embodiment, the rate of recovery that the rate of recovery of Li is 99.4%, Co is 90.4%.
Embodiment 3
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, in acid-leaching reaction, the molar concentration of dilute sulfuric acid is 4mol/L；
Other modes are identical.
In the present embodiment, the rate of recovery that the rate of recovery of Li is 99.9%, Co is 73.6%.
Embodiment 4
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, the molar concentration of dilute sulfuric acid is 6mol/L；
Other modes are identical.
In the present embodiment, the rate of recovery that the rate of recovery of Li is 99.9%, Co is 70.9%.
Embodiment 5
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, by solid-to-liquid ratio, cobalt acid lithium solid powder: acidleach mixed liquor=30g/L,
Other modes are identical.
In the present embodiment, the rate of recovery that the rate of recovery of Li is 94.6%, Co is 72.2%.
Embodiment 6
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, comprising the following steps:
Step 1: pretreatment
Disused mobile battery electrode tip is impregnated to 12h to be substantially discharged in saturated sodium chloride solution, later dismantling manually, so
The positive plate after dismantling is sufficiently dissolved with 2mol/LNaOH solution afterwards, aluminium is separated, obtains cobalt acid lithium black powder mixed liquor；
By cobalt acid lithium black powder mixed liquor, filtering obtains the filter residue of positive electrode.Then, by the filter residue of positive electrode
80 DEG C of dry 8h in drying box calcine 10h, then grind 40min later 550 DEG C in Muffle furnace, and obtaining partial size is 200-
The cobalt acid lithium solid powder of 300 mesh.
Step 2: acidleach
Acid dip solution is made of ethyl alcohol and dilute sulfuric acid, wherein in acid dip solution, dilute sulfuric acid concentration is 5mol/L, ethyl alcohol body
Fraction is 20%, and surplus is dilute sulfuric acid.
2g cobalt acid lithium solid powder is added in 50mL acid dip solution and is reacted, in reaction unit, condensing plant is housed,
In reaction process, speed of agitator 200r/min, bath temperature is 90 DEG C, and it is molten to obtain acid-leaching reaction by reaction time 90min
Liquid；Every being sampled in 10min, by elemental composition analyzer, analyze in acid-leaching reaction solution, the content of Co and Li, when
After the content of Co and Li is not further added by or when increasing variable less than 1%, stop reaction；
Wherein, the condensing unit of setting guarantees that the amount of ethyl alcohol in device is steady by the alcohol reflux of evaporation into reaction unit
It is fixed.
Step 3: separation
(1) precipitate C o
Acid-leaching reaction solution after taking above-mentioned reaction carries out first time filtering, retains filtrate, adds 2mol/L's into filtrate
NaOH solution, adjust pH value be 6.5, be then slowly added dropwise from begin with precipitating occur be not further added by stoppings to precipitation capacity, progress
Second of filtering, obtains Co (OH)2The filter residue of precipitating and contain Li+Filtrate, by Co (OH)2The filter residue of precipitating is calcined to obtain
Co3O4；
(2) Li: Xiang Hanyou Li is precipitated+Filtrate in, continue plus 2mol/LNaOH solution to pH be 9-10, then pass through water
Heating evaporation concentration is bathed by Li+Concentration is adjusted to 10g/L, and saturation Na is then added2CO3Additional amount is CO3 2-With Li+Reaction obtains
Li2CO31.1 times of theoretical amount, stirring obtains precipitating Li2CO3, filtration drying obtains Li2CO3。
In the present embodiment, the rate of recovery that the rate of recovery of Li is 99.4%, Co is 90.4%.
Comparative example 1
A kind of hydrometallurgic recovery is given up the method for Co and Li in lithium battery, and with embodiment 1, difference is:
In step 2, in acid dip solution, ethyl alcohol is not added.
Other modes are identical.
In this comparative example, the rate of recovery that the rate of recovery of Li is 93.4%, Co is 55.5%.Ethyl alcohol is added with embodiment 1
The rate of recovery compares, and illustrates that the addition of ethyl alcohol significantly improves the leaching rate of cobalt and lithium.Prove that ethyl alcohol, which is added, to be played
The effect for promoting cobalt and lithium to leach.
Comparative example 2
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, in acid dip solution, reaction temperature is 70 DEG C；
Other modes are identical.
In this comparative example, the rate of recovery that the rate of recovery of Li is 83.1%, Co is 50.1%.Pass through this comparative example and embodiment
1 compares, and illustrates that acid-leaching reaction temperature has a great impact to the rate of recovery.
Comparative example 3
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, in acid dip solution, reaction temperature is 60 DEG C；
Other modes are identical.
In this comparative example, the rate of recovery that the rate of recovery of Li is 80.1%, Co is 42.3%.Pass through this comparative example and embodiment
1 compares, and illustrates the decline of acid-leaching reaction temperature so that the rate of recovery reduces.
Comparative example 4
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
(1) in step 2, in acid-leaching reaction, the molar concentration of dilute sulfuric acid is 2mol/L；
Other modes are identical.
In this comparative example, the rate of recovery that the rate of recovery of Li is 91.4%, Co is 51.3%.Pass through this comparative example and embodiment
1 compares, and during illustrating acidleach, the additional amount of dilute sulfuric acid is very big to acidleach influential effect, to affect Li's and Co
The rate of recovery of the rate of recovery, especially Co.
