CN108550944A - A method of recycling valuable metal from waste and old lithium ion battery - Google Patents
A method of recycling valuable metal from waste and old lithium ion battery Download PDFInfo
- Publication number
- CN108550944A CN108550944A CN201810594940.6A CN201810594940A CN108550944A CN 108550944 A CN108550944 A CN 108550944A CN 201810594940 A CN201810594940 A CN 201810594940A CN 108550944 A CN108550944 A CN 108550944A
- Authority
- CN
- China
- Prior art keywords
- absorption carrier
- waste
- ion battery
- lithium ion
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
The invention belongs to waste and old lithium ion battery recovery technology fields, and in particular to a method of recycling valuable metal from waste and old lithium ion battery, including：(1) preparation of absorption carrier；(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and be put into ball mill to crush and obtains grain size and be less than 0.5 μm of powder mixture；The powder mixture is immersed into the alkaline solution of 3~5 times of amounts, absorption carrier is constantly added during stirring, the absorption carrier of enriched in metals ion is obtained by filtration, which can be obtained using acid solution elution rich in the solution for having metal ion；The present invention detaches the metal ion in waste and old lithium ion battery using absorption carrier, is enriched with, and the organic efficiency of metal is improved；Meanwhile acid-base solution being only used only in the removal process；Used absorption carrier can be recycled, and reduce the cost of metal recovery.
Description
Technical field
The invention belongs to waste and old lithium ion battery recovery technology fields, and in particular to one kind is returned from waste and old lithium ion battery
The method for receiving valuable metal.
Background technology
Lithium battery can substantially be divided into lithium metal battery and lithium ion battery, although the safety of lithium metal battery, ratio
Capacity, self-discharge rate and the ratio of performance to price are superior to lithium ion battery, but since the high-tech of its own requires to limit, lithium gold
Belong to the application of battery much not as good as lithium ion battery.Lithium ion battery is a kind of secondary cell (rechargeable battery), it is relied primarily on
Movement comes work, during charge and discharge, Li to lithium ion between a positive electrode and a negative electrode+It is round-trip embedded between two electrodes and
Deintercalation：When charging, Li+From positive deintercalation, it is embedded in cathode by electrolyte, cathode is in rich lithium state；It is then opposite when electric discharge.With
Ni-Cd, Ni-MH battery are compared, and lithium ion battery has voltage height, bigger than energy, has extended cycle life, security performance is high, self discharge
It is small, memory-less effect, can fast charging and discharging, many advantages, such as operating temperature range is wide is widely used in electric vehicle, electronic
The multiple fields such as bicycle.
While the yield of lithium ion battery increasingly increases, product is largely launched, a technology that can not be ignored
Problem is put in face of us, that is, the recycling problem about waste and old lithium ion battery.Constitute lithium ion battery ingredient and
Structure is complex, including steel/aluminum hull, aluminium collector anode load cobalt acid lithium/LiFePO4/nickle cobalt lithium manganate etc., and copper/nickel/
Steel collector loads dimethyl carbonate/ethylene carbonate/carbonic acid of carbon, polyolefin porous separator, lithium hexafluoro phosphate/lithium perchlorate
First and second ester solutions etc., if do not recycled, it will environment is produced a very large impact, and after recycling, it is extracted by technology, Hen Duocai
Material can also be used again, as there is the precious metal of recovery value in waste and old lithium ion battery containing there are many, such as cobalt, copper, lithium
With aluminium etc., therefore, from the aspect of environmental protection and resource reutilization, the recycling of waste and old lithium ion battery be it is very necessary,
But also lacks be simple and efficient at present, the recovery and treatment method of low cost.
Invention content
For the problems of the prior art, the purpose of the present invention is to provide one kind to recycle from waste and old lithium ion battery has
The method of valence metal, this method have the advantages that it is at low cost, be simple and efficient.
To achieve the goals above, the present invention is achieved by the following scheme：
A method of it recycling valuable metal from waste and old lithium ion battery, includes the following steps：
(1) preparation of absorption carrier：
(1.1) will chitosan and pyroglutamic acid mix after be dissolved in water, be then added acid solution adjust pH value to 4.0~
5.0, it is heated to 40~45 DEG C and insulated and stirred reacts 30~40min, then add manganese dioxide and thiocarbohydrazide, continue
Filter residue is sent into freeze drier by 2~3h of insulation reaction through centrifugal filtration, dries obtained solid and through ultramicro grinding mechanism
At micro mist；
(1.2) above-mentioned micro mist and soluble metallic salt dissolving are distributed in aqueous acetic acid, are stirred at 50~60 DEG C
3~5h is reacted, absorption carrier presoma is prepared；
(1.3) the absorption carrier presoma is impregnated with acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is less than 0.5 μm；
The powder mixture is immersed into the alkaline solution of 3~5 times of amounts, is constantly added during stirring
The absorption carrier of enriched in metals ion is obtained by filtration in absorption carrier, which can be obtained using acid solution elution
Rich in the solution for having metal ion.
Preferably, in step (1.1), the micro mist includes that the material of following parts by weight is prepared：Chitosan 33~
50 parts, 3~15 parts of pyroglutamic acid, 20~30 parts of manganese dioxide, 0.1~0.5 part of thiocarbohydrazide.
Preferably, in step (1.2), the metal in the soluble metallic salt includes in copper, cobalt, nickel, cadmium, chromium, lithium
It is any or combinations thereof；
The mass ratio of the soluble metallic salt and micro mist is 1：(20~30).
Preferably, in step (1.2), the mass fraction of the aqueous acetic acid is 0.5~5%.
Preferably, in step (2), the additive amount of the absorption carrier is 1~2.5 times of powder mixture total weight.
Compared with prior art, the present invention has the following technical effects：
The method provided by the invention that valuable metal is recycled from waste and old lithium ion battery, using absorption carrier to waste and old lithium
Metal ion in ion battery is detached, is enriched with, and the organic efficiency of metal is improved；Meanwhile in the removal process only
Using only acid-base solution；Used absorption carrier can be recycled, and reduce the cost of metal recovery.
Other features and advantages of the present invention will be described in detail in subsequent specific implementation mode.
Specific implementation mode
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Specific embodiment is closed, the present invention is furture elucidated.
The method that the present invention provides a kind of to recycle valuable metal from waste and old lithium ion battery, includes the following steps：
(1) preparation of absorption carrier：
(1.1) will chitosan and pyroglutamic acid mix after be dissolved in water, be then added acid solution adjust pH value to 4.0~
5.0, it is heated to 40~45 DEG C and insulated and stirred reacts 30~40min, then add manganese dioxide and thiocarbohydrazide, continue
Filter residue is sent into freeze drier by 2~3h of insulation reaction through centrifugal filtration, dries obtained solid and through ultramicro grinding mechanism
At micro mist；
(1.2) above-mentioned micro mist and soluble metallic salt dissolving are distributed in aqueous acetic acid, are stirred at 50~60 DEG C
3~5h is reacted, absorption carrier presoma is prepared；
(1.3) the absorption carrier presoma is impregnated with acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is less than 0.5 μm；
The powder mixture is immersed into the alkaline solution of 3~5 times of amounts, is constantly added during stirring
The absorption carrier of enriched in metals ion is obtained by filtration in absorption carrier, which can be obtained using acid solution elution
Rich in the solution for having metal ion.
In the present invention, the chitosan is also known as chitosan, is passed through by the chitin that nature is widely present
Deacetylation obtains；There are active hydroxyl and amino in chitosan macromolecular, they have stronger chemical reaction ability；This
Invention carries out chemical modification using pyroglutamic acid to chitosan, the carboxylic in hydroxyl, amino and pyroglutamic acid structure in chitosan
Esterification and amide condensed reaction occur respectively for base, to improve the water solubility of chitosan；Further, by the way that dioxy is added
Change manganese, and using thiocarbohydrazide as crosslinking agent, cross-linked chitosan-manganese dioxide composite material of formation has excellent absorption
Ability, while the adsorption capacity of the composite material is big, adsorption effect is high, and acid resistance ability is strong and convenient for being separated by solid-liquid separation.
Micro mist is obtained by being crushed after above-mentioned cross-linked chitosan-manganese dioxide composite material freeze-drying, it is further to increase
The surface area of the cross-linked chitosan-manganese dioxide composite material.
Micro mist and soluble metallic salt dissolving are distributed in aqueous acetic acid, the micro mist of metal ion has been adsorbed,
Then micro mist is impregnated using acid solution, during dipping, H+It is immersed in micro mist, and replaces and be embedded in micro mist
Metal ion obtains being enriched H+Absorption carrier；
Above-mentioned absorption carrier is added in the powder mixture in alkaline environment, since alkaline condition forces absorption
H in carrier+Continuous be precipitated participates in neutralization reaction, and be dissolved out in powder mixture metal ion by continuous absorption,
Be enriched on absorption carrier, can be obtained by filtering and be enriched the absorption carrier of metal ion, then by acid solution into
Row elution, you can obtain the eluent for being enriched metal ion.
According to the present invention, the usage amount of the chitosan, pyroglutamic acid and manganese dioxide and thiocarbohydrazide can be
Selection in wider range, it is described micro- in step (1.1) in order to ensure the micro mist being prepared has a preferable adsorption effect
Powder includes that the material of following parts by weight is prepared：33~50 parts of chitosan, 3~15 parts of pyroglutamic acid, manganese dioxide 20~
30 parts, 0.1~0.5 part of thiocarbohydrazide.
Further, according to the present invention, in the step (1.2), the metal in the soluble metallic salt includes
Any of or a combination of copper, cobalt, nickel, cadmium, chromium, lithium；
The mass ratio of the soluble metallic salt and micro mist is 1：(20~30).
In the present invention, the selection of the soluble metallic salt is selected according to the type of metal in specific raw material to be recycled
It selects, or disposably needs the type of the metal of separation, enrichment to be selected as needed.
In step (1.3), during the absorption carrier presoma being prepared is impregnated with acid solution, absorption carries
Metal ion in body presoma can be precipitated, meanwhile, the H in acid solution+It is embedded into absorption carrier presoma, to be formed
Compound with certain regular texture, it is this to carry H+Compound target is imported for original, i.e. virgin metal ion has
Remember the function of identification, therefore in the alkaline solution of powder mixture dispersion, the metal ion meeting contained in powder mixture
In embedded absorption carrier, the enrichment of metal ion is realized；
When eluting the absorption carrier using acid solution, the metal ion adsorbed in absorption carrier is displaced again
Come, and H+Again it is embedded into absorption carrier, completes living again for absorption carrier.
Specifically, the only Call Provision metal for example from waste and old lithium ion battery, can select soluble cobalt and micro mist
It carries out reaction and is used to prepare absorption carrier presoma；The soluble cobalt can be enumerated specifically as in cobalt nitrate, cobaltous sulfate
One kind；
Copper metal is for another example only recycled from waste and old lithium ion battery, soluble copper salt can be selected to be reacted with micro mist
It is used to prepare absorption carrier presoma；The soluble copper salt can specifically enumerate one kind in such as copper sulphate, copper nitrate；
According to above-mentioned principle, the soluble metallic salt can also include soluble nickel salt, soluble cadmium salt, solubility
One kind or combinations thereof in chromic salts, soluble lithium salt.
The soluble nickel salt can specifically enumerate one kind in nickelous carbonate, nickel acetate, nickel chloride, nickel nitrate；
The soluble cadmium salt can specifically enumerate one kind in cadmium carbonate, cadmium sulfate, cadmium nitrate；
The soluble chromic salts can specifically enumerate one kind in chromic nitrate, chromium sulfate, chromium chloride；
The soluble lithium salt can specifically enumerate one kind in lithium carbonate, hexafluoro lithium carbonate.
In the present invention, the soluble metallic salt can disposably be added one kind in above-mentioned soluble metallic salt or
It is a variety of, to realize to disposable separation, the enrichment of various metals ion in powder mixture, improve waste and old lithium ion battery
The organic efficiency of middle valuable metal.
Further, the absorption carrier carries out liberation of hydrogen engaged column ion in powder mixture, in elution process
The process for carrying out the analysis embedding hydrogen of metal ion relates merely to the use of acid-base solution in whole process, waste and old compared to traditional
The method of lithium ion battery material recycling, has Environmental Safety, simple and convenient, the high advantage of resource utilization.
According to the present invention, in of the invention, in step (1.2), the mass fraction of the aqueous acetic acid is 0.5~5%.
According to the present invention, in of the invention, in step (2), the additive amount of the absorption carrier is powder mixture total weight
1~2.5 times.
Heretofore described acid solution, effect have the pH for adjusting solution or provide H+, the present invention do not have its type
There is special requirement, can often know for one of ordinary skill in the art, such as the acid solution can be inorganic acid and/or have
Machine acid, the inorganic acid can be hydrochloric acid, nitric acid, sulfuric acid, boric acid, perchloric acid, thiocyanic acid, sulfurous acid, phosphoric acid, phosphorous acid, secondary
At least one of chloric acid etc.；The organic acid can be at least one of formic acid, acetic acid, benzoic acid, benzene sulfonic acid etc..Into one
Step is preferred, and the acid solution selects the hydrochloric acid solution of a concentration of 1mol/L.
Heretofore described alkaline solution plays the role of adjusting pH value of solution, and the present invention does not have it special requirement,
Can be well known to one of ordinary skill in the art, for example, the alkaline solution can be alkali hydroxide soln, alkaline earth
Metal hydroxide solutions, urea and its at least one of derivative and organic amine, it is further preferred that the alkaline solution
For at least one of sodium hydroxide solution, potassium hydroxide solution.In the present invention, the sodium hydroxide that preferable ph is 10~12 is molten
Liquid.
Below by way of specific embodiment to the side provided by the invention for recycling valuable metal from waste and old lithium ion battery
Method is described further.
The waste and old lithium ion battery recycled in following embodiment is waste and old nickle cobalt lithium manganate NCM523 batteries (power god's power electric
Cell system Co., Ltd produces).
Embodiment 1
A method of recycling valuable metal from waste and old lithium ion battery：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition hydrochloric acid solution adjusting pH value to 4.5,
42 DEG C and insulated and stirred reaction 30min are heated to, manganese dioxide and thiocarbohydrazide is then added, continues insulation reaction 3h,
Through centrifugal filtration, filter residue is sent into freeze drier, simultaneously micro mist is made through micronizer in dry obtained solid；
The micro mist includes that the material of following parts by weight is prepared：40 parts of chitosan, 8 parts of pyroglutamic acid, titanium dioxide
25 parts of manganese, 0.3 part of thiocarbohydrazide；
(1.2) above-mentioned micro mist and cobaltous sulfate dissolving are distributed in the aqueous acetic acid that mass fraction is 2%, at 55 DEG C
It is stirred to react 4h, absorption carrier presoma is prepared；
The mass ratio of the cobaltous sulfate and micro mist is 1：25；
(1.3) the absorption carrier presoma is impregnated with hydrochloric acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is 0.4 μm；
The powder mixture is immersed into the sodium hydroxide solution that 4 times of amount pH value are 11, during stirring
Continuous that absorption carrier is added, the additive amount of the absorption carrier is 1.5 times of powder mixture total weight；Enrichment is obtained by filtration
The absorption carrier of metal ion can be obtained the absorption carrier rich in the solution for having metal ion using hydrochloric acid solution elution.
Absorption carrier is measured using ICP-OES (inductively coupled plasma atomic emission spectrometry instrument), and powder mixture is added
Before and the eluent of absorption carrier in corresponding metal ion content, the rate of recovery that cobalt ions is calculated is 98.5%.
Embodiment 2
A method of recycling valuable metal from waste and old lithium ion battery：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition hydrochloric acid solution adjusting pH value to 4.0,
40 DEG C and insulated and stirred reaction 30min are heated to, manganese dioxide and thiocarbohydrazide is then added, continues insulation reaction 2h,
Through centrifugal filtration, filter residue is sent into freeze drier, simultaneously micro mist is made through micronizer in dry obtained solid；
The micro mist includes that the material of following parts by weight is prepared：33 parts of chitosan, 3 parts of pyroglutamic acid, titanium dioxide
20 parts of manganese, 0.1 part of thiocarbohydrazide；
(1.2) above-mentioned micro mist and cobaltous sulfate dissolving are distributed in the aqueous acetic acid that mass fraction is 0.5%, at 50 DEG C
Under be stirred to react 3h, absorption carrier presoma is prepared；
The mass ratio of the cobaltous sulfate and micro mist is 1：20；
(1.3) the absorption carrier presoma is impregnated with hydrochloric acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is 0.4 μm；
The powder mixture is immersed into the sodium hydroxide solution that 3 times of amount pH value are 11, during stirring
Continuous that absorption carrier is added, the additive amount of the absorption carrier is 1 times of powder mixture total weight；Concentration of Gold is obtained by filtration
The absorption carrier for belonging to ion can be obtained the absorption carrier rich in the solution for having metal ion using hydrochloric acid solution elution.
Absorption carrier is measured using ICP-OES (inductively coupled plasma atomic emission spectrometry instrument), and powder mixture is added
Before and the eluent of absorption carrier in corresponding metal ion content, the rate of recovery that cobalt ions is calculated is 98.3%.
Embodiment 3
A method of recycling valuable metal from waste and old lithium ion battery：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition hydrochloric acid solution adjusting pH value to 5.0,
45 DEG C and insulated and stirred reaction 40min are heated to, manganese dioxide and thiocarbohydrazide is then added, continues insulation reaction 3h,
Through centrifugal filtration, filter residue is sent into freeze drier, simultaneously micro mist is made through micronizer in dry obtained solid；
The micro mist includes that the material of following parts by weight is prepared：50 parts of chitosan, 15 parts of pyroglutamic acid, titanium dioxide
30 parts of manganese, 0.5 part of thiocarbohydrazide；
(1.2) above-mentioned micro mist and cobaltous sulfate dissolving are distributed in the aqueous acetic acid that mass fraction is 5%, at 60 DEG C
It is stirred to react 5h, absorption carrier presoma is prepared；
The mass ratio of the cobaltous sulfate and micro mist is 1：30；
(1.3) the absorption carrier presoma is impregnated with hydrochloric acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is 0.4 μm；
The powder mixture is immersed into the sodium hydroxide solution that 5 times of amount pH value are 11, during stirring
Continuous that absorption carrier is added, the additive amount of the absorption carrier is 2.5 times of powder mixture total weight；Enrichment is obtained by filtration
The absorption carrier of metal ion can be obtained the absorption carrier rich in the solution for having metal ion using hydrochloric acid solution elution.
Absorption carrier is measured using ICP-OES (inductively coupled plasma atomic emission spectrometry instrument), and powder mixture is added
Before and the eluent of absorption carrier in corresponding metal ion content, the rate of recovery that cobalt ions is calculated is 98.4%.
Embodiment 4
A method of recycling valuable metal from waste and old lithium ion battery：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition hydrochloric acid solution adjusting pH value to 4.5,
42 DEG C and insulated and stirred reaction 30min are heated to, manganese dioxide and thiocarbohydrazide is then added, continues insulation reaction 3h,
Through centrifugal filtration, filter residue is sent into freeze drier, simultaneously micro mist is made through micronizer in dry obtained solid；
The micro mist includes that the material of following parts by weight is prepared：40 parts of chitosan, 8 parts of pyroglutamic acid, titanium dioxide
25 parts of manganese, 0.3 part of thiocarbohydrazide；
(1.2) above-mentioned micro mist, cobaltous sulfate, nickelous carbonate dissolving are distributed in the aqueous acetic acid that mass fraction is 2%,
It is stirred to react 4h at 55 DEG C, absorption carrier presoma is prepared；
The mass ratio of the cobaltous sulfate, nickelous carbonate and micro mist is 0.5：0.5：25；
(1.3) the absorption carrier presoma is impregnated with hydrochloric acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is 0.4 μm；
The powder mixture is immersed into the sodium hydroxide solution that 4 times of amount pH value are 11, during stirring
Continuous that absorption carrier is added, the additive amount of the absorption carrier is 1.5 times of powder mixture total weight；Enrichment is obtained by filtration
The absorption carrier of metal ion can be obtained the absorption carrier rich in the solution for having metal ion using hydrochloric acid solution elution.
Absorption carrier is measured using ICP-OES (inductively coupled plasma atomic emission spectrometry instrument), and powder mixture is added
Before and the eluent of absorption carrier in corresponding metal ion content, the rate of recovery that cobalt ions is calculated is 98.8%,
The rate of recovery of nickel ion is 97.8%.
