CN116926572A - Method for recovering lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair - Google Patents
Method for recovering lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000008439 repair process Effects 0.000 title claims abstract description 23
- 230000002687 intercalation Effects 0.000 title claims abstract description 16
- 238000009830 intercalation Methods 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 11
- 230000001360 synchronised effect Effects 0.000 title claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 7
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- 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
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
A method for recovering lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair belongs to the field of waste lithium battery recovery. The method is characterized in that: the coupling double-flow recovery process for carrying out selective lithium removal of the anode and lithium supplement repair of the cathode in an aqueous solution electrolytic cell is formed by taking the lithium iron phosphate anode plate as an anode and a cathode respectively and taking a salt solution as an electrolyte. And (3) obtaining ferric phosphate at the anode, further recovering the ferric phosphate by adopting a wet process, and obtaining the repaired lithium iron phosphate at the cathode. The lithium removed by the anode can be effectively inserted into the cathode failure lithium iron phosphate through the electrolyte, and no extra lithium source is needed. In addition, the lithium concentration and the pH value in the electrolyte are basically constant in the whole electrolysis process, and the electrolyte can be directly recycled for secondary use. The method has low energy consumption and good economic and environmental benefits.
Description
Technical Field
The invention relates to the technical field of recovery of waste lithium ion batteries and recycling of electrode materials, in particular to a method for recovering a failed lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair.
Background
The lithium iron phosphate anode material is widely applied to the field of electric automobiles or energy storage due to low toxicity, thermal stability, long cycle life and economy. At present, the lithium iron phosphate battery occupies more than half of the market share of the whole lithium battery, namely, the lithium iron phosphate battery is out of service and climax, and if the lithium iron phosphate battery is improperly processed, environmental pollution and resource waste are caused. Meanwhile, the lithium battery anode waste concentrates a large amount of valuable metal resources, and the recovery of the valuable metals is the key of sustainable development of the battery industry.
At present, the recovery of the invalid lithium iron phosphate battery is mainly wet recovery, but the process is complex, the acid consumption is high, secondary pollution is generated, and the economy is not high. In contrast, the direct repair method directly carries out lithium supplementing repair on the ineffective lithium iron phosphate material, restores the electrochemical performance of the ineffective lithium iron phosphate material, carries out secondary utilization, greatly reduces the environmental pressure and has considerable economical efficiency.
Patent CN201710446047.4 proposes a solid phase repair method for lithium iron phosphate positive electrode material, which repairs the failed lithium iron phosphate at high temperature by adding a missing element source (lithium source), but the high temperature reaction energy consumption is higher. The patent CN102208707B, CN112174107A and the patent CN111547697A both propose a hydrothermal repair method for the invalid lithium iron phosphate anode material, wherein invalid lithium iron phosphate powder, a lithium source and a reducing agent are mixed and then placed in a hydrothermal kettle to react for 2-48 hours at about 200 ℃. The product obtained by the method has good uniformity and better electrochemical performance, but the hydrothermal method needs to use a high-pressure reaction vessel.
Patent CN113086961a proposes an electrochemical repair method, by constructing an aqueous solution H-type electrolytic cell, the anode plate of which is made of a metal material (such as zinc, aluminum, magnesium) having a lower oxidation-reduction potential than lithium iron phosphate, and the electrolyte of the anode cell is made of a metal salt corresponding to the anode. The cathode isThe waste lithium iron phosphate particles dispersed in the electrolyte at the positive electrode side, the negative plate is made of inert materials, and the electrolyte at the cathode tank is lithium salt solution (lithium source is provided). Ion exchange between the cathode and anode cells is achieved by ion exchange membranes. Electrolyzing an aqueous solution primary cell by setting a constant current, and anodizing: zn-2e - ＝Zn 2+ Lithium ions in the cathode side lithium salt intercalate into the spent lithium iron phosphate under discharge conditions: li (Li) 1-x FePO 4 +xLi + +xe - ＝LiFePO 4 . The method is environment-friendly and low in energy consumption, but as the repair process is carried out, the lithium concentration of the cathode side electrolyte is reduced, a commercial lithium source is required to be additionally added, and the anode plate is taken as a consumable, so that the cost is definitely increased.
Disclosure of Invention
The invention provides a method for recovering a lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair. According to the invention, the dead lithium iron phosphate positive plate, the direct-current power supply and the electrolyte form an aqueous solution electrolytic cell, so that selective lithium extraction of the anode and lithium supplement repair of the cathode dead lithium iron phosphate are synchronously realized.
In order to achieve the above purpose, the invention adopts the following specific technical scheme:
s1, discharging and disassembling a failure lithium iron phosphate battery to obtain a lithium iron phosphate positive plate;
s2, the invalid lithium iron phosphate positive plate can be directly used as a cathode and a positive electrode respectively without additional treatment, and forms an aqueous solution electrolytic cell together with a direct current power supply and electrolyte;
s3, electrifying to carry out electrolysis, carrying out lithium removal reaction on the anode, and embedding lithium ions removed from the anode into the invalid lithium iron phosphate under the drive of potential, so as to realize the repair and regeneration of the cathode. The electrolyte is slowly stirred in the electrolysis process so as to keep the concentration of lithium in the solution and the pH uniformity.
S4, collecting the iron phosphate obtained by the anode and the lithium iron phosphate pole piece after cathode lithium intercalation repair. The method comprises the steps of recovering the iron phosphate pole piece by a wet process, immersing the iron phosphate pole piece in deionized water to separate aluminum foil and lithium iron phosphate, drying and crushing the lithium iron phosphate to obtain lithium iron phosphate powder, and calcining the lithium iron phosphate powder in vacuum to improve the crystallinity of the material to obtain the regenerated lithium iron phosphate material.
Further, the electrolyte in step S2 is a lithium salt electrolyte including lithium sulfate, lithium nitrate, lithium phosphate, lithium acetate, etc., and the lithium ion concentration is preferably 1-5 g/L.
Further, the constant voltage in step S3 is in the range of 0.2V to 1.0V, and the electrolysis time is in the range of 0.5 to 5 hours.
The key points of the technology of the invention are as follows:
the method is characterized in that any treatment is not needed to be carried out on the waste lithium iron phosphate positive electrode sheet before electrolysis, an electrolysis system with anode and cathode being the invalid lithium iron phosphate positive electrode materials is directly constructed, and selective lithium removal of the anode and lithium intercalation repair of the cathode are synchronously realized through external constant voltage. Anode selective lithium removal: li (Li) x FePO 4 -xe - ＝FePO 4 +xLi + The method comprises the steps of carrying out a first treatment on the surface of the Lithium ions extracted from the anode are embedded into the invalid lithium iron phosphate under the drive of potential, and the repair and regeneration of the cathode are synchronously realized: li (Li) x FePO 4 +xe - +xLi + ＝LiFePO 4 . The invention is characterized in that no additional lithium source is needed and the pH value of the electrolyte is constant in the reaction process, so that no salt-containing wastewater is discharged. In addition, the oxygen evolution reaction of the anode is avoided, so that the method can be realized under the condition of low voltage (0.2V-1.0V), and the energy consumption of the process is further reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention discloses a method for recovering a spent lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair. The cathode can obtain a cathode material with excellent electrochemical performance. The method does not need to provide a commercial lithium source additionally, and can utilize the ineffective lithium iron phosphate anode material to the maximum extent.
(2) Compared with other recovery methods or repair methods of the invalid lithium iron phosphate anode material, the method has the advantages of low energy consumption, no waste water and waste gas discharge, environmental friendliness, no need of adding additional commercial lithium source, cyclic utilization of electrolyte and capability of obtaining better economic benefit.
Drawings
Fig. 1 is a schematic diagram of a recovery device principle corresponding to a method for recovering a failed lithium iron phosphate positive electrode material based on electrochemical lithium removal synchronous lithium intercalation repair in the embodiment.
Detailed Description
For a further understanding of the present invention, the present invention will be described more fully hereinafter with reference to preferred embodiments, but the scope of the present invention is not limited to the following specific embodiments. It should be noted that variations and modifications can be made by those skilled in the art without departing from the spirit of the invention, but these are within the scope of the invention.
Example 1
Discharging and disassembling the invalid lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, taking the invalid lithium iron phosphate positive plate as a positive electrode and a negative electrode respectively, and forming an aqueous solution electrolytic cell together with a direct current power supply and electrolyte. And (3) taking a salt solution with lithium concentration of 5g/L as electrolyte, setting constant pressure of 0.2V for electrolysis for 5 hours, carrying out lithium removal reaction on an anode to obtain ferric phosphate, carrying out lithium intercalation reaction on a cathode to obtain repaired lithium iron phosphate, and slowly stirring the electrolyte in the electrolysis process to keep the concentration and pH uniformity of lithium in the solution. ICP composition test analysis shows that the molar ratio of lithium to iron in the anode is 0.12, and the lithium removal rate is 88%; the molar ratio of lithium to iron of the cathode is 1.01. The repaired lithium iron phosphate material is then made into a button cell, and the initial-week discharge specific capacity at 0.1C is measured to be 132.44mAh/g, and the capacity retention rate after 100 weeks of circulation is measured to be 98.32%.
Example 2
Discharging and disassembling the invalid lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, taking the invalid lithium iron phosphate positive plate as a positive electrode and a negative electrode respectively, and forming an aqueous solution electrolytic cell together with a direct current power supply and electrolyte. And (3) taking a salt solution with the lithium concentration of 2g/L as an electrolyte, setting a constant voltage of 1.0V for electrolysis for 4 hours, carrying out lithium removal reaction on an anode to obtain ferric phosphate, carrying out lithium intercalation reaction on a cathode to obtain repaired lithium iron phosphate, and slowly stirring the electrolyte in the electrolysis process to keep the lithium concentration and pH uniformity in the solution. ICP composition test analysis shows that the molar ratio of lithium to iron in the anode is 0.08, and the lithium removal rate is 92%; the molar ratio of cathode lithium iron is 1.03. The repaired lithium iron phosphate material is then made into a button cell, and the initial cycle discharge specific capacity at 0.1C is 144.81mAh/g, and the capacity retention rate after 100 cycles is 99.1%.
Example 3
Discharging and disassembling the invalid lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, taking the invalid lithium iron phosphate positive plate as a positive electrode and a negative electrode respectively, and forming an aqueous solution electrolytic cell together with a direct current power supply and electrolyte. And (3) taking a salt solution with the lithium concentration of 3g/L as an electrolyte, setting a constant voltage of 0.8V for electrolysis for 2 hours, carrying out a lithium removal reaction on an anode to obtain ferric phosphate, carrying out a lithium intercalation reaction on a cathode to obtain repaired lithium iron phosphate, and slowly stirring the electrolyte in the electrolysis process to keep the lithium concentration and the pH value in the solution uniform. ICP composition test analysis shows that the molar ratio of lithium to iron in the anode is 0.08, and the lithium removal rate is 92%; the molar ratio of cathode lithium iron is 1.06. The repaired lithium iron phosphate material is then made into a button cell, and the initial cycle discharge specific capacity at 0.1C is 142.64mAh/g, and the capacity retention rate after 100 cycles is 98.8%.
Example 4
Discharging and disassembling the invalid lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, taking the invalid lithium iron phosphate positive plate as a positive electrode and a negative electrode respectively, and forming an aqueous solution electrolytic cell together with a direct current power supply and electrolyte. And (3) taking a salt solution with the lithium concentration of 4g/L as an electrolyte, setting a constant voltage of 0.6V for electrolysis for 0.5 hours, carrying out lithium removal reaction on an anode to obtain ferric phosphate, carrying out lithium intercalation reaction on a cathode to obtain repaired lithium iron phosphate, and slowly stirring the electrolyte in the electrolysis process to keep the concentration of lithium and the pH uniformity in the solution. ICP composition test analysis shows that the molar ratio of lithium to iron in the anode is 0.09, and the lithium removal rate is 91%; the molar ratio of cathode lithium to iron is 1.08. The repaired lithium iron phosphate material is then made into a button cell, and the initial cycle discharge specific capacity at 0.1C is 138.61mAh/g, and the capacity retention rate after 100 cycles is 99.0%.
Claims (2)
1. The method for recovering the lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair is characterized by comprising the following steps of:
(1) Discharging and disassembling the invalid lithium iron phosphate battery to obtain a lithium iron phosphate positive plate;
(2) Respectively taking the invalid lithium iron phosphate positive plate as a positive electrode and a negative electrode, and forming an aqueous solution electrolytic cell together with a direct current power supply and electrolyte;
(3) Electrifying to perform electrolysis so that the anode generates lithium removal reaction and the cathode generates lithium intercalation reaction; slowly stirring the electrolyte in the electrolysis process to keep the lithium concentration and the pH uniformity in the solution;
(4) Collecting the iron phosphate powder obtained by the anode and the lithium iron phosphate powder after cathode lithium intercalation repair; the ferric phosphate is further recovered by adopting a wet process, and the lithium iron phosphate powder is subjected to vacuum calcination to obtain the regenerated lithium iron phosphate material.
2. The electrochemical-based restoration and recovery method for a failed lithium iron phosphate positive electrode material according to claim 1, wherein the electrolyte in the step (2) is a lithium salt electrolyte, and the lithium salt comprises lithium sulfate, lithium nitrate, lithium phosphate and lithium acetate; the concentration of lithium ions is 1-5 g/L; the voltage range of the step (3) is 0.2V-1.0V, and the electrolysis time is 0.5-5 hours.
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| CN202310831880.6A CN116926572A (en) | 2023-07-07 | 2023-07-07 | Method for recovering lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair |
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| CN202310831880.6A CN116926572A (en) | 2023-07-07 | 2023-07-07 | Method for recovering lithium iron phosphate positive electrode material by electrochemical lithium removal and synchronous lithium intercalation repair |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117525661A (en) * | 2023-12-25 | 2024-02-06 | 武汉大学 | Ferrocene-mediated waste lithium iron phosphate anode direct repair regeneration method and application |
| CN117810588A (en) * | 2024-01-09 | 2024-04-02 | 科立鑫(珠海)新能源有限公司 | Method for recycling lithium iron phosphate in waste lithium battery |
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2023
- 2023-07-07 CN CN202310831880.6A patent/CN116926572A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117525661A (en) * | 2023-12-25 | 2024-02-06 | 武汉大学 | Ferrocene-mediated waste lithium iron phosphate anode direct repair regeneration method and application |
| CN117810588A (en) * | 2024-01-09 | 2024-04-02 | 科立鑫(珠海)新能源有限公司 | Method for recycling lithium iron phosphate in waste lithium battery |
| CN117810588B (en) * | 2024-01-09 | 2024-06-04 | 科立鑫(珠海)新能源有限公司 | Method for recycling lithium iron phosphate in waste lithium battery |
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