Comparative example 5
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, in acid-leaching reaction, the molar concentration of dilute sulfuric acid is 3mol/L；
Other modes are identical.
In this comparative example, the rate of recovery that the rate of recovery of Li is 99.1%, Co is 67.1%.Pass through this comparative example and embodiment
1 compares, and during illustrating acidleach, the additional amount of dilute sulfuric acid is very big to acidleach influential effect, to affect the recycling of Co
Rate.
Comparative example 6
A kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, with embodiment 1, difference is:
In step 2, by solid-to-liquid ratio, cobalt acid lithium solid powder: acidleach mixed liquor=10g/L,
Other modes are identical.
In this comparative example, the rate of recovery that the rate of recovery of Li is 95.8%, Co is 66%, passes through this comparative example and embodiment 1
It compares, during illustrating acidleach, the additional amount of cobalt acid lithium solid powder has the rate of recovery that will affect Co.
Claims (10)
1. a kind of method that ethyl alcohol is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which comprises the following steps:
Step 1: pretreatment
Useless lithium battery is discharged, is disassembled, positive plate is obtained；
Positive plate is put into sodium hydroxide solution, dissolution removal aluminium obtains cobalt acid lithium black powder mixed liquor；
By cobalt acid lithium black powder mixed liquor, filtering by filter residue and drying, calcining, grinding, obtains the solid powder of cobalt acid lithium；
Step 2: acid-leaching reaction
Dilute sulfuric acid and ethyl alcohol are mixed, acidleach mixed liquor is obtained；Wherein, in acidleach mixed liquor, the volume fraction of ethyl alcohol is 5~
20%, surplus is dilute sulfuric acid；The molar concentration of dilute sulfuric acid is 4~6mol/L；
Cobalt acid lithium solid powder is added in acidleach mixed liquor, in 80~90 DEG C of lasting stirrings, and in real-time monitoring reaction solution
Co and the rate of recovery of Li obtain acid-leaching reaction solution after the rate of recovery of Co and Li no longer changes；Wherein, by solid-to-liquid ratio, cobalt
Sour lithium solid powder: acidleach mixed liquor=(20~40) g:1L；
Step 3: precipitating
Acid-leaching reaction solution is subjected to first time filtering, obtains lixivium；
NaOH solution is added into lixivium, Co is precipitated, and obtains Co (OH)2The mixed liquor of precipitating carries out second and filters, obtains
Contain Co (OH)2The filter residue of precipitating and contain Li+Filtrate；
Co (OH) will be contained2Residue washing, it is dry, after calcining, obtain Co3O4；
To containing Li+Filtrate in, be added dropwise NaOH, adjust pH value be 9~10, be then concentrated by evaporation, until Li in filtrate+Concentration is
Saturation Na is added in 10g/L or more2CO3, it is stirred to react, obtains Li2CO3Sediment is filtered, and is then dried, and is obtained
Li2CO3；Wherein, it is saturated Na2CO3Additional amount be 1~1.2 times of reaction theory amount.
2. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 1, be by the method that useless lithium battery discharges, by useless lithium battery be put into saturated sodium chloride solution impregnate 10~
12h。
3. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 1, cobalt acid lithium is attached on aluminium foil on the positive plate, uses molar concentration for 2~3mol/L's
NaOH, which dissolves aluminium, to be removed, and dosage is that can sufficiently dissolve the amount of aluminium foil.
4. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 1, dry is 50~80 DEG C, and drying time is 8~12h, and calcination temperature is 500~600 DEG C, and calcination time is
6~8h.
5. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 1, the grinding, milling time is 30~40min, and the particle size of cobalt acid lithium solid powder is 200-
300 mesh.
6. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 2, the stirring, stirring rate is 200~400r/min.
7. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 2, the method for the rate of recovery of Co and Li in real-time monitoring reaction solution are as follows: to reaction solution carry out element at
Analysis, and calculate the content of Co and Li.
8. the method that ethyl alcohol as described in claim 1 is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery, which is characterized in that
In the step 3, the molar concentration of the NaOH solution is 2~4mol/L, and Adding Way is the first pH by lixivium
Value is adjusted to 6.0~6.5, current when being settled out, and NaOH is added dropwise until precipitating is not further added by.
9. the ethyl alcohol as described in claim 1~8 any one is the method for Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery,
It is characterized in that, the ethyl alcohol is the Co of generation in the useless lithium battery of reducing agent hydrometallurgic recovery in the method for Co and Li3O4Molten
Melt in carbonate Electrochemical separation into Co and oxygen.
10. the side that the ethyl alcohol as described in claim 1~8 any one is Co and Li in the useless lithium battery of reducing agent hydrometallurgic recovery
Method, which is characterized in that use ethyl alcohol of the invention to give up the method for Co and Li in lithium battery for reducing agent hydrometallurgic recovery, wherein Co
The rate of recovery that the rate of recovery is 70.9%~90.4%, Li is 94.6%~99.9%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960480A (en) * | 2020-08-28 | 2020-11-20 | 四川省有色冶金研究院有限公司 | Method for preparing nickel-cobalt-manganese ternary material by using waste lithium ion battery |
| CN112225260A (en) * | 2020-10-28 | 2021-01-15 | 江门市长优实业有限公司 | Process for recovering cobalt from waste lithium batteries |
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