CN115663180A - Method for recycling waste lithium iron phosphate batteries by using salt lake lithium extraction technology - Google Patents
Method for recycling waste lithium iron phosphate batteries by using salt lake lithium extraction technology Download PDFInfo
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- CN115663180A CN115663180A CN202211488079.8A CN202211488079A CN115663180A CN 115663180 A CN115663180 A CN 115663180A CN 202211488079 A CN202211488079 A CN 202211488079A CN 115663180 A CN115663180 A CN 115663180A
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- iron phosphate
- lithium iron
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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 invention mainly relates to two parts 1. An in-situ recovery technology of waste lithium iron phosphate. 2. And (3) selecting the material of the salt lake lithium extraction electrode by an electrochemical de-intercalation method. The rapid development of new energy industry is accompanied by the generation of a large amount of waste lithium ions. The method realizes the in-situ regeneration of the waste lithium iron phosphate battery by utilizing the electrochemical lithium extraction technology in the salt lake from the perspective of comprehensive utilization. The method is characterized in that waste lithium iron phosphate anode material is used as a cathode, normal lithium iron phosphate is used as an anode, and salt lake water is used as electrolyte. Due to the existence of the vacancy of lithium, the waste lithium iron phosphate can embed lithium in brine into the waste lithium iron phosphate at the cathode, so that the waste lithium iron phosphate is regenerated in situ, and the purposes of the in-situ regeneration of the waste lithium iron phosphate cathode material and the 'dual benefits' of brine lithium extraction are realized.
Description
Technical Field
The invention belongs to the field of lithium ion anode materials and the field of lithium extraction in salt lakes, and particularly relates to in-situ regeneration of waste lithium iron phosphate and lithium extraction in salt lakes.
Background
The lithium iron phosphate material is widely applied to secondary lithium ion batteries due to the advantages of good safety performance, long cycle life, wide raw material source, high energy density, environmental protection, no toxicity, no pollution and the like, but with the development of new energy industry, the lithium iron phosphate material is accompanied by the generation of a large amount of waste lithium iron phosphate lithium ion batteries
The traditional recycling of waste lithium iron phosphate materials mainly adopts a roasting or acid leaching method, for example, chinese patent CN108996484 a discloses a method for preparing lithium iron phosphate by using a lithium iron phosphate positive plate. The patent relates to the use of reagents such as ammonia water, acid and the like in the production process, the recovery process is complex, the flow is long, the cost is high, the yield of the lithium recovery resource is low, and the production of a large amount of waste acid and waste water is accompanied, so that the patent is not beneficial to environmental protection.
How to efficiently recycle lithium ion batteries is a difficult problem in the new energy industry at present. Based on the lithium ion battery de-intercalation principle, the invention adopts the treated waste lithium iron phosphate material as the cathode to carry out size mixing and coating process optimization, thereby realizing the in-situ regeneration of the waste lithium iron phosphate battery. The invention not only solves the problem of recycling the lithium extracted from the waste phosphoric acid, but also can promote the high-efficiency separation of magnesium and lithium in the salt lake, reduce the investment of capital and realize the purpose of 'win-win'.
Disclosure of Invention
The invention provides a method for extracting lithium from regenerated lithium iron phosphate and a salt lake, which not only solves the problem of recovering waste lithium phosphate, but also can promote the efficient separation of magnesium and lithium in the salt lake, reduce the investment and realize the 'win-win' purpose.
The present invention solves the above-mentioned problems in the following manner
Firstly, disassembling waste lithium iron phosphate, separating out an anode, a cathode and a diaphragm, taking the anode, cleaning the anode for multiple times by using one or more organic materials (dimethyl carbonate, diethyl carbonate and propylene carbonate), removing side reaction products on an interface, and drying in an oven for later use. Then the dried FePO is put into 4 Annealing the material at low temperature (600 deg.C for 30 min) under inert gas to remove partial organic matter on the surface, cooling to natural temperature, and performing FePO treatment 4 Conductive carbon black: the polyethylene glycol is prepared into slurry according to the proportion of 90. And (3) setting up a device, wherein the anode is normal lithium iron phosphate, the cathode is a treated waste lithium iron phosphate electrode, an anion membrane is arranged in the middle, the anolyte is a certain amount of NaCl solution, and the catholyte is salt lake brine, and finally, working is carried out, and the applied potential is-0.02 to 0.4v.
Detailed Description
1. Preparation of lithium iron phosphate electrode
a. Analysis of failure mechanism of waste lithium iron phosphate battery
Lithium deficiency of the positive electrode material is a pain point of all lithium ion battery positive electrode materials. The root of the method is that lithium ions in the anode material travel lithium dendrites or participate in forming a solid electrolyte interface on the surface of a cathode in the charging and discharging process, the lithium ions can finally become electrochemically inert lithium ions, and the interface reflection is more serious along with the increase of circulation, so that the capacity of the battery is reduced, and the battery is invalid.
However, the structure of the lithium iron phosphate material is not damaged in the failure process, and a lithium supplement method is generally adopted for repairing in the repairing process.
Therefore, the failure of lithium iron phosphate batteries is closely related to the "vacancy" of lithium ions inside the positive electrode material.
b. Preparation of waste lithium iron phosphate electrode
Firstly, disassembling waste lithium iron phosphate, separating out an anode, a cathode and a diaphragm, taking the anode, cleaning the anode for multiple times by using one or more organic materials (dimethyl carbonate, diethyl carbonate and propylene carbonate), removing side reaction products on an interface, and drying in an oven for later use. And then doping LiOH into the dried lithium iron phosphate material according to a certain proportion, sintering in an inert atmosphere (formula 1), naturally cooling, detecting the structural performance of the material through XRD, assembling into a button cell, detecting the electrochemical performance of the material, and further verifying the feasibility of a 'lithium supplement' process.
4 +- →xLiFePO 4 +(1-x)FePO 4
On the basis of the previous experiment, the dried FePO is added 4 Annealing the material at low temperature (600 deg.C for 30 min) under inert gas to remove partial organic matter on the surface, cooling to natural temperature, and performing FePO treatment 4 Conductive carbon black: the polyethylene glycol is prepared into slurry according to the proportion of 90.
2. In-situ regeneration of waste lithium iron phosphate
Placing normal lithium iron phosphate and the treated waste lithium iron phosphate pole piece in a specific electrolytic tank, isolating the pole piece by adopting an anion diaphragm, placing a sodium chloride aqueous solution with a certain concentration at the positive pole part, placing salt lake brine containing lithium ions with a certain concentration in the negative pole direction, and carrying out charging treatment within a certain voltage range of-0.02 to 0.4v. Because lithium vacancy exists in the lithium iron phosphate material in the cathode, lithium ions in the salt lake can be inserted into the cathode material, so that the in-situ regeneration of the waste lithium iron phosphate is realized, and the process of extracting lithium from the salt lake is completed.
3. Testing electrochemical performance of lithium iron phosphate and detecting lithium concentration of salt lake brine
a. Lithium iron phosphate battery performance test
Wiping one surface of the repaired lithium iron phosphate electrode obtained in the step 2 by using NMP, cutting a pole piece into a circular shape by using a cutting machine, annealing at 600 ℃ for 2 hours under inert gas, assembling a button battery by using a metal lithium cathode and electrolyte lithium hexafluorophosphate, testing a blue-electricity system of the battery, and further detecting the repaired lithium iron phosphate anode material.
b. Concentration detection of lithium salt lake brine
The flame atomic absorption and emission spectrometry is adopted, firstly, a standard lithium solution is prepared, a blank is sprayed into the flame to be used as a contrast, the working conditions of the instrument are that the wavelength of lithium element is 670.8nm, the width of a slit is 0.5nm, the lamp current is 5.0mA, the air flow is 10L/min, the acetylene flow is 2L/min, the absorbance and the emission intensity are measured, and a working curve is drawn. The linear regression equations for lithium absorption and emission are A =0.03756+0.13106 + C and E =0.16647+0.16787 + C \ correlation coefficients of 0.99968 and 0.99976, respectively, with sensitivities of 0.13ml/μ g and 0.17ml/μ g. And respectively testing the salt lake brine before and after the potential is applied, comparing the salt lake brine with a standard solution to obtain the concentration of the lithium in the solution, and subtracting the two values to obtain the content of the lithium iron phosphate intercalation lithium.
Claims (1)
1. A new method for realizing in-situ regeneration of waste lithium iron phosphate batteries by utilizing an electrochemical salt lake lithium extraction technology is characterized by comprising the following steps: 1, firstly, disassembling waste lithium iron phosphate, washing a positive electrode for multiple times by using one or more organic materials (dimethyl carbonate, diethyl carbonate and propylene carbonate), removing side reaction products on an interface, drying the positive electrode in an oven for standby, placing normal lithium iron phosphate and the waste lithium iron phosphate pole piece of the 1 in a specific electrolytic cell, isolating the positive electrode by using an anion diaphragm, placing a sodium chloride aqueous solution with a certain concentration in the positive electrode part, placing a salt lake brine containing lithium ions with a certain concentration in the negative electrode direction, and applying the salt lake brine in the voltage range of-0.02 v to 0.4v for a certain time to obtain the lithium iron phosphate positive electrode material regenerated in situ and separating lithium in the brine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211488079.8A CN115663180A (en) | 2022-11-25 | 2022-11-25 | Method for recycling waste lithium iron phosphate batteries by using salt lake lithium extraction technology |
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| CN202211488079.8A CN115663180A (en) | 2022-11-25 | 2022-11-25 | Method for recycling waste lithium iron phosphate batteries by using salt lake lithium extraction technology |
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| CN115663180A true CN115663180A (en) | 2023-01-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116565448A (en) * | 2023-07-04 | 2023-08-08 | 西北工业大学 | Preparation method of PP-based lithium supplementing diaphragm and cathode-free lithium ion battery |
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- 2022-11-25 CN CN202211488079.8A patent/CN115663180A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116565448A (en) * | 2023-07-04 | 2023-08-08 | 西北工业大学 | Preparation method of PP-based lithium supplementing diaphragm and cathode-free lithium ion battery |
| CN116565448B (en) * | 2023-07-04 | 2023-10-20 | 西北工业大学 | Preparation method of PP-based lithium supplementing diaphragm and cathode-free lithium ion battery |
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