CN116315219A - Method for preparing carbon-based catalyst by recycling conductive agent from waste lithium iron phosphate battery and application of method - Google Patents
Method for preparing carbon-based catalyst by recycling conductive agent from waste lithium iron phosphate battery and application of method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 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 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 239000006258 conductive agent Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000002386 leaching Methods 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005192 partition Methods 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
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- 239000005457 ice water Substances 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 244000137852 Petrea volubilis Species 0.000 claims description 3
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010926 waste battery Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 9
- 239000005955 Ferric phosphate Substances 0.000 description 8
- 229940032958 ferric phosphate Drugs 0.000 description 8
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- 229910000510 noble metal Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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 application relates to the technical field of recycling of waste batteries, and particularly discloses a method for preparing a carbon-based catalyst by recycling conductive agents from waste lithium iron phosphate batteries. The method comprises the following steps: s1: taking out the positive electrode of the lithium ion battery after discharge disassembly, and separating the lithium iron phosphate positive electrode material from the aluminum foil; s2: drying and grinding the lithium iron phosphate anode material to obtain lithium iron phosphate anode material powder; s3: acid leaching; s4: filtering and separating the heated and stirred mixed solution, and treating filtrate obtained after filtering to recover lithium; s5: cleaning, drying and grinding the filter residue after filtering and separating to obtain filter residue powder; s6: weighing 100-300mg of filter residue powder, placing into a high-temperature crucible, and roasting for 3-5 hours at 900 ℃ in a nitrogen atmosphere to obtain the Fe-N-P co-doped carbon catalyst. Provides a new thought for recycling the waste lithium iron phosphate lithium ion battery, has high lithium recovery rate, and also obtains high-value recycling of the recovered conductive agent.
Description
Technical Field
The application relates to the technical field of recycling of waste batteries, in particular to a method for recycling conductive agents from waste lithium iron phosphate batteries and preparing carbon-based catalysts by using the conductive agents.
Background
The upcoming power cell decommissioning has attracted global attention. Early power lithium ion batteries used in electric and hybrid vehicles can be briefly classified into two types, i.e., nickel cobalt lithium manganate ternary material (NCM) and lithium iron phosphate (LFP), according to the positive electrode material. Wherein, nickel, cobalt and lithium are all high-value rare resources. At present, the recovery method of the anode material comprises processes of pyrometallurgy, hydrometallurgy, biological metallurgy and the like, wherein the hydrometallurgy combined separation technology has the advantages of low reaction temperature, low energy consumption and high recovery rate. However, the conductive agent serving as the high-value auxiliary material anode material is not reasonably utilized, and is mainly used as solid waste or plastic filler at present.
The conductive agent is distributed in the gaps between the positive electrode active materials to form a conductive network, so that the conductivity of the positive electrode materials is improved. The common conductive agent mainly comprises traditional conductive agents such as carbon black, conductive graphite and the like and novel conductive agents such as carbon nano tubes, graphene and the like. The conductive agent is generally required to be prepared into a slurry, mixed with the positive electrode material and the binder, and coated on the aluminum foil substrate. The lithium ion battery conductive agent has higher oil absorption value and lower metal impurity content than common carbon black. The novel conductive agent carbon nano tube and graphene are in line-point and surface-point contact with the positive electrode material, which is superior to the traditional conductive carbon black in point-point contact, so that the resistance is low, the required addition amount is small, and the disadvantage is higher price. In recent years, a novel composite conductive paste of conductive carbon black and carbon nanotubes or graphene is paid attention to, so that the cost is effectively reduced, and the electronic conduction is enhanced. It is expected that the recoverable value of the conductive agent will become greater with the rapid increase in the size of retired power cells and the use of new conductive agents.
The recovered conductive agent is contaminated with metal ions, compounds, electrolyte decomposition products, and the like, and the re-purification has technical and cost problems due to multiple charge and discharge, so that it is difficult to re-use the conductive agent in the manufacture of lithium ion batteries. Therefore, the key point of recycling and high-value utilization of the waste conductive agent is to find a proper application direction. At present, more than 90% of nearly 1 ten thousand domestic fuel cell vehicles use imported noble metal catalysts Pt/C and RuO 2 Etc. account for 36% of the total cost of the fuel cell. Therefore, the preparation of the carbon-based catalyst by recycling the conductive agent from the waste lithium iron phosphate anode material has important economic and scientific research values.
Disclosure of Invention
The invention provides a method for preparing a carbon-based catalyst by recycling a conductive agent from a waste lithium iron phosphate battery, which is used for recycling a lithium iron phosphate anode material of a lithium ion battery, separating conductive carbon black and ferric phosphate after lithium is recycled, and performing heat treatment to obtain an oxygen reduction catalyst with excellent performance, and can be used for fuel cells, metal air batteries and water electrolysis.
In a first aspect, the present disclosure provides a method for preparing a carbon-based catalyst from a waste lithium iron phosphate battery using a recovered conductive agent, the method comprising the steps of:
s1: taking out the positive electrode of the lithium ion battery after discharge disassembly, and separating the lithium iron phosphate positive electrode material from the aluminum foil;
s2: drying and grinding the lithium iron phosphate anode material to obtain lithium iron phosphate anode material powder;
s3: acid leaching: weighing lithium iron phosphate anode material powder, adding the lithium iron phosphate anode material powder into sulfuric acid and hydrogen peroxide solution to obtain a mixed solution, heating the mixed solution to 60-80 ℃ in a water bath, and continuously stirring for 120-240min;
s4: filtering and separating the heated and stirred mixed solution, and treating the filtrate obtained after filtering to further recover lithium;
s5: cleaning, drying and grinding the filter residue after filtering and separating to obtain filter residue powder;
s6: weighing 100-300mg of filter residue powder, placing into a high-temperature crucible, roasting for 3-5 hours at 600-900 ℃ in a nitrogen atmosphere, cooling to room temperature after power failure, and taking out to obtain the Fe-N-P co-doped carbon catalyst.
The lithium ion battery lithium iron phosphate cathode material is recovered by an acid leaching process, wherein lithium is dissolved in the leaching solution in the form of sulfate, and ferric phosphate and a conductive agent exist in leaching residues. After solid-liquid separation, the leaching solution is used for lithium recovery, the leaching slag is subjected to heat treatment in a nitrogen atmosphere after being cleaned and dried, the conductive agent carbon material generally has large specific surface area, rich pore structure, high corrosion resistance, good thermal and mechanical stability and excellent conductivity, active sites are formed through doping of hetero atoms (such as N, P, B and the like), topological defects, co-doping of metal-nitrogen-carbon (M-N-C) and the like, and N, P double-coordinated Fe sites are beneficial to the adsorption/desorption process of an oxygen intermediate, can obtain higher catalytic activity of oxygen reduction reaction than single N doping, has low cost, is hopeful to replace noble metal catalysts such as Pt, ru and Ir, further obtains the Fe-N-C oxygen reduction catalyst with low cost, can be used in the fields of fuel cells, metal-air cells, water electrolysis, super (pseudo) capacitors and the like, and is an effective way for recycling the conductive agent for high-value utilization.
In some possible embodiments, the acid leaching of the lithium iron phosphate positive electrode material powder comprises the steps of:
a: weighing 5-10g of lithium iron phosphate positive electrode material powder, adding into 100-300mL of 1-3mol L -1 Dissolving powder in sulfuric acid solution to obtain initial acid leaching solution;
b: slowly adding 6-15mL of hydrogen peroxide solution into the initial acid leaching solution to obtain a mixed solution;
c: heating the mixed solution to 60-80 ℃ in a water bath, and continuously stirring the mixed solution while heating for 120-240min.
In some possible embodiments, the hydrogen peroxide solution is present in an amount of 10% to 30%.
In some possible embodiments, the treatment of the filtrate comprises acid-base neutralization or carbonate precipitation treatment.
In some possible implementationsIn the mode, the oil absorption value of the conductive carbon black is more than or equal to 250mLg -1 。
In some possible embodiments, the main component of the lithium iron phosphate positive electrode material of the waste lithium ion battery is lithium iron phosphate, and the main component of the filter residue after leaching is ferric phosphate (FePO 4 ) And carbon black.
In some possible embodiments, the catalyst comprises a composition of Fe 2 P and Fe 2 P 2 O 7 And the carbon black surface after calcination forms C-N, C-P, fe-N, pyridine N, pyrrole N and graphite N groups.
In a second aspect, the disclosure provides an application of a waste lithium iron phosphate battery to prepare a carbon-based catalyst by recycling a conductive agent, wherein the carbon-based catalyst prepared by recycling the conductive agent is used for a battery, a working electrode of the battery is a catalyst-modified glassy carbon electrode, a counter electrode is a platinum wire, a reference electrode is an Hg/HgO electrode, and an electrolyte is 0.1MKOH solution.
The Fe-N-P co-doped carbon catalyst obtained by heat treatment has the advantages of simple preparation method, low cost, excellent oxygen reduction catalytic activity and stability, and can be used for replacing noble metal catalysts in fuel cells, metal-air cells and water electrolysis.
In some possible embodiments, the glassy carbon working electrode is modified with a pre-prepared slurry, and the working electrode of the battery is a catalyst modified glassy carbon electrode, comprising the following processing steps:
weighing 4-6mg of catalyst powder, adding into a glass bottle, adding 800-1000 mu L of deionized water, 200-400 mu L of alcohol and 100-200 mu L of 5% Nafion solution, and performing ultrasonic treatment in ice water bath for 30-60min to prepare working electrode modification slurry; and sucking 5-8 mu L of the modified slurry by using a pipetting gun, dripping the modified slurry on a glassy carbon electrode, and naturally drying to prepare the battery working electrode.
In some possible embodiments, the carbon-based catalyst is used in a zinc-air cell, and the method of preparing the zinc-air cell comprises the steps of: respectively weighing 25mg of the Fe-N-P co-doped catalyst and reference carbon black powder, ultrasonically dispersing in 10mL of ethanol, and collectingUniformly spraying on the surface of carbon paper with the thickness of 5cm multiplied by 5cm by using a spray gun to prepare the catalyst with the loading capacity of 1mgcm -2 Is dried for later use; before the zinc negative plate is used, sand paper polishing is needed, the zinc air battery is assembled from the negative electrode, negative plate-zinc plate-partition frame (for charging electrolyte) -positive electrode-positive plate are sequentially arranged from left to right, the negative plate-zinc plate-partition frame is fixedly packaged, and 6mol L is filled in the partition frame in the middle of the battery -1 KOH and 0.2mol L -1 Zn (Ac) 2 And standing the electrolyte for 2 hours to obtain the electrolyte.
In summary, the present application has the following beneficial effects:
1. according to the method, the lithium iron phosphate anode material of the waste lithium ion battery is recycled, so that after the lithium iron phosphate anode material is subjected to acid leaching treatment by sulfuric acid and hydrogen peroxide, leaching liquid and filter residues are separated, lithium can be recycled from the filter residues through treatment after filtration and separation, the filter residues comprise ferric phosphate and conductive carbon black, the filter residues are subjected to cleaning, drying and grinding, then the filter residue powder is baked for 3 hours at 900 ℃ in a nitrogen atmosphere through high-temperature heat treatment, nitrogen doping can also catalyze ORR, and nitrogen-containing inert gas with stable chemical property is added, after stable Fe-N centers are formed in the inert atmosphere, more nitrogen-containing micropores are formed in the nitrogen heat treatment process, so that the activity is remarkably improved, the catalyst obtained through heat treatment at 900 ℃ has large specific surface area and micropore specific surface area, the best activity is shown, the specific surface area is continuously improved, the activity is reduced, and the Fe-N-P co-doped carbon catalyst is obtained;
2. the Fe-N-P co-doped carbon catalyst preferably obtained by heat treatment has the advantages of simple preparation method, low cost, excellent oxygen reduction catalytic activity and stability, can be used for replacing noble metal catalysts in fuel cells, metal air cells and water electrolysis, generally has large specific surface area, rich pore structures, high corrosion resistance, good thermal and mechanical stability and excellent conductivity, forms active sites through doping of hetero atoms (such as N, P, B and the like), topological defects, co-doping of metal-nitrogen-carbon (M-N-C) and the like, and N, P double-coordinated Fe sites are beneficial to the adsorption/desorption process of oxygen intermediates, can obtain higher oxygen reduction catalytic activity than single N doping, has low cost, is hopeful to replace noble metal catalysts such as Pt, ru and Ir and the like, and is used for fuel cells, metal air cells and water electrolysis;
3. the method provides a new thought for recycling the waste lithium iron phosphate lithium ion battery, has high lithium recycling rate, and also obtains high-value recycling of the recycled conductive agent.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the scope of the disclosure.
Drawings
1. Schematic of the preparation flow of the catalyst;
2. SEM image of leaching residue after leaching and extracting lithium;
3. SEM images of the catalyst after heat treatment of the present application;
4. XRD analysis of the lithium iron phosphate anode material;
5. XRD analysis of leaching residues of the lithium iron phosphate anode material;
6. XRD analysis of the catalyst is obtained by heat treatment of leaching residues;
7. XPS fitting map of C peak of C-FP catalyst;
8. XPS fitting map of N peak of C-FP catalyst;
9. conductive carbon black (SUPERP) was compared to the voltammogram of the C-FP catalyst of the present application in oxygen saturated 0.1 MKOH; 10. conductive carbon black (SUPERP) is compared with the linear scanning curve of the C-FP catalyst of the application in oxygen saturation of 0.1 MKOH;
11. the C-FP catalyst of the application rotates a disk electrode Koutecky-Levic plot in oxygen saturated 0.1 MKOH; 12. the C-FP catalyst of the present application was analyzed for H in oxygen saturated 0.1MKOH by rotating disk electrode 2 O 2 % yield and electron transfer number;
13. the current time i-t curve of the C-FP catalyst in oxygen saturated 0.1 MKOH;
14. the conductive carbon black (SUPERP) and the C-FP catalyst are applied to open circuit voltage test of zinc-air batteries; 15. the conductive carbon black (SUPERP) and the C-FP catalyst are applied to the charge-discharge cycle test of the zinc-air battery; 16. the conductive carbon black (SUPERP) and the C-FP catalyst are applied to the full discharge capacity test of the zinc-air battery;
17. conductive carbon black (SUPERP) and the C-FP catalysts of the present application are used in zinc air cell polarization and power density curves.
18. RDE scan plots at different sweep rates for the SUPER P catalyst;
19. RDE scan graphs at different sweep rates for the C-FP catalyst;
20. the SUPER P catalyst rotates the disk electrode Koutecky-Levic plot in oxygen saturated 0.1 MKOH;
21. C-FP catalyst rotating disk electrode Koutecky-Levic plot in oxygen saturated 0.1 MKOH;
22. the SUPER P catalyst was analyzed for H in an oxygen saturated 0.1MKOH by rotating disk electrode 2 O 2 % yield and electron transfer number;
23. C-FP catalyst rotating disk electrode in oxygen saturated 0.1MKOH analyzed H 2 O 2 % yield and number of electron transfer.
Detailed Description
The present application is further described in detail with reference to the following examples, which are specifically described: the following examples, in which no specific conditions are noted, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
Placing the high-temperature crucible for heat treatment of the filter residue powder into a tubular furnace for continuous heating; the old lithium iron phosphate battery is firstly discharged to below 2.0V.
Examples of preparation of starting materials and/or intermediates
Preparation example 1
The acid leaching treatment of the lithium iron phosphate positive electrode material powder comprises the following steps:
a: 5g of lithium iron phosphate positive electrode material powder was weighed and added to 100mL of 1mol L -1 Dissolving powder in sulfuric acid solution to obtain initial acid leaching solution;
b: slowly adding 6mL of hydrogen peroxide solution with the content of 30% into the initial acid leaching solution to obtain a mixed solution;
c: heating the mixed solution to 60 ℃ in a water bath, and continuously stirring the mixed solution while heating for 120min.
Preparation example 2
The acid leaching treatment of the lithium iron phosphate positive electrode material powder comprises the following steps:
a: 8g of lithium iron phosphate positive electrode material powder was weighed and added to 200mL of 2mol L -1 Dissolving powder in sulfuric acid solution to obtain initial acid leaching solution;
b: slowly adding 12mL of 30% hydrogen peroxide solution into the initial acid leaching solution to obtain a mixed solution;
c: heating the mixed solution to 60 ℃ in a water bath, and continuously stirring the mixed solution while heating for 180min.
Preparation example 3
The acid leaching treatment of the lithium iron phosphate positive electrode material powder comprises the following steps:
a: 10g of lithium iron phosphate positive electrode material powder was weighed and added to 300mL of 3mol L -1 Dissolving powder in sulfuric acid solution to obtain initial acid leaching solution;
b: slowly adding 15mL of 30% hydrogen peroxide solution into the initial acid leaching solution to obtain a mixed solution;
c: heating the mixed solution to 60 ℃ in a water bath, and continuously stirring the mixed solution while heating for 240min.
Preparation example 4
A method for preparing a carbon-based catalyst by utilizing a recovered conductive agent in a waste lithium iron phosphate battery comprises the following steps:
s1: taking out the positive electrode of the lithium ion battery after discharge disassembly, and separating the lithium iron phosphate positive electrode material from the aluminum foil;
s2: drying and grinding the lithium iron phosphate anode material to obtain lithium iron phosphate anode material powder;
s3: acid leaching: the acid-leached mixed solution obtained in preparation example 2;
s4: filtering and separating the heated and stirred mixed solution, and treating the filtrate obtained after filtering to further recover lithium;
s5: cleaning, drying and grinding the filter residue after filtering and separating to obtain filter residue powder;
s6: 100mg of filter residue powder is weighed, placed into a high-temperature crucible, further baked for 3 hours at 900 ℃ in a nitrogen atmosphere, and taken out after power-off cooling to room temperature, so as to obtain the Fe-N-P co-doped carbon catalyst.
Preparation example 5
A method for preparing a carbon-based catalyst by utilizing a recovered conductive agent in a waste lithium iron phosphate battery comprises the following steps:
s1: taking out the positive electrode of the lithium ion battery after discharge disassembly, and separating the lithium iron phosphate positive electrode material from the aluminum foil;
s2: drying and grinding the lithium iron phosphate anode material to obtain lithium iron phosphate anode material powder;
s3: acid leaching: the acid-leached mixed solution obtained in preparation example 2;
s4: filtering and separating the heated and stirred mixed solution, and treating the filtrate obtained after filtering to further recover lithium;
s5: cleaning, drying and grinding the filter residue after filtering and separating to obtain filter residue powder;
s6: 200mg of filter residue powder is weighed, placed into a high-temperature crucible, further baked for 4 hours at 900 ℃ in a nitrogen atmosphere, and taken out after power-off cooling to room temperature, so as to obtain the Fe-N-P co-doped carbon catalyst.
Preparation example 6
A method for preparing a carbon-based catalyst by utilizing a recovered conductive agent in a waste lithium iron phosphate battery comprises the following steps:
s1: taking out the positive electrode of the lithium ion battery after discharge disassembly, and separating the lithium iron phosphate positive electrode material from the aluminum foil;
s2: drying and grinding the lithium iron phosphate anode material to obtain lithium iron phosphate anode material powder;
s3: acid leaching: the acid-leached mixed solution obtained in preparation example 2;
s4: filtering and separating the heated and stirred mixed solution, and treating the filtrate obtained after filtering to further recover lithium;
s5: cleaning, drying and grinding the filter residue after filtering and separating to obtain filter residue powder;
s6: 300mg of filter residue powder is weighed, placed into a high-temperature crucible, further baked for 5 hours at 900 ℃ in a nitrogen atmosphere, and taken out after power-off cooling to room temperature, so as to obtain the Fe-N-P co-doped carbon catalyst.
Comparative preparation example 1
A Fe-N-P co-doped carbon catalyst was obtained in the same manner as in preparation example 5 except that the residue powder was calcined at 700℃for 4 hours in a nitrogen atmosphere.
Comparative preparation example 2
A Fe-N-P co-doped carbon catalyst was obtained in the same manner as in preparation example 5 except that the residue powder was calcined at 900℃for 4 hours in an ammonia atmosphere.
Examples
Example 1
The working electrode of the lithium ion battery with the carbon-based catalyst is a catalyst modified glassy carbon electrode obtained in preparation example 5, the counter electrode is a platinum wire, the reference electrode is an Hg/HgO electrode, and the electrolyte is 0.1MKOH solution;
the glass carbon working electrode is modified by adopting the prepared slurry, and comprises the following processing steps: weighing 4mg of the catalyst powder obtained in preparation example 5, adding into a glass bottle, adding 800 mu L of deionized water, 200 mu L of alcohol and 100 mu L of 5% Nafion solution, and performing ultrasonic treatment in ice water bath for 30min to prepare working electrode modification slurry; and sucking 5 mu L of the modified slurry by a pipetting gun, dripping the modified slurry on a glass carbon electrode, and naturally drying to prepare the battery working electrode.
Example 2
The working electrode of the lithium ion battery with the carbon-based catalyst is a catalyst modified glassy carbon electrode obtained in preparation example 5, the counter electrode is a platinum wire, the reference electrode is an Hg/HgO electrode, and the electrolyte is 0.1MKOH solution;
the glass carbon working electrode is modified by adopting the prepared slurry, and comprises the following processing steps: weighing 5mg of the catalyst powder obtained in preparation example 5, adding into a glass bottle, adding 900 mu L of deionized water, 300 mu L of alcohol and 150 mu L of 5% Nafion solution, and performing ultrasonic treatment in an ice water bath for 40min to prepare working electrode modification slurry; and sucking 7 mu L of the modified slurry by a pipetting gun, dripping the modified slurry on a glass carbon electrode, and naturally drying to prepare the battery working electrode.
Example 3
The working electrode of the lithium ion battery with the carbon-based catalyst is a catalyst modified glassy carbon electrode obtained in preparation example 5, the counter electrode is a platinum wire, the reference electrode is an Hg/HgO electrode, and the electrolyte is 0.1MKOH solution;
the glass carbon working electrode is modified by adopting the prepared slurry, and comprises the following processing steps: weighing 6mg of the catalyst powder obtained in preparation example 5, adding into a glass bottle, adding 1000 mu L of deionized water, 400 mu L of alcohol and 200 mu L of 5% Nafion solution, and performing ultrasonic treatment in an ice water bath for 60min to prepare working electrode modification slurry; and sucking 8 mu L of the modified slurry by using a pipetting gun, dripping the modified slurry on a glassy carbon electrode, and naturally drying to prepare the battery working electrode.
Example 4
A preparation method of a zinc-air battery taking Fe-N-P co-doped catalyst and conductive carbon black as positive electrodes respectively comprises the following steps: respectively weighing 25mg of Fe-N-P co-doped catalyst obtained in preparation example 5 and reference carbon black powder, ultrasonically dispersing in 10mL of ethanol, uniformly spraying on the surface of carbon paper with the thickness of 5cm multiplied by 5cm by adopting a spray gun, and preparing the catalyst with the loading capacity of 1mgcm -2 Is dried for later use; before the zinc negative plate is used, sand paper polishing is needed, the zinc air battery is assembled from the negative electrode, negative plate-zinc plate-partition frame (for charging electrolyte) -positive electrode-positive plate are sequentially arranged from left to right, the negative plate-zinc plate-partition frame is fixedly packaged, and 6mol L is filled in the partition frame in the middle of the battery -1 KOH and 0.2mol L -1 Zn (Ac) 2 And standing the electrolyte for 2 hours to obtain the electrolyte.
Comparative example
Comparative example 1
A lithium ion battery of carbon-based catalyst prepared according to the method of example 2, except that the glassy carbon working electrode was not modified with a pre-prepared slurry.
Comparative example 2
A lithium ion battery of carbon-based catalyst prepared according to the method of example 2, except that when the glassy carbon working electrode was modified with a slurry prepared in advance, the catalyst was an Fe-N-C catalyst.
Comparative example 3
A lithium ion battery with a carbon-based catalyst prepared according to the method of example 2, except that when the glassy carbon working electrode was modified with a pre-prepared slurry, the catalyst was a PANI-Fe-C catalyst.
Comparative example 4
A zinc air cell was prepared as in example 4, except that no reference carbon black powder was added.
The morphology change of the materials before (filter residue) and after (catalyst) roasting is represented by a scanning electron microscope, and the composition components of the waste lithium ion battery lithium iron phosphate anode material, the filter residue after leaching and the catalyst after heat treatment are represented by X-ray diffraction analysis.
Analysis by X-ray diffraction (XRD) shows that the main component of the positive electrode material of the waste lithium ion battery is lithium iron phosphate, which is shown in figure 4, and the component of the leaching residue is mainly ferric phosphate (FePO) 4 ) And carbon black referring to fig. 5, the lithium leaching rate reaches 99.3%. XRD analysis shows FePO after calcination of leaching residue in N2 atmosphere 4 Vanishing and Fe is generated 2 P and Fe 2 P 2 O 7 Refer to fig. 6.
X-ray photoelectron spectroscopy (XPS) analysis shows that C-N, C-P, fe-N, pyridine N, pyrrole N, graphite N and other groups are formed on the surface of the calcined carbon black, and referring to fig. 7 and 8, the reaction of recovering the conductive agent carbon black after heat treatment on FePO4 is illustrated, so that the Fe-N-P co-doped catalyst (C-FP) is formed. Wherein, graphite N can improve ORR limit current density, pyridine N is favorable for increasing initial potential, and Fe atoms are easy to coordinate with pyridine N to generate Fe-N structure, and work together with C-N to strengthen oxygen reduction catalysis.
Cyclic Voltammogram (CV), time current curve (i-t), rotating disk electrode (RDE, LSV) and rotating ring disk electrode (RRDE, LSV) analyses were performed with an electrochemical workstation of the CHI760 type, with the electrolyte being a 0.1m koh solution, which was used for 30 minutes with oxygen bubbling.
In cyclic voltammogram test, the voltage window is set to be-0.6V-0.2V, and the scanning rate is 20mVs -1 . The test results showed that both the catalyst (C-FP) and the conductive carbon black (SUPERP) exhibited oxygen reduction peaks in CV cycles, but the catalyst (C-FP) had an oxygen reduction peak current density and voltage greater than those of the conductive carbon black (SUPERP), indicating that the oxygen reduction performance of the catalyst (C-FP) was better than that of FIG. 9.
When the rotating disc electrode and the rotating ring disc electrode are tested, the voltage window is set to be-0.6V-0.2V, and the scanning speed is set to be 5mVs -1 The potential of the ring electrode was set to 0.9V. The test results showed that the initial potential of the catalyst (C-FP) was 0.845V, which was 0.81V higher than the initial potential of the conductive carbon black (SUPERP), and the current density of the catalyst (C-FP) was also greater than the conductive carbon black (SUPERP), as shown in FIG. 10. Analysis of the rotating disk electrode and rotating ring disk electrode also showed that the number of electron transfer during ORR for the catalyst (C-FP) was between 3.5 and 3.8, see fig. 11 and 12. It can be seen that ORR on the catalyst (C-FP) is a process approaching four electron transfer, i.e. the reduction of oxygen molecules mainly to water.
The current time curve test set voltage 0.3V, test time is 80000s (22.2 h). The catalyst stability was found to be high in the long-term i-t curve test, and the current decayed only to the initial 73.5% referring to fig. 13.
The test results show that the open circuit voltage of the zinc-air cell using the C-FP catalyst as the positive electrode is 1.44V with reference to fig. 14, the charge-discharge voltage difference is 1.04V, and the cycle can be stabilized over 100h with reference to fig. 15; when the battery is completely discharged, the specific density is 581mAhg according to the mass of the consumed zinc foil Zn -1 Referring to FIG. 16, the power density reached 80mWcm -2 Refer to fig. 17. In contrast, the open circuit voltage of the zinc-air cell using conductive carbon black as the positive electrode was 1.37V with reference to fig. 14, the charge-discharge voltage difference was 1.19V, and only the stable cycle 18h was possible with reference to fig. 15; when the battery is completely discharged, the specific density is 453mAhg according to the mass of the consumed zinc foil Zn -1 Referring to FIG. 16, the power density reached 11mWcm -2 Refer to fig. 17. It can be seen that the recovery guideThe C-FP catalyst prepared by the electric agent is superior to conductive carbon black in strengthening a rechargeable zinc-air battery.
RDE analysis of the SUPER P (FIG. 18) and C-FP (FIG. 19) catalysts was performed at a scan rate of 5mV/s at 400-1600rpm, and then the electron transfer numbers during ORR were calculated to be 1.9 (FIG. 20) and 3.7 (FIG. 21) by the Koutesky-Levich (K-L) equation, respectively. RRDE analysis showed that ORR on SUPERP catalyst (FIG. 22) was a near 2 electron transfer process with a yield of H2O2 higher than 80% and ORR on C-FP catalyst (FIG. 23) was a near 4 electron transfer process with H production in the range of-0.8-0.4V 2 O 2 The yield of (2) is lower than 40%, i.e. O 2 Is mainly reduced to H 2 O。
The ICP test showed that the iron content of the solids was almost unchanged before and after the acid leaching, and the lithium leaching rate was 99.37% (tables 1 and 2).
TABLE 1 ICP of waste lithium iron phosphate anode
TABLE 2 ICP of residue after acid leaching
While the present disclosure has been described with respect to exemplary embodiments thereof, it should be understood that the scope of the present disclosure is not limited thereto, but rather, any changes or substitutions that would occur to one skilled in the art within the scope of the present disclosure should be included in the scope of the present disclosure. Therefore, the protection scope of the present disclosure should be subject to the protection scope of the claims.
Claims (10)
1. The method for preparing the carbon-based catalyst by utilizing the recovered conductive agent in the waste lithium iron phosphate battery is characterized by comprising the following steps of:
s1: taking out the positive electrode of the lithium ion battery after discharge disassembly, and separating the lithium iron phosphate positive electrode material from the aluminum foil;
s2: drying and grinding the lithium iron phosphate anode material to obtain lithium iron phosphate anode material powder;
s3: acid leaching: weighing lithium iron phosphate anode material powder, adding the lithium iron phosphate anode material powder into sulfuric acid and hydrogen peroxide solution to obtain a mixed solution, heating the mixed solution to 60-80 ℃ in a water bath, and continuously stirring for 120-240min;
s4: filtering and separating the heated and stirred mixed solution, and treating the filtrate obtained after filtering to further recover lithium;
s5: cleaning, drying and grinding the filter residue after filtering and separating to obtain filter residue powder;
s6: weighing 100-300mg of filter residue powder, placing into a high-temperature crucible, roasting for 3-5 hours at 600-900 ℃ in a nitrogen atmosphere, cooling to room temperature after power failure, and taking out to obtain the Fe-N-P co-doped carbon catalyst.
2. The method for preparing a carbon-based catalyst according to claim 1, wherein the acid leaching of the lithium iron phosphate positive electrode material powder comprises the steps of:
a: weighing 5-10g of lithium iron phosphate positive electrode material powder, adding into 100-300mL of 1-3mol L -1 Dissolving powder in sulfuric acid solution to obtain initial acid leaching solution;
b: slowly adding 6-15mL of hydrogen peroxide solution into the initial acid leaching solution to obtain a mixed solution;
c: heating the mixed solution to 60-80 ℃ in a water bath, and continuously stirring the mixed solution while heating for 120-240min.
3. The method for preparing a carbon-based catalyst according to claim 2, wherein the hydrogen peroxide solution is contained in an amount of 10 to 30%.
4. The method for preparing a carbon-based catalyst according to claim 1, wherein the treatment method of the filtrate comprises acid-base neutralization or carbonate precipitation treatment.
5. The method of preparing a carbon-based catalyst according to claim 1, wherein the conductive carbon black has an oil absorption value of 250mLg or more -1 。
6. The method for preparing a carbon-based catalyst according to claim 5, wherein the main component of the lithium iron phosphate positive electrode material of the waste lithium ion battery is lithium iron phosphate, and the main component of the leached filter residue is iron phosphate (FePO 4 ) And carbon black.
7. The method for producing a carbon-based catalyst according to claim 5, wherein the composition of the catalyst is Fe 2 P and Fe 2 P 2 O 7 And the carbon black surface after calcination forms C-N, C-P, fe-N, pyridine N, pyrrole N and graphite N groups.
8. The application of the waste lithium iron phosphate battery to the preparation of the carbon-based catalyst is characterized in that the carbon-based catalyst prepared by the waste lithium iron phosphate battery to the recovery of the conductive agent is used for a battery, a working electrode of the battery is a catalyst modified glassy carbon electrode, a counter electrode is a platinum wire, a reference electrode is an Hg/HgO electrode, and an electrolyte is 0.1MKOH solution.
9. The application of the waste lithium iron phosphate battery to prepare the carbon-based catalyst according to claim 8, wherein the working electrode of the battery is a catalyst modified glassy carbon electrode, and the application comprises the following processing steps:
weighing 4-6mg of catalyst powder, adding into a glass bottle, adding 800-1000 mu L of deionized water, 200-400 mu L of alcohol and 100-200 mu L of 5% Nafion solution, and performing ultrasonic treatment in ice water bath for 30-60min to prepare working electrode modification slurry; and sucking 5-8 mu L of the modified slurry by using a pipetting gun, dripping the modified slurry on a glassy carbon electrode, and naturally drying to prepare the battery working electrode.
10. The application of the waste lithium iron phosphate battery to the preparation of the carbon-based catalyst by recycling the conductive agent is characterized in that the carbon-based catalyst is used for a zinc-air battery, and the preparation method of the zinc-air battery comprises the following steps: respectively weighing 25mg of the Fe-N-P co-doped catalyst and reference carbon black powder, dispersing in 10mL of ethanol by ultrasonic, and uniformly spraying on the surface of carbon paper with the thickness of 5cm multiplied by 5cm by adopting a spray gun to prepare the catalyst with the loading capacity of 1mgcm -2 Is dried for later use; before the zinc negative plate is used, sand paper polishing is needed, the zinc air battery is assembled from the negative electrode, negative plate-zinc plate-partition frame (for charging electrolyte) -positive electrode-positive plate are sequentially arranged from left to right, the negative plate-zinc plate-partition frame is fixedly packaged, and 6mol L is filled in the partition frame in the middle of the battery -1 KOH and 0.2mol L -1 Zn (Ac) 2 And standing the electrolyte for 2 hours to obtain the electrolyte.
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