CN117393874A - Waste lithium iron phosphate recycling method based on redox targeted flow battery - Google Patents
Waste lithium iron phosphate recycling method based on redox targeted flow battery Download PDFInfo
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- iron phosphate
- lithium iron
- flow battery
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- 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 59
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000003792 electrolyte Substances 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000012695 Interfacial polymerization Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 230000007812 deficiency Effects 0.000 claims 1
- 229920000867 polyelectrolyte Polymers 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 238000002386 leaching Methods 0.000 abstract description 7
- 230000001172 regenerating effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000010297 mechanical methods and process Methods 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention provides a waste lithium iron phosphate recycling method based on a redox targeted flow battery, and belongs to the technical field of waste lithium ion battery recycling. The invention aims to solve the problem of secondary pollution of the recycled waste liquid in the existing reutilization of the waste lithium iron phosphate anode. The method comprises the following steps: s1, disassembling a waste lithium iron phosphate battery, separating out a positive plate, washing and drying; s2, calculating the shortage, the surface load and the surface capacity of lithium ions in the waste LFP positive plate; s3, constructing a zinc-iron flow battery; s4, the positive plate is arranged in a positive storage tank of the flow battery, constant-current discharge is carried out on the flow battery, and the discharge is naturally cooled to room temperature. The method is simple, convenient and quick, omits complicated steps such as a mechanical method, acid leaching or alkaline leaching, reduces the cost and avoids secondary pollution to the environment. In addition, the invention has low requirements on equipment and is very suitable for recycling and regenerating lithium batteries in an industrial scale.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a waste lithium iron phosphate recovery and regeneration method based on a redox targeted flow battery.
Background
Lithium Ion Batteries (LIBs) are one of the most impressive and successful energy storage systems, playing an important role in our daily lives. As a main positive electrode of lithium ion batteries, lithium iron phosphate (LFP) has a large market share. The LFP can maintain a stable olivine crystal structure due to stronger Fe-O and P-O bond energy, thereby having good high temperature stability. Furthermore, the core elements Fe and P of LFP are cost-effective and widely distributed worldwide as natural resources. Accordingly, lithium ion batteries based on lithium iron phosphate are widely used in Electric Vehicles (EV) and Energy Storage Systems (ESS), and as the application scale is expanded, it is necessary to face the situation that lithium iron phosphate batteries are discarded on a large scale in the future, and it is confirmed that their recycling becomes very urgent and necessary.
To date, many recycling processes have focused on valuable elements and positive electrode materials, in particular, the recycling of spent lithium iron phosphate positive electrode materials. Two recovery routes are generally employed: pyrometallurgical and hydrometallurgical processes. Both strategies have advantages and disadvantages. The pyrogenic process directly promotes the physicochemical conversion and further regeneration of the LFP positive electrode material. For example, the used LFP material is combined with Li 2 CO 3 Mixing by ball milling and then drying at high temperature. While effective pyrometallurgical techniques can achieve recovery, the process requires significant energy consumption. In addition, in the case of the optical fiber,the high temperatures required for this process may lead to structural damage and reduced electrochemical performance, thereby impeding the sustainable development of waste lithium iron phosphate cathode materials. Pyrometallurgy cannot therefore be regarded as a sustainable recovery process within the industry. In the case of hydrometallurgy, most lithium extraction processes are based on oxidative leaching, including acid leaching, alkaline leaching and bioleaching. The remaining elements are recovered from the leachate by various combinations of solvent extraction, chemical precipitation and electrochemical deposition. However, hydrometallurgical techniques are always cumbersome as they involve pretreatment, resulting in increased chemical consumption and higher costs. Therefore, it is imperative to find a simple, efficient, suitable method for mass production. It is also more desirable that the recovered material be used directly as the positive electrode material of a battery without complex secondary treatments.
Disclosure of Invention
The invention provides a low-cost pollution-free continuous controllable lithium iron phosphate positive electrode material regeneration method, and aims to solve the problem of secondary pollution of recycled waste liquid in the existing reutilization of waste lithium iron phosphate positive electrodes. The method of the invention directly utilizes the recovered lithium iron phosphate as the positive electrode and matches the positive electrode to manufacture the lithium iron phosphate battery without any secondary treatment. The whole process can not produce secondary pollution, and completely meets the requirements of clean production and recycling green economy.
In order to realize the technical problems, the invention adopts the following technical scheme:
the invention aims to provide a waste lithium iron phosphate recycling method based on a redox targeted flow battery, which is realized by the following steps:
s1, disassembling a waste lithium iron phosphate battery, separating out a positive plate, washing and drying;
s2, calculating the shortage, the surface load and the surface capacity of lithium ions in the waste LFP positive plate;
s3, constructing a zinc-iron flow battery, wherein the flow battery comprises a diaphragm, an anode storage tank and a cathode storage tank, the anode storage tank is filled with anode electrolyte, the cathode storage tank is filled with cathode electrolyte, and the anode electrolyte contains [ Fe (CN) 6 ] 3- ；
And S4, placing the positive plate processed in the step S1 in a positive storage tank of the flow battery, discharging the flow battery in a constant current manner, and naturally cooling to room temperature after discharging is finished, so as to obtain the repaired and regenerated lithium iron phosphate positive plate.
Further defined, in S1, the separated positive electrode sheet is rinsed with DMC solvent.
Further defined, in S1, the drying is performed in a vacuum oven at a temperature of 70℃to 90℃for at least 1 hour.
Further limiting, in S2, testing the loss degree of lithium ions in the waste lithium iron phosphate electrode slice by ICP-MS, and measuring the load capacity and the surface capacity of the electrode slice in unit area by using an analytical balance.
Further defined, in S3, [ Fe (CN) 6 ] 3- The concentration of (2) is 0.01M to 0.7M.
Further defined, in S3, the positive electrode electrolyte further includes a co-electrolyte.
Further defined, the co-electrolyte is LiCl, the concentration of LiCl being 3M.
Further defined, in S3, the catholyte consists of ZnBr 2 And LiOH and deionized water.
Further defined, znBr 2 Is 0.4M and LiOH is 3M.
Further defined, in S3, the steps of preparing the separator are as follows:
(1) Mixing a polymer, carbon black and a solvent according to the mass ratio of (0.05-1) to (2-8) to (100-1000) to obtain a solution;
(2) Forming a solution on the surface of an ion exchange membrane through spraying, spin coating, roll coating, brush coating, knife coating or interfacial polymerization, and volatilizing the solvent to obtain the membrane;
wherein the polymer is PVDF, PTFE or acrylic polyurethane; the carbon black is super carbon black, ketjen black or common carbon black, and the solvent is one or more of water, isopropanol, ethanol, N-methyl pyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide.
Further defined, in S4, the constant current discharge time is 1h to 24h, the reaction temperature is 25-60 ℃, and the current density is controlled to be 1mA/cm 2 ～100mA/cm 2 The voltage range is controlled between 0.01V and 2V.
The invention aims to provide a waste lithium iron phosphate recycling method based on a redox targeted flow battery. The method utilizes [ Fe (CN) generated by discharge of an alkaline zinc-iron flow battery 6 ] 4- And reacting with the waste lithium iron phosphate positive plate to realize the regeneration of the waste lithium iron phosphate positive plate. Compared with other recycling methods, the method can directly recycle the recycled positive electrode material, and is matched with the negative electrode to manufacture the battery, and secondary processes such as calcination and the like are not needed, so that pollution and energy consumption are reduced. In addition, the method has continuous production capacity, can improve recycling efficiency, has strong economic driving force, is suitable for large-scale mass production, and can be directly used for industrial application.
Another object of the present invention is to provide a lithium iron phosphate battery, that is, a lithium iron phosphate battery assembled from positive electrode sheets obtained by a recycling method. The discharge capacity and cycle life of the battery are almost equivalent to those of a completely new lithium iron phosphate positive electrode assembled battery. This proves that the recovery and regeneration method provided by the invention can successfully repair the waste lithium iron phosphate anode material.
Compared with the prior art, the invention has the following beneficial effects:
compared with the existing recycling method, the method can directly recycle the waste lithium iron phosphate positive electrode material, is matched with the negative electrode for manufacturing the battery, and does not need secondary processes such as calcination, thereby reducing pollution and energy consumption. The method is simple, convenient and quick, omits complicated steps such as a mechanical method, acid leaching or alkaline leaching, reduces the cost and avoids secondary pollution to the environment. In addition, the invention has low requirements on equipment and is very suitable for recycling and regenerating lithium batteries in an industrial scale.
According to the invention, the target flow battery is utilized to carry out electrochemical lithium supplementation on the waste lithium iron phosphate material, so that lithium lost in the process of using the waste lithium iron phosphate material in a plurality of charging and discharging processes is compensated, and the electrochemical performance of the lithium iron phosphate positive electrode material is repaired, and is different from the conception of the existing recycling method.
For a further understanding of the nature and the technical aspects of the present invention, reference should be made to the following detailed description of the invention and the accompanying drawings, which are provided for reference and illustration only and are not intended to limit the invention.
Drawings
FIG. 1 is a schematic diagram of a system for recycling and regenerating anode materials of a waste lithium iron phosphate battery;
FIG. 2 is an XRD pattern of a prosthetic regenerated lithium iron phosphate positive electrode material obtained by electrochemical lithium replenishment;
FIG. 3 is a charge-discharge curve at 1C current density for a button cell prepared from a reconditioned regenerated lithium iron phosphate positive electrode material and a brand-new lithium iron phosphate positive electrode material;
fig. 4 is a graph of the rate capability of a button cell prepared by repairing a regenerated lithium iron phosphate positive electrode material and a brand new lithium iron phosphate positive electrode material.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
For a better understanding of the present invention, reference is made to the following examples. The invention is not limited to what has been described in the detailed description.
The method for recycling and regenerating the waste lithium iron phosphate based on the redox targeted flow battery in the embodiment 1 is realized by the following steps:
s1, after the waste lithium iron phosphate battery is disassembled step by step, separating out 1g of positive plate; and cleaning the positive plate by using DMC solvent, removing the residual electrolyte on the positive plate, and drying the positive plate with the residual electrolyte removed in a vacuum oven at 80 ℃.
S2, testing the loss degree of lithium ions in the waste lithium iron phosphate electrode slice through ICP-MS, and measuring the load capacity and the surface capacity of the electrode slice in unit area by using an analytical balance.
For Zn/[ Fe (CN) 6 ] 3- -SLFP hybrid flow battery with an effective area of 2.0cm 2 ×2.0cm 2 . The cation exchange membrane is a compact cation exchange membrane coated by a carbon layer/a hydrophobic layer and is used for separating positive electrolyte and negative electrolyte. The electrochemically treated carbon felt was used as an electrode.
S3, constructing a zinc-iron flow battery, wherein the flow battery comprises a diaphragm, a positive electrode storage tank and a negative electrode storage tank (see figure 1), the positive electrode storage tank is filled with positive electrode electrolyte, the negative electrode storage tank is filled with negative electrode electrolyte, and the positive electrode electrolyte comprises [ Fe (CN) 6 ] 3 ， - 11.5ml of 0.3M [ Fe (CN) 6 ] 3- And 3M LiCl support salt as positive electrode electrolyte, 40mL of 0.4M ZnBr 2 And an alkaline solution of a 3M LiOH supporting salt as a negative electrode electrolyte.
S4, placing the positive plate processed in the S1 in a positive storage tank of the flow battery, performing constant-current discharge on the flow battery, and performing constant-current discharge test on a NEWARE battery tester with the voltage range of 0.01-2.0V, wherein the current density range is 20mA/cm 2 And (3) naturally cooling the lithium iron phosphate anode sheet to room temperature after the discharge is ended at the reaction temperature of 50 ℃, thus obtaining the repaired and regenerated lithium iron phosphate anode sheet (RLFP).
The dense cation exchange membrane coated by the carbon layer/the hydrophobic layer is prepared by the following steps: 4g of Ketjen black and 0.5g of PVDF are dissolved in 20.5g of NMP solvent to obtain a blend solution with the mass concentration of 18%, the blend solution is spin-coated on an ion exchange membrane Nafion117, and the solvent is volatilized for 2 hours at the temperature of 50 ℃ to prepare a carbon/hydrophobic layer functional composite membrane with the thickness of 10 mu m, which is used as the membrane.
The method comprises the steps of adopting a recovered and regenerated lithium iron phosphate sheet or a brand new lithium iron phosphate sheet as a positive electrode, adopting a lithium sheet as a negative electrode, adopting a diaphragm as a polypropylene film (Cellgard 2400), adding a proper amount of electrolyte (1M LiPF) 6 Dissolved in organic solvent with volume ratio EC: DEC: dmc=1:1:1), 2032 button cell was assembled in a glove box under argon protection, and the performance of the assembled full cell was tested.
The XRD diagram of the regenerated lithium iron phosphate positive electrode material obtained by electrochemical lithium supplementing is shown in figure 2; as can be seen from FIG. 2, the diffraction peak of the restored and regenerated lithium iron phosphate obtained by electrochemical lithium supplementation is consistent with the PDF standard card (JPCDS: 40-1499) and accords with the crystal form structure of the lithium iron phosphate.
The charge-discharge curves of the button cell prepared by the regenerated lithium iron phosphate positive electrode material and the brand-new lithium iron phosphate positive electrode material under the current density of 1C are shown in figure 3; as can be seen from FIG. 3, the charge and discharge capacities of the restored and regenerated lithium iron phosphate positive electrode material are 145.4mAh/g and 135.3mAh/g respectively, which are equivalent to 140.5mAh/g and 140.3mAh/g of the completely new lithium iron phosphate positive electrode material.
The rate performance diagram of the button cell prepared by repairing the regenerated lithium iron phosphate positive electrode material and the brand-new lithium iron phosphate positive electrode material is shown in fig. 4; as can be seen from FIG. 4, the discharge capacities of the repair regenerated lithium iron phosphate positive electrode materials at 0.1C, 0.5C, 1C, 2C, 4C, 10C and 20C are respectively 163.6mAh/g, 155.5mAh/g, 143.2mAh/g, 128.9mAh/g, 117.2mAh/g, 101.4mAh/g and 89.6mAh/g, which are equivalent to 163.2mAh/g, 155.2mAh/g, 142.4mAh/g, 128.8mAh/g, 122.3mAh/g, 112.4mAh/g and 95.7mAh/g of the completely new lithium iron phosphate positive electrode materials.
Claims (10)
1. A method for recycling waste lithium iron phosphate based on redox targeted flow batteries is characterized by comprising the following steps:
s1, disassembling a waste lithium iron phosphate battery, separating out a positive plate, washing and drying;
s2, calculating the shortage, the surface load and the surface capacity of lithium ions in the waste LFP positive plate
S3, constructing a zinc-iron flow battery, wherein the flow battery comprises a diaphragm, an anode storage tank and a cathode storage tank, the anode storage tank is filled with anode electrolyte, the cathode storage tank is filled with cathode electrolyte, and the anode electrolyte contains [ Fe (CN) 6 ] 3- ；
And S4, placing the positive plate processed in the step S1 in a positive storage tank of the flow battery, discharging the flow battery in a constant current manner, and naturally cooling to room temperature after discharging is finished, so as to obtain the repaired and regenerated lithium iron phosphate positive plate.
2. The method according to claim 1, wherein in S2, the lithium ion deficiency degree in the waste lithium iron phosphate electrode sheet is tested by ICP-MS, and the load capacity and the surface capacity of the electrode sheet per unit area are measured by using an analytical balance.
3. The method according to claim 1, wherein in S3, [ Fe (CN) 6 ] 3- The concentration of (2) is 0.01M to 0.7M.
4. The method of claim 1, wherein in S3, the positive electrode electrolyte further comprises a co-electrolyte.
5. The method of claim 4, wherein the polyelectrolyte is LiCl, and the concentration of LiCl is 3M.
6. The method according to claim 1, wherein in S3, the negative electrode electrolyte consists of ZnBr 2 And LiOH and deionized water.
7. The method according to claim 6, wherein ZnBr 2 Is 0.4M and LiOH is 3M.
8. The method according to claim 1, wherein in S3, the separator is prepared by the steps of:
(1) Mixing a polymer, carbon black and a solvent according to the mass ratio of (0.05-1) to (2-8) to (100-1000) to obtain a solution;
(2) Forming a solution on the surface of an ion exchange membrane through spraying, spin coating, roll coating, brush coating, knife coating or interfacial polymerization, and volatilizing the solvent to obtain the membrane;
wherein the polymer is PVDF, PTFE or acrylic polyurethane; the carbon black is super carbon black, ketjen black or common carbon black, and the solvent is one or more of water, isopropanol, ethanol, N-methyl pyrrolidone, dimethyl sulfoxide and N, N-dimethylformamide.
9. The method according to claim 1, wherein in S4, constant current discharge is performedThe reaction time is 1-24 h, the reaction temperature is 25-60 ℃, and the current density is controlled at 1mA/cm 2 ～100mA/cm 2 The voltage range is controlled between 0.01V and 2V.
10. The method according to claim 1, wherein in S4, the reaction temperature is 50℃and the current density is controlled at 20mA/cm 2 。
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