CN114744192A - Regeneration method of lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode material and application - Google Patents
Regeneration method of lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode material and application Download PDFInfo
- Publication number
- CN114744192A CN114744192A CN202210394871.0A CN202210394871A CN114744192A CN 114744192 A CN114744192 A CN 114744192A CN 202210394871 A CN202210394871 A CN 202210394871A CN 114744192 A CN114744192 A CN 114744192A
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- lithium iron
- positive electrode
- powder
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 54
- 238000011069 regeneration method Methods 0.000 title claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 title claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 20
- 239000008103 glucose Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000010406 cathode material Substances 0.000 claims abstract description 6
- 238000007670 refining Methods 0.000 claims abstract description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 4
- 230000008929 regeneration Effects 0.000 abstract description 15
- 239000002699 waste material Substances 0.000 abstract description 13
- 239000002033 PVDF binder Substances 0.000 abstract description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000010926 waste battery Substances 0.000 abstract description 2
- 239000002071 nanotube Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The disclosure belongs to the field of new energy, and particularly relates to a regeneration method of a lithium iron phosphate anode material, the lithium iron phosphate anode material and application; comprises carbon nano-tubes and lithium iron phosphate powder, uses 1:1 ethanol water solution as a dispersant, and uses 2-10% (wt) of carbon nano-tubes, 5-30% (wt) of glucose and 10% (at) of Li2CO3Adding the mixture into lithium iron phosphate powder, and completely mixing; drying the mixture at 80 deg.C, grinding and refining; and keeping the ground powder at 200-600 ℃ for 2h under the condition of argon, and then heating to 400-800 ℃ for 12h to obtain the lithium iron phosphate cathode material. And (4) disassembling the waste battery after pre-discharging to obtain the positive electrode plate. And then heating the positive electrode powder in the air to remove carbon components and electrolytes such as polyvinylidene fluoride (PVDF), and washing and drying to obtain the waste LFP material. And (3) performing one-step high-temperature calcination regeneration to obtain the regenerated LFP. At the same time, at the same timeCarbon nanotubes are doped in the growing process, and the regenerated LFP material shows higher rate performance and capacity retention rate.
Description
Technical Field
The disclosure belongs to the field of new energy, and particularly relates to a regeneration method of a lithium iron phosphate anode material, the lithium iron phosphate anode material and application.
Background
At present, the recycling method of the waste lithium ion battery is widely developed, such as an extraction method, a chemical precipitation method, an electrolysis method and a cooperative recycling method. