CN109461984A - A method of recycling Metal Values From Spent Lithium-ion Batteries - Google Patents
A method of recycling Metal Values From Spent Lithium-ion Batteries Download PDFInfo
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- CN109461984A CN109461984A CN201811222014.2A CN201811222014A CN109461984A CN 109461984 A CN109461984 A CN 109461984A CN 201811222014 A CN201811222014 A CN 201811222014A CN 109461984 A CN109461984 A CN 109461984A
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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
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- 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
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- 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
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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
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Abstract
The present invention relates to a kind of method for recycling Metal Values From Spent Lithium-ion Batteries, this method successively carries out alkali leaching processing, acidleach processing to the positive electrode of waste and old lithium ion battery first, obtains the leachate containing valuable metal ions；Then the valuable metal ions in the leachate are adsorbed using the graphene oxide colloid of dialysis membrane sealing, obtains the adsorption and oxidation graphene colloid of dialysis membrane sealing；The adsorption and oxidation graphene colloid that the dialysis membrane seals is put into the acid solution of default pH value, desorption processing is carried out under certain temperature, obtains the desorption liquid for being enriched with single valuable metal ions.The present invention realizes the classification recycling of the valuable metals such as nickel cobalt manganese in waste and old lithium ion battery, and not only the rate of recovery is high, but also recycles purity is high, does not generate secondary pollution in removal process.
Description
Technical field
The present invention relates to battery recycling technical field more particularly to a kind of recycling Metal Values From Spent Lithium-ion Batteries
Method.
Background technique
Lithium ion battery is born from nineteen ninety, in short more than the 20 years time, realizes to lead-acid battery, ni-Cd electricity
The gradually substitution of the secondary cells such as pond, nickel-metal hydride battery is widely used in mobile communication, number, portable charged power supply, electronic work
Tool and toy, electronic cigarette and the more automotive fields of point.China oneself become maximum lithium ion battery production in the world today, consumption and
Exported country, it is contemplated that the demand to the year two thousand twenty power lithium-ion battery is up to 125Gwh, and learies are up to 2.2Gwh, about 50
Ten thousand tons.By 2023, learies were up to 101Gwh, and about 1,160,000 tons.Currently, annual about 5,000,000,000 lithium batteries of output in the whole world, greatly
Most lithium ion batteries will be scrapped at charge and discharge cycles 1000 times or so.Due to containing harmful gold such as cobalt nickel manganese in lithium ion battery
Belong to, it will significant damage is caused to environment.Realize that valuable metal cobalt nickel manganese lithium recycles in waste lithium cell, it can not only
Economic interests are brought, and the problem of environmental pollution being on the rise can be alleviated.
However, being in the prior art also concentrated mainly on the recycling of lithium ion battery for the recycling of elemental lithium and sharp again
With, for other valuable metals such as nickel cobalt manganese etc. in lithium ion battery cannot achieve efficiently, the classification of high-purity recycles；And
And existing recovery method, there is also recycling energy consumption height, process is tedious, and serialization degree is low, and separation loss is greatly and seriously polluted
Defect.
Summary of the invention
In view of the above-mentioned problems, the object of the present invention is to provide a kind of recycling Metal Values From Spent Lithium-ion Batteries
Method, the method achieve the classification of the valuable metals such as nickel cobalt manganese in waste and old lithium ion battery recycling, and not only the rate of recovery is high, but also
Recovery product is with high purity, does not generate secondary pollution in removal process.
In order to solve the above-mentioned technical problems, the present invention provides a kind of sides for recycling Metal Values From Spent Lithium-ion Batteries
Method, this method comprises:
Alkali leaching processing, acidleach processing are successively carried out to the positive electrode of the waste and old lithium ion battery, obtained containing valuable gold
Belong to the leachate of ion；
Valuable metal ions in the leachate are adsorbed using the graphene oxide colloid that dialysis membrane seals, are dialysed
The adsorption and oxidation graphene colloid of film sealing；
The adsorption and oxidation graphene colloid that the dialysis membrane seals is put into the acid solution of default pH value, in certain temperature
Desorption processing is carried out under degree, obtains the desorption liquid for being enriched with single valuable metal ions.
Further, the valuable metal ions include Ni2+,Co2+And Mn2+；
The adsorption and oxidation graphene colloid that the dialysis membrane is sealed is put into the acid solution of default pH value, Yu Yi
Determine to carry out desorption processing at temperature, the desorption liquid for obtaining being enriched with single valuable metal ions includes:
(1) adjusting acid solution to default pH value is 1~3；The adsorption and oxidation graphene colloid that the dialysis membrane is sealed
It is put into the acid solution that the pH value is 1~3, desorption processing 1~5 hour at a temperature of 60~95 DEG C obtains enrichment Co2+
Desorption liquid；
(2) adjusting acid solution to default pH value is 3~5；It will the dialysis membrane sealing by step (1) treated
Adsorption and oxidation graphene colloid is put into the acid solution that the pH value is 3~5, the desorption processing 1 at a temperature of 60~95 DEG C
~5 hours, obtain enrichment of N i2+Desorption liquid；
(3) adjusting acid solution to default pH value is 5~6；It will the dialysis membrane sealing by step (2) treated
Adsorption and oxidation graphene colloid is put into the acid solution that the pH value is 5~6, the desorption processing 1 at a temperature of 60~95 DEG C
~5 hours, obtain enrichment Mn2+Desorption liquid.
Further, the positive electrode to the waste and old lithium ion battery successively carries out alkali leaching processing, acidleach handles it
Before, the method also includes pre-processing to the waste and old lithium ion battery, the pretreatment includes:
Waste and old lithium ion battery is carried out self discharge or immersed in electrolyte solution to be discharged to electroless state, is inactivated
Battery；
The positive electrode is sub-elected from the inactivation battery.
Further, the alkali leaching, which is handled, includes:
It is 40~60 DEG C that the positive electrode, which is put into temperature, and it is small to impregnate 10~15 in the strong base solution that pH value is 8~10
Positive electrode active material solid is obtained by filtration in Shi Hou.
Further, the mixed solution of excessive inorganic acid and hydrogen peroxide is added in Xiang Suoshu positive electrode active material solid, adds
Heat is to 50~70 DEG C, and after impregnating 1~3 hour, the leachate containing valuable metal ions is obtained by filtration.
Further, in the mixed solution hydrogen peroxide mass fraction be 15~25%, the inorganic acid with it is described
The mass ratio of hydrogen peroxide is (5~8): (1~3).
Further, the inorganic acid is the sulfuric acid of 2~5mol/L of concentration, and the positive electrode active material solid is mixed with described
The mass ratio of solution is 1:(3~5).
Further, the molecular cut off of the dialysis membrane is greater than 8000；The concentration of the graphene oxide colloid is 0.5
~5.0mg/ml, pH value are 5.5~6.5；The volume ratio of the graphene oxide colloid and the leachate is (2~3): 1.
Further, the acid solution is one of hydrochloric acid, sulfuric acid, nitric acid or a variety of mixing.
Further, the method also includes: be added and correspond into the desorption liquid of the single valuable metal ions of the enrichment
Precipitating reagent carry out precipitation process, obtain the sediment corresponding to the single valuable metal ions.
A kind of method of recycling Metal Values From Spent Lithium-ion Batteries of the invention, has the following beneficial effects:
Graphene oxide colloid that the present invention is sealed using dialysis membrane adsorbs the valuable metal ions in leachate, due to
The oxygen-containing groups such as widely distributed hydroxyl, carboxyl, epoxy group in the monolithic layer of graphene oxide, have large specific surface area, structure
Multiplicity, the advantages of pore size is adjustable and metal complexing groups have absorption well to the valuable metal ions in leachate
Effect；Adsorption and oxidation graphene colloid is put into the acid solution of default pH value and carries out desorption processing, is adjusted so as to pass through
The pH value of acid solution is saved to realize the successively classification abjection of the valuable metal ions of absorption, obtain being enriched with single valuable metal from
The desorption liquid of son not only increases the rate of recovery of the classification recycling of valuable metal in waste lithium ion cell anode material, and
The purity of the valuable metal of recycling is quite high.
Further, since valuable metal ions in leachate can pass through dialysis membrane, and graphene oxide colloid lamella
Dialysis membrane can not be passed through, so as to avoid secondary pollution and the absorption carrier of absorption carrier from being difficult to the problem of separating.This hair
In bright, after adsorption and oxidation graphene colloid carries out desorption processing, that is, graphene oxide colloid may make to regenerate, can be recycled,
Battery production cost is advantageously reduced, is economized on resources.
Detailed description of the invention
It, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical solution of the present invention
The attached drawing used is briefly described.It should be evident that drawings in the following description are only some embodiments of the invention, it is right
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings
Its attached drawing.
Fig. 1 is the flow chart of the method for nickel cobalt manganese in recycling waste and old lithium ion battery provided in an embodiment of the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art without making creative work it is obtained it is all its
His embodiment, shall fall within the protection scope of the present invention.
Embodiment 1
The preparation of graphene oxide colloid:
Assemble the reaction flask of 250ml in ice-water bath, the 90ml concentrated sulfuric acid be added, be added under stirring condition 2g graphite powder and
The solid mixture of 1g sodium nitrate, is slow added into 5g potassium permanganate, and control reaction temperature is no more than 20 DEG C, then heats to 35
It is stirred to react 30min under the conditions of DEG C, is slow added into 100ml deionized water, continues after stirring 20min, is slowly added dropwise 30% pair
Oxygen water restores remaining oxidant, and solution is made to become glassy yellow, stands 10 hours, outwells supernatant, repetition deionized water
Washing is not layered until standing, obtains graphene oxide colloid first product.
Above-mentioned graphene oxide colloid first product is fitted into bag filter and is put into deionized water and is dialysed, during which when one section
Between change a deionized water, until graphene oxide colloid pH close to 6.0, can be configured to the oxygen that concentration is 0.5-5.0mg/ml
Graphite alkene colloid.
Below by taking positive electrode active material in waste and old lithium ion battery is nickle cobalt lithium manganate as an example, to describe the waste and old lithium of recycling in detail
The method of valuable metal in ion battery, as shown in Figure 1, method includes the following steps:
(1) waste and old lithium ion battery is pre-processed, obtains nickel-cobalt lithium manganate cathode material.
Specifically, can first waste and old lithium ion battery be carried out self discharge or be immersed in electrolyte solution to be discharged to no electricity
State obtains inactivation battery so that battery inactivates.It is 2~8% that electrolyte solution, which can be mass fraction, in the present embodiment
NaCl solution.Then positive electrode is sub-elected from above-mentioned inactivation battery, specific method for separating can be straight to inactivation battery
Capable dismantling is tapped into, shell, diaphragm and positive/negative plate are separated, positive electrode is then picked out；Also it is direct that pulverizer can be used
Inactivation battery is crushed, positive electrode is then sub-elected by multiple tracks removal of impurities process.
(2) alkali leaching is handled: it is 50 DEG C that above-mentioned nickel-cobalt lithium manganate cathode material, which is put into temperature, in the KOH solution that pH value is 9
It impregnates 13 hours, copper, the aluminium in collector is dissolved, nickle cobalt lithium manganate solid is obtained by filtration later.
(3) acidleach is handled: being 1:5 according to the mass ratio of solid and liquid, was added in Xiang Shangshu nickle cobalt lithium manganate solid
The sulfuric acid of amount and the mixed liquor of hydrogen peroxide are obtained by filtration after being heated to 60 DEG C and impregnating 2 hours at such a temperature containing Ni+、Mn2 +、Co2+Leachate.
The mass fraction of hydrogen peroxide is 20% in the mixed liquor of above-mentioned sulfuric acid and hydrogen peroxide, and the concentration of sulfuric acid is
The mass ratio of 2mol/L, sulfuric acid and hydrogen peroxide is 7:2.
(4) absorption of valuable metal ions: it is 2:1 according to the volume ratio of graphene oxide colloid and leachate, takes aforementioned
The graphene oxide colloid of preparation, and it is in 10000 bag filter and close that the graphene oxide colloid, which is fitted into the molecular weight that shuts off,
It is honored as a queen, is put into the leachate of step (3), process is static, vibrates or is ultrasonically treated, the Ni in leachate+、Mn2+、Co2+It wears
It crosses dialysis membrane and enters in bag filter and be oxidized the absorption of graphene colloid, obtain the adsorption and oxidation graphene glue of dialysis membrane sealing
Leachate after body and adsorption treatment.
(5) desorption of valuable metal ions
S51 obtains enrichment Co2+Desorption liquid: prepare pH value be 1 sulfuric acid solution, absorption oxygen will be sealed in step (4)
In the sulfuric acid solution that the pH value that the bag filter of graphite alkene colloid is put under static, oscillation or ultrasonic treatment state is 1, in 60 DEG C
At a temperature of desorption processing 5 hours after, can be obtained enrichment Co2+Desorption liquid.
S52 obtains enrichment of N i2+Desorption liquid: prepare pH value be 3 sulfuric acid solution, will by above-mentioned steps S51 processing after
The bag filter for being sealed with adsorption and oxidation graphene colloid be put into it is static, oscillation or ultrasonic treatment state under pH value be 3 sulphur
In acid solution, at a temperature of 60 DEG C after desorption processing 5 hours, enrichment of N i can be obtained2+Desorption liquid.
S53 obtains enrichment Mn2+Desorption liquid: prepare pH value be 5 sulfuric acid solution, will by above-mentioned steps S52 processing after
The bag filter for being sealed with adsorption and oxidation graphene colloid be put into it is static, oscillation or ultrasonic treatment state under pH value be 5 sulphur
In acid solution, at a temperature of 60 DEG C after desorption processing 5 hours, enrichment Mn can be obtained2+Desorption liquid.It can be regenerated simultaneously
Graphene oxide colloid afterwards, can be recycled.
(6) precipitation process
S61, Co2+Precipitating: the enrichment Co that regulating step S51 is obtained2+Desorption liquid pH value to after 1.8, according to solvable
Property sulfide and desorption liquid in cobalt ions molar ratio be 1.1:1, to enrichment Co2+Desorption liquid in vulcanized sodium is added, in temperature
It reacts 5 hours under the conditions of being 45 DEG C, is filtered after reaction, collecting filter residue can be obtained cobalt sulfide precipitating.
S62, Ni2+Precipitating: the enrichment of N i obtained to step S522+Desorption liquid in oxalic acid solution is added, the oxalic acid with
The molar ratio of nickel ion is 1.05:1 in desorption liquid, and oxalic acid is added by enrichment of N i2+Desorption liquid pH value be adjusted to 1.8, then will be warm
Degree is adjusted to 35 DEG C, is filtered after reacting for 3 hours, and collecting filter residue can be obtained nickel oxalate precipitating.
S63, Mn2+Precipitating: the enrichment Mn obtained to step S532+Desorption liquid in soluble bicarbonate carbonic acid is added
PH value is adjusted to 6 by hydrogen potassium, is reacted 4 hours under the conditions of temperature is 35 DEG C, is filtered after reaction, and collecting filter residue can be obtained carbon
Sour manganese precipitating.
Embodiment 2
It is useless to describe recycling in detail so that positive electrode active material in waste and old lithium ion battery is nickle cobalt lithium manganate as an example for the present embodiment
The method of valuable metal in old lithium ion battery, as shown in Figure 1, method includes the following steps:
(1) waste and old lithium ion battery is pre-processed, obtains nickel-cobalt lithium manganate cathode material.
Specifically, can first waste and old lithium ion battery be carried out self discharge or be immersed in electrolyte solution to be discharged to no electricity
State obtains inactivation battery so that battery inactivates.It is 2~8% that electrolyte solution, which can be mass fraction, in the present embodiment
NaCl solution.Then positive electrode is sub-elected from above-mentioned inactivation battery, specific method for separating can be straight to inactivation battery
Capable dismantling is tapped into, shell, diaphragm and positive/negative plate are separated, positive electrode is then picked out；Also it is direct that pulverizer can be used
Inactivation battery is crushed, positive electrode is then sub-elected by multiple tracks removal of impurities process.
(2) alkali leaching is handled: it is 40 DEG C that above-mentioned nickel-cobalt lithium manganate cathode material, which is put into temperature, in the KOH solution that pH value is 8
It impregnates 15 hours, copper, the aluminium in collector is dissolved, nickle cobalt lithium manganate solid is obtained by filtration later.
(3) acidleach is handled: being 1:3 according to the mass ratio of solid and liquid, was added in Xiang Shangshu nickle cobalt lithium manganate solid
The sulfuric acid of amount and the mixed liquor of hydrogen peroxide are obtained by filtration after being heated to 50 DEG C and impregnating 3 hours at such a temperature containing Ni+、Mn2 +、Co2+Leachate.
The mass fraction of hydrogen peroxide is 15% in the mixed liquor of above-mentioned sulfuric acid and hydrogen peroxide, and the concentration of sulfuric acid is
The mass ratio of 5mol/L, sulfuric acid and hydrogen peroxide is 5:1.
(4) absorption of valuable metal ions: it is 3:1 according to the volume ratio of graphene oxide colloid and leachate, takes aforementioned
The graphene oxide colloid of preparation, and it is in 12000 bag filter and close that the graphene oxide colloid, which is fitted into the molecular weight that shuts off,
It is honored as a queen, is put into the leachate of step (3), process is static, vibrates or is ultrasonically treated, the Ni in leachate+、Mn2+、Co2+It wears
It crosses dialysis membrane and enters in bag filter and be oxidized the absorption of graphene colloid, obtain the adsorption and oxidation graphene glue of dialysis membrane sealing
Leachate after body and adsorption treatment.
(5) desorption of valuable metal ions
S51 obtains enrichment Co2+Desorption liquid: prepare pH value be 3 hydrochloric acid solution, absorption oxygen will be sealed in step (4)
In the hydrochloric acid solution that the pH value that the bag filter of graphite alkene colloid is put under static, oscillation or ultrasonic treatment state is 3, in 80 DEG C
At a temperature of desorption processing 3 hours after, can be obtained enrichment Co2+Desorption liquid.
S52 obtains enrichment of N i2+Desorption liquid: prepare pH value be 5 hydrochloric acid solution, will by above-mentioned steps S51 processing after
The bag filter for being sealed with adsorption and oxidation graphene colloid be put into it is static, oscillation or ultrasonic treatment state under pH value be 5 salt
In acid solution, at a temperature of 80 DEG C after desorption processing 3 hours, enrichment of N i can be obtained2+Desorption liquid.
S53 obtains enrichment Mn2+Desorption liquid: prepare pH value be 6 hydrochloric acid solution, will by above-mentioned steps S52 processing after
The bag filter for being sealed with adsorption and oxidation graphene colloid be put into it is static, oscillation or ultrasonic treatment state under pH value be 6 salt
In acid solution, at a temperature of 80 DEG C after desorption processing 3 hours, enrichment Mn can be obtained2+Desorption liquid.It can be regenerated simultaneously
Graphene oxide colloid afterwards, can be recycled.
(6) precipitation process
S61, Co2+Precipitating: the enrichment Co that regulating step S51 is obtained2+Desorption liquid pH value to after 2.8, according to solvable
Property sulfide and desorption liquid in cobalt ions molar ratio be 1.4:1, to enrichment Co2+Desorption liquid in potassium sulfide is added, in temperature
It reacts 2 hours under the conditions of being 65 DEG C, is filtered after reaction, collecting filter residue can be obtained cobalt sulfide precipitating.
S62, Ni2+Precipitating: the enrichment of N i obtained to step S522+Desorption liquid in oxalic acid solution is added, the oxalic acid with
The molar ratio of nickel ion is 1.2:1 in desorption liquid, and oxalic acid is added by enrichment of N i2+Desorption liquid pH value be adjusted to 2.5, then by temperature
60 DEG C are adjusted to, reaction is filtered after 1 hour, and collecting filter residue can be obtained nickel oxalate precipitating.
S63, Mn2+Precipitating: the enrichment Mn obtained to step S532+Desorption liquid in soluble bicarbonate carbonic acid is added
PH value is adjusted to 8 by hydrogen sodium, is reacted 2 hours under the conditions of temperature is 65 DEG C, is filtered after reaction, and collecting filter residue can be obtained carbon
Sour manganese precipitating.
Embodiment 3
It is useless to describe recycling in detail so that positive electrode active material in waste and old lithium ion battery is nickle cobalt lithium manganate as an example for the present embodiment
The method of valuable metal in old lithium ion battery, as shown in Figure 1, method includes the following steps:
(1) waste and old lithium ion battery is pre-processed, obtains nickel-cobalt lithium manganate cathode material.
Specifically, can first waste and old lithium ion battery be carried out self discharge or be immersed in electrolyte solution to be discharged to no electricity
State obtains inactivation battery so that battery inactivates.It is 2~8% that electrolyte solution, which can be mass fraction, in the present embodiment
NaCl solution.Then positive electrode is sub-elected from above-mentioned inactivation battery, specific method for separating can be straight to inactivation battery
Capable dismantling is tapped into, shell, diaphragm and positive/negative plate are separated, positive electrode is then picked out；Also it is direct that pulverizer can be used
Inactivation battery is crushed, positive electrode is then sub-elected by multiple tracks removal of impurities process.
(2) alkali leaching is handled: it is 60 DEG C that above-mentioned nickel-cobalt lithium manganate cathode material, which is put into temperature, the NaOH solution that pH value is 10
It is middle to impregnate 10 hours, copper, the aluminium in collector are dissolved, nickle cobalt lithium manganate solid is obtained by filtration later.
(3) acidleach is handled: being 1:4 according to the mass ratio of solid and liquid, was added in Xiang Shangshu nickle cobalt lithium manganate solid
The sulfuric acid of amount and the mixed liquor of hydrogen peroxide are obtained by filtration after being heated to 70 DEG C and impregnating 1 hour at such a temperature containing Ni+、Mn2 +、Co2+Leachate.
The mass fraction of hydrogen peroxide is 25% in the mixed liquor of above-mentioned sulfuric acid and hydrogen peroxide, and the concentration of sulfuric acid is
The mass ratio of 3mol/L, sulfuric acid and hydrogen peroxide is 8:3.
(4) absorption of valuable metal ions: it is 2:1 according to the volume ratio of graphene oxide colloid and leachate, takes aforementioned
The graphene oxide colloid of preparation, and it is in 15000 bag filter and close that the graphene oxide colloid, which is fitted into the molecular weight that shuts off,
It is honored as a queen, is put into the leachate of step (3), process is static, vibrates or is ultrasonically treated, the Ni in leachate+、Mn2+、Co2+It wears
It crosses dialysis membrane and enters in bag filter and be oxidized the absorption of graphene colloid, obtain the adsorption and oxidation graphene glue of dialysis membrane sealing
Leachate after body and adsorption treatment.
(5) desorption of valuable metal ions
S51 obtains enrichment Co2+Desorption liquid: prepare pH value be 2 nitric acid solution, absorption oxygen will be sealed in step (4)
In the nitric acid solution that the pH value that the bag filter of graphite alkene colloid is put under static, oscillation or ultrasonic treatment state is 2, in 95 DEG C
At a temperature of desorption processing 1 hour after, can be obtained enrichment Co2+Desorption liquid.
S52 obtains enrichment of N i2+Desorption liquid: prepare pH value be 4 nitric acid solution, will by above-mentioned steps S51 processing after
The bag filter for being sealed with adsorption and oxidation graphene colloid be put into it is static, oscillation or ultrasonic treatment state under pH value be 4 nitre
In acid solution, at a temperature of 95 DEG C after desorption processing 1 hour, enrichment of N i can be obtained2+Desorption liquid.
S53 obtains enrichment Mn2+Desorption liquid: prepare pH value be 6 nitric acid solution, will by above-mentioned steps S52 processing after
The bag filter for being sealed with adsorption and oxidation graphene colloid be put into it is static, oscillation or ultrasonic treatment state under pH value be 6 nitre
In acid solution, at a temperature of 95 DEG C after desorption processing 1 hour, enrichment Mn can be obtained2+Desorption liquid.It can be regenerated simultaneously
Graphene oxide colloid afterwards, can be recycled.
(6) precipitation process
S61, Co2+Precipitating: the enrichment Co that regulating step S51 is obtained2+Desorption liquid pH value to after 2.8, according to solvable
Property sulfide and desorption liquid in cobalt ions molar ratio be 1.4:1, to enrichment Co2+Desorption liquid in ammonium sulfide is added, in temperature
It reacts 3 hours under the conditions of being 55 DEG C, is filtered after reaction, collecting filter residue can be obtained cobalt sulfide precipitating.
S62, Ni2+Precipitating: the enrichment of N i obtained to step S522+Desorption liquid in oxalic acid solution is added, the oxalic acid with
The molar ratio of nickel ion is 1.1:1 in desorption liquid, and oxalic acid is added by enrichment of N i2+Desorption liquid pH value be adjusted to 2.0, then by temperature
50 DEG C are adjusted to, reaction is filtered after 2 hours, and collecting filter residue can be obtained nickel oxalate precipitating.
S63, Mn2+Precipitating: the enrichment Mn obtained to step S532+Desorption liquid in soluble bicarbonate carbonic acid is added
PH value is adjusted to 7 by hydrogen ammonium, is reacted 3 hours under the conditions of temperature is 50 DEG C, is filtered after reaction, and collecting filter residue can be obtained carbon
Sour manganese precipitating.
Comparative example 1
Referring to the method for recycling Metal Values From Spent Lithium-ion Batteries in embodiment 1, the difference is that, step
(3) after, graphene oxide colloid is not used to carry out the enrichment of valuable metal ions, but it is heavy directly to carry out substep to leachate
It forms sediment, i.e., the precipitating reagent in step (6) is successively added into leachate, so that Co2+、Ni2+And Mn2+Precipitation and separation goes out respectively, and
Solution after obtaining precipitation process.
Determination of recovery rates
With Ni2+For, the 10ml leachate in (1) Example 1, using inductively coupled plasma atomic emission spectrum
Instrument measures the Ni in (ICP-AES) leachate2+Concentration C0(Ni2+)；(2) leaching after the 10ml adsorption treatment in Example 1
Solution after 10ml precipitation process in liquid and comparative example 1 out, using inductively coupled plasma atomic emission spectrometer point
It Ce Ding not Ni in the leachate in embodiment 1 after adsorption treatment2+Concentration C1(Ni2+) and comparative example 1 in after precipitation process
Solution in Ni2+Concentration C2(Ni2+)；Then Ni in embodiment 12+The rate of recovery=(C0-C1)/C0, Ni in comparative example 12+'s
The rate of recovery=(C0-C2)/C0。
Similarly, the Co in embodiment 1 and comparative example 12+And Mn2+The rate of recovery can also measure through the above way, have
The rate of recovery of each valuable metal of body is as shown in table 1 below:
1 recovery rate of valuable metals of table
| Ni2+(%) | Co2+(%) | Mn2+(%) | |
| Embodiment 1 | 81.5 | 73.7 | 60.3 |
| Comparative example 1 | 60.2 | 49.2 | 35.4 |
Recycle purity testing
To the purity difference of the precipitating of cobalt sulfide obtained in embodiment 1 and comparative example 1, nickel oxalate precipitating and manganese carbonate precipitating
It is detected, the results are shown in Table 2.
The recycling purity of 2 valuable metal of table
| Nickel oxalate (%) | Cobalt sulfide (%) | Manganese carbonate (%) | |
| Embodiment 1 | 99.5 | 99.7 | 98.5 |
| Comparative example 1 | 60.6 | 71.3 | 65.5 |
To sum up, the graphene oxide colloid that the present invention is sealed using dialysis membrane come adsorb the valuable metal in leachate from
Son has specific surface area due to oxygen-containing groups such as hydroxyl, carboxyl, epoxy groups widely distributed in the monolithic layer of graphene oxide
Greatly, the advantages of various structures, pore size be adjustable and metal complexing groups has the valuable metal ions in leachate fine
Adsorption effect；Adsorption and oxidation graphene colloid is put into the acid solution of default pH value and carries out desorption processing, so as to
The successively classification abjection that the valuable metal ions of absorption are realized by adjusting the pH value of acid solution, obtains being enriched with single valuable
The desorption liquid of metal ion not only increases the rate of recovery of valuable metal classification recycling in waste lithium ion cell anode material,
And the purity of the valuable metal of recycling is quite high.
Further, since valuable metal ions in leachate can pass through dialysis membrane, and graphene oxide colloid lamella
Dialysis membrane can not be passed through, so as to avoid secondary pollution and the absorption carrier of absorption carrier from being difficult to the problem of separating.This hair
In bright, after adsorption and oxidation graphene colloid carries out desorption processing, that is, graphene oxide colloid may make to regenerate, can be recycled,
Battery production cost is advantageously reduced, is economized on resources.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (10)
1. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries, which is characterized in that the described method includes:
To the positive electrode of the waste and old lithium ion battery successively carry out alkali leaching processing, acidleach processing, obtain containing valuable metal from
The leachate of son；
Valuable metal ions in the leachate are adsorbed using the graphene oxide colloid that dialysis membrane seals, it is close to obtain dialysis membrane
The adsorption and oxidation graphene colloid of envelope；
The adsorption and oxidation graphene colloid that the dialysis membrane seals is put into the acid solution of default pH value, under certain temperature
Desorption processing is carried out, the desorption liquid for being enriched with single valuable metal ions is obtained.
2. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 1, which is characterized in that institute
Stating valuable metal ions includes Ni2+,Co2+And Mn2+；
The adsorption and oxidation graphene colloid that the dialysis membrane is sealed is put into the acid solution of default pH value, in certain temperature
Desorption processing is carried out under degree, the desorption liquid for obtaining being enriched with single valuable metal ions includes:
(1) adjusting acid solution to default pH value is 1~3；The adsorption and oxidation graphene colloid that the dialysis membrane seals is put into
In the acid solution that the pH value is 1~3, desorption processing 1~5 hour at a temperature of 60~95 DEG C obtains enrichment Co2+It is de-
Attached liquid；
(2) adjusting acid solution to default pH value is 3~5；Will by step (1) treated the dialysis membrane sealing absorption
Graphene oxide colloid is put into the acid solution that the pH value is 3~5, and desorption processing 1~5 is small at a temperature of 60~95 DEG C
When, obtain enrichment of N i2+Desorption liquid；
(3) adjusting acid solution to default pH value is 5~6；Will by step (2) treated the dialysis membrane sealing absorption
Graphene oxide colloid is put into the acid solution that the pH value is 5~6, and desorption processing 1~5 is small at a temperature of 60~95 DEG C
When, obtain enrichment Mn2+Desorption liquid.
3. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 1, which is characterized in that
Before successively carrying out alkali leaching processing, acidleach processing to the positive electrode of the waste and old lithium ion battery, the method also includes right
The waste and old lithium ion battery is pre-processed, and the pretreatment includes:
Waste and old lithium ion battery is carried out self discharge or immersed in electrolyte solution to be discharged to electroless state, obtains inactivation electricity
Pond；
The positive electrode is sub-elected from the inactivation battery.
4. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 1, which is characterized in that institute
Stating alkali leaching processing includes:
It is 40~60 DEG C that the positive electrode, which is put into temperature, after being impregnated 10~15 hours in the strong base solution that pH value is 8~10,
Positive electrode active material solid is obtained by filtration.
5. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 4, which is characterized in that institute
Stating acidleach processing includes:
The mixed solution of excessive inorganic acid and hydrogen peroxide is added to the positive electrode active material solid, is heated to 50~70 DEG C,
After impregnating 1~3 hour, the leachate containing valuable metal ions is obtained by filtration.
6. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 5, which is characterized in that institute
The mass fraction for stating hydrogen peroxide in mixed solution is 15~25%, and the mass ratio of the inorganic acid and the hydrogen peroxide is (5
~8): (1~3).
7. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 5 or 6, feature exist
In the inorganic acid is the sulfuric acid of 2~5mol/L of concentration, and the mass ratio of the positive electrode active material solid and the mixed solution is
1:(3~5).
8. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 1, which is characterized in that institute
The molecular cut off for stating dialysis membrane is greater than 8000；The concentration of the graphene oxide colloid is 0.5~5.0mg/ml, and pH value is
5.5~6.5；The volume ratio of the graphene oxide colloid and the leachate is (2~3): 1.
9. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 1 or 2, feature exist
In the acid solution is one of hydrochloric acid, sulfuric acid, nitric acid or a variety of mixing.
10. a kind of method for recycling Metal Values From Spent Lithium-ion Batteries according to claim 1 or 2, feature exist
In, the method also includes: corresponding precipitating reagent is added into the desorption liquid of the single valuable metal ions of enrichment and is sunk
Shallow lake processing, obtains the sediment corresponding to the single valuable metal ions.
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| CN114797344A (en) * | 2022-05-27 | 2022-07-29 | 武汉青江化工黄冈有限公司 | Lithium bis (fluorosulfonyl) imide purification device and application method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736157A (en) * | 2009-12-14 | 2010-06-16 | 北京有色金属研究总院 | Process for absorbing and extracting valuable metal ions in leachate of laterite nickel ore by applying immobilized room temperature ionic liquid |
| CN101982433A (en) * | 2010-11-09 | 2011-03-02 | 南京大学 | Method for harmless and recycling treatment of stainless steel acid washing waste water neutralization sludge |
| CN103339271A (en) * | 2011-01-27 | 2013-10-02 | 住友金属矿山株式会社 | Valuable metal leaching method, and valuable metal collection method employing the leaching method |
| KR20130128080A (en) * | 2012-05-16 | 2013-11-26 | 한국지질자원연구원 | Method for removing of copper-ion from solutions containing low concentration copper |
| CN103663601A (en) * | 2013-08-05 | 2014-03-26 | 南昌大学 | Method for absorptively separating low-concentration heavy-metal ions by utilizing graphene oxide colloid |
| CN104437677A (en) * | 2013-09-25 | 2015-03-25 | 工信华鑫科技有限公司 | Method for separating cobalt and manganese by virtue of heavy metal adsorption material |
| CN106785159A (en) * | 2016-11-18 | 2017-05-31 | 池州西恩新材料科技有限公司 | A kind of recovery method of nickel and cobalt containing anode material of lithium battery |
| CN107754771A (en) * | 2017-11-14 | 2018-03-06 | 成都新柯力化工科技有限公司 | A kind of bark ion colloidal sol and preparation method and application for lithium battery recovery |
| WO2018084723A2 (en) * | 2016-11-03 | 2018-05-11 | Mint Innovation Limited | Process for recovering metal |
| CN108550944A (en) * | 2018-06-11 | 2018-09-18 | 四会市恒星智能科技有限公司 | A method of recycling valuable metal from waste and old lithium ion battery |
| CN108636375A (en) * | 2018-06-11 | 2018-10-12 | 四会市恒星智能科技有限公司 | Absorption carrier and preparation method thereof for metal recovery in waste and old lithium ion battery |
-
2018
- 2018-10-19 CN CN201811222014.2A patent/CN109461984B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101736157A (en) * | 2009-12-14 | 2010-06-16 | 北京有色金属研究总院 | Process for absorbing and extracting valuable metal ions in leachate of laterite nickel ore by applying immobilized room temperature ionic liquid |
| CN101982433A (en) * | 2010-11-09 | 2011-03-02 | 南京大学 | Method for harmless and recycling treatment of stainless steel acid washing waste water neutralization sludge |
| CN103339271A (en) * | 2011-01-27 | 2013-10-02 | 住友金属矿山株式会社 | Valuable metal leaching method, and valuable metal collection method employing the leaching method |
| KR20130128080A (en) * | 2012-05-16 | 2013-11-26 | 한국지질자원연구원 | Method for removing of copper-ion from solutions containing low concentration copper |
| CN103663601A (en) * | 2013-08-05 | 2014-03-26 | 南昌大学 | Method for absorptively separating low-concentration heavy-metal ions by utilizing graphene oxide colloid |
| CN104437677A (en) * | 2013-09-25 | 2015-03-25 | 工信华鑫科技有限公司 | Method for separating cobalt and manganese by virtue of heavy metal adsorption material |
| WO2018084723A2 (en) * | 2016-11-03 | 2018-05-11 | Mint Innovation Limited | Process for recovering metal |
| CN106785159A (en) * | 2016-11-18 | 2017-05-31 | 池州西恩新材料科技有限公司 | A kind of recovery method of nickel and cobalt containing anode material of lithium battery |
| CN107754771A (en) * | 2017-11-14 | 2018-03-06 | 成都新柯力化工科技有限公司 | A kind of bark ion colloidal sol and preparation method and application for lithium battery recovery |
| CN108550944A (en) * | 2018-06-11 | 2018-09-18 | 四会市恒星智能科技有限公司 | A method of recycling valuable metal from waste and old lithium ion battery |
| CN108636375A (en) * | 2018-06-11 | 2018-10-12 | 四会市恒星智能科技有限公司 | Absorption carrier and preparation method thereof for metal recovery in waste and old lithium ion battery |
Non-Patent Citations (4)
| Title |
|---|
| JULIANA RIBEIRO DO CARMO等: "Recovery of copper (II) absorbed in biomass of Cladosporium cladosporioides", 《SCIENTIA AGRICOLA》 * |
| 吴越等: "废旧锂离子电池中有价金属的回收技术进展", 《稀有金属》 * |
| 李通: "锂、锰、稀土等有价金属分离、富集过程研究", 《中国优秀硕士学位论文全文数据库（电子期刊）》 * |
| 谢光炎等: "废旧锂离子电池回收处理技术研究进展", 《环境科学与技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797344A (en) * | 2022-05-27 | 2022-07-29 | 武汉青江化工黄冈有限公司 | Lithium bis (fluorosulfonyl) imide purification device and application method thereof |
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