Embodiment 5
A method of recycling valuable metal from waste and old lithium ion battery：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition hydrochloric acid solution adjusting pH value to 4.0,
40 DEG C and insulated and stirred reaction 30min are heated to, manganese dioxide and thiocarbohydrazide is then added, continues insulation reaction 2h,
Through centrifugal filtration, filter residue is sent into freeze drier, simultaneously micro mist is made through micronizer in dry obtained solid；
The micro mist includes that the material of following parts by weight is prepared：33 parts of chitosan, 3 parts of pyroglutamic acid, titanium dioxide
20 parts of manganese, 0.1 part of thiocarbohydrazide；
(1.2) above-mentioned micro mist and chromic nitrate, lithium carbonate dissolving are distributed to the aqueous acetic acid that mass fraction is 0.5%
In, it is stirred to react 3h at 50 DEG C, absorption carrier presoma is prepared；
The mass ratio of the chromic nitrate, lithium carbonate and micro mist is 0.5：0.5：20；
(1.3) the absorption carrier presoma is impregnated with hydrochloric acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is 0.4 μm；
The powder mixture is immersed into the sodium hydroxide solution that 3 times of amount pH value are 11, during stirring
Continuous that absorption carrier is added, the additive amount of the absorption carrier is 1 times of powder mixture total weight；Concentration of Gold is obtained by filtration
The absorption carrier for belonging to ion can be obtained the absorption carrier rich in the solution for having metal ion using hydrochloric acid solution elution.
Absorption carrier is measured using ICP-OES (inductively coupled plasma atomic emission spectrometry instrument), and powder mixture is added
Before and the eluent of absorption carrier in corresponding metal ion content, the rate of recovery that chromium ion is calculated is 99.1%,
The rate of recovery of lithium ion is 98.7%.
Embodiment 6
A method of recycling valuable metal from waste and old lithium ion battery：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition hydrochloric acid solution adjusting pH value to 5.0,
45 DEG C and insulated and stirred reaction 40min are heated to, manganese dioxide and thiocarbohydrazide is then added, continues insulation reaction 3h,
Through centrifugal filtration, filter residue is sent into freeze drier, simultaneously micro mist is made through micronizer in dry obtained solid；
The micro mist includes that the material of following parts by weight is prepared：50 parts of chitosan, 15 parts of pyroglutamic acid, titanium dioxide
30 parts of manganese, 0.5 part of thiocarbohydrazide；
(1.2) above-mentioned micro mist and nickel chloride, lithium carbonate dissolving are distributed in the aqueous acetic acid that mass fraction is 5%,
It is stirred to react 5h at 60 DEG C, absorption carrier presoma is prepared；
The mass ratio of the nickel chloride, lithium carbonate and micro mist is 0.5：0.5：30；
(1.3) the absorption carrier presoma is impregnated with hydrochloric acid solution, the metal in absorption carrier presoma is precipitated
The absorption carrier is prepared in ion；
(2) waste and old lithium ion battery is substantially discharged, takes out anode material for lithium-ion batteries and being put into ball mill and crushes
Obtain the powder mixture that grain size is 0.4 μm；
The powder mixture is immersed into the sodium hydroxide solution that 5 times of amount pH value are 11, during stirring
Continuous that absorption carrier is added, the additive amount of the absorption carrier is 2.5 times of powder mixture total weight；Enrichment is obtained by filtration
The absorption carrier of metal ion can be obtained the absorption carrier rich in the solution for having metal ion using hydrochloric acid solution elution.
Absorption carrier is measured using ICP-OES (inductively coupled plasma atomic emission spectrometry instrument), and powder mixture is added
Before and the eluent of absorption carrier in corresponding metal ion content, the rate of recovery that nickel ion is calculated is 98.2%,
The rate of recovery of lithium ion is 98.8%.
To sum up, method provided by the invention, it can be ensured that metal is targetedly recycled from waste and old lithium ion battery；Together
When, the utilization that the absorption carrier for recycling metal ion can be repeated, to effectively reduce the cost of metal recovery,
Also, the recovery method is simple and convenient, efficient.
The basic principles and main features and the features of the present invention of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement is both fallen in the range of claimed invention.The scope of protection of present invention is by appended claims
And its equivalent thereof.
Claims (5)
1. a kind of method recycling valuable metal from waste and old lithium ion battery, it is characterised in that：Include the following steps：
(1) preparation of absorption carrier：
(1.1) it is dissolved in water after mixing chitosan and pyroglutamic acid, then addition acid solution adjusting pH value to 4.0~5.0,
It is heated to 40~45 DEG C and insulated and stirred reacts 30~40min, then add manganese dioxide and thiocarbohydrazide, continue to keep the temperature
2~3h is reacted, through centrifugal filtration, filter residue is sent into freeze drier, dry obtained solid is simultaneously made micro- through micronizer
Powder；
(1.2) above-mentioned micro mist and soluble metallic salt dissolving are distributed in aqueous acetic acid, 3 is stirred to react at 50~60 DEG C
Absorption carrier presoma is prepared in~5h；
(1.3) the absorption carrier presoma is impregnated with acid solution, the metal ion in absorption carrier presoma is precipitated,
The absorption carrier is prepared；
(2) waste and old lithium ion battery is substantially discharged, take out anode material for lithium-ion batteries and be put into ball mill crush obtain
Grain size is less than 0.5 μm of powder mixture；
The powder mixture is immersed into the alkaline solution of 3~5 times of amounts, absorption is constantly added during stirring
The absorption carrier of enriched in metals ion is obtained by filtration in carrier, which can be obtained using acid solution elution and be rich in
There is the solution of metal ion.
2. the method according to claim 1 for recycling valuable metal from waste and old lithium ion battery, it is characterised in that：Step
(1.1) in, the micro mist includes that the material of following parts by weight is prepared：33~50 parts of chitosan, pyroglutamic acid 3~15
Part, 20~30 parts of manganese dioxide, 0.1~0.5 part of thiocarbohydrazide.
3. the method according to claim 1 for recycling valuable metal from waste and old lithium ion battery, it is characterised in that：Step
(1.2) in, the metal in the soluble metallic salt includes any of or a combination of copper, cobalt, nickel, cadmium, chromium, lithium；
The mass ratio of the soluble metallic salt and micro mist is 1：(20~30).
4. the method according to claim 1 for recycling valuable metal from waste and old lithium ion battery, it is characterised in that：Step
(1.2) in, the mass fraction of the aqueous acetic acid is 0.5~5%.
5. the method according to claim 1 for recycling valuable metal from waste and old lithium ion battery, it is characterised in that：Step
(2) in, the additive amount of the absorption carrier is 1~2.5 times of powder mixture total weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810594940.6A CN108550944B (en) | 2018-06-11 | 2018-06-11 | Method for recovering valuable metals from waste lithium ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810594940.6A CN108550944B (en) | 2018-06-11 | 2018-06-11 | Method for recovering valuable metals from waste lithium ion batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108550944A true CN108550944A (en) | 2018-09-18 |
| CN108550944B CN108550944B (en) | 2020-01-10 |
Family
ID=63492536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810594940.6A Active CN108550944B (en) | 2018-06-11 | 2018-06-11 | Method for recovering valuable metals from waste lithium ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108550944B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461984A (en) * | 2018-10-19 | 2019-03-12 | 浙江衡远新能源科技有限公司 | A method of recycling Metal Values From Spent Lithium-ion Batteries |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451771A (en) * | 2003-05-09 | 2003-10-29 | 武汉理工大学 | Method for recovery of lithium from used lithium ion cell with ion sieve |
| CN101327424A (en) * | 2008-04-29 | 2008-12-24 | 上海博物馆 | Formaldehyde adsorbing agent containing chitosan |
| CN103041787A (en) * | 2013-01-08 | 2013-04-17 | 山东大学 | Preparation method of crosslinked chitosan-manganese dioxide composite adsorbing material |
| CN103316623A (en) * | 2013-07-10 | 2013-09-25 | 华东理工大学 | Method for preparing spherical lithium ion sieve adsorbent |
| KR20150049561A (en) * | 2013-10-30 | 2015-05-08 | 한국지질자원연구원 | Granulated lithium adsorbent using freezing-dry technique and chitosan, and method for preparing the same |
| CN107413114A (en) * | 2017-08-03 | 2017-12-01 | 福州大学 | The manganese dioxide di-iron trioxide of a kind of Chitosan-coated/PPS composite denitration filtrates and preparation method thereof |
-
2018
- 2018-06-11 CN CN201810594940.6A patent/CN108550944B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451771A (en) * | 2003-05-09 | 2003-10-29 | 武汉理工大学 | Method for recovery of lithium from used lithium ion cell with ion sieve |
| CN101327424A (en) * | 2008-04-29 | 2008-12-24 | 上海博物馆 | Formaldehyde adsorbing agent containing chitosan |
| CN103041787A (en) * | 2013-01-08 | 2013-04-17 | 山东大学 | Preparation method of crosslinked chitosan-manganese dioxide composite adsorbing material |
| CN103316623A (en) * | 2013-07-10 | 2013-09-25 | 华东理工大学 | Method for preparing spherical lithium ion sieve adsorbent |
| KR20150049561A (en) * | 2013-10-30 | 2015-05-08 | 한국지질자원연구원 | Granulated lithium adsorbent using freezing-dry technique and chitosan, and method for preparing the same |
| CN107413114A (en) * | 2017-08-03 | 2017-12-01 | 福州大学 | The manganese dioxide di-iron trioxide of a kind of Chitosan-coated/PPS composite denitration filtrates and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109461984A (en) * | 2018-10-19 | 2019-03-12 | 浙江衡远新能源科技有限公司 | A method of recycling Metal Values From Spent Lithium-ion Batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108550944B (en) | 2020-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105428745B (en) | A kind of innoxious comprehensive reutilization method of applying waste lithium ionic power battery | |
| CN101916889B (en) | Method for preparing iron lithium phosphate by recovering water-system waste lithium-ion power battery | |
| CN109439904A (en) | A method of the leaching valuable metal from waste lithium cell positive electrode | |
| CN108636375A (en) | Absorption carrier and preparation method thereof for metal recovery in waste and old lithium ion battery | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN104953200A (en) | Method for recycling battery-grade iron phosphate in lithium iron phosphate battery and preparing lithium iron phosphate positive material by utilizing waste lithium ion phosphate battery | |
| KR102214423B1 (en) | Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells | |
| CN102208707A (en) | Method for repair and regeneration of waste lithium iron phosphate battery cathode material | |
| CN112164834B (en) | Regeneration method of waste lithium iron phosphate battery positive electrode material | |
| CN108933308B (en) | Comprehensive recycling method for anode and cathode of scrapped lithium battery | |
| CN104112882A (en) | Method for electrochemically extracting lithium from positive electrode material of lithium ion battery | |
| WO2023071396A1 (en) | Positive electrode material for sodium-ion battery, and preparation method therefor and application thereof | |
| CN111517340B (en) | Method for recycling lithium carbonate from NCM111 positive electrode material of waste ternary lithium ion battery | |
| CN112310502A (en) | Method for recycling and reusing anode material of waste lithium manganate lithium ion battery | |
| Fatima et al. | A short overview of recycling and treatment of spent LiFePO4 battery | |
| CN109524735B (en) | Recovery method of waste lithium iron phosphate-lithium titanate battery | |
| Wang et al. | Recycling methods for different cathode chemistries–A critical review | |
| Wang et al. | A review of processes and technologies for the recycling of spent lithium-ion batteries | |
| CN102569791B (en) | A kind of LiFePO4 with flower-like structure and preparation method thereof | |
| CN108461859A (en) | A method of from extraction lithium in waste liquid containing lithium | |
| CN108550944A (en) | A method of recycling valuable metal from waste and old lithium ion battery | |
| CN104981552A (en) | Method for the hydrometallurgical recovery of lithium from the lithium manganese oxide-containing fraction of used galvanic cells | |
| WO2023040010A1 (en) | Method for repairing cathode material of spent lithium ion battery | |
| CN115092902A (en) | Method for preparing lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag | |
| CN106495122A (en) | A kind of method that waste lithium iron phosphate positive plate reclaims iron phosphate presoma |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191218 Address after: 554300 intersection of trunk road No. 2 and No. 1 road, DLONG Economic Development Zone, Tongren, Guizhou Applicant after: Guizhou Zhongwei resource recycling industry development Co., Ltd. Address before: 526299 No. 537, South times Commercial Plaza, Sihui Road, Dongcheng District, Sihui City, Zhaoqing, Guangdong (two floor) Applicant before: SIHUI HENGXING INTELLIGENT TECHNOLOGY CO., LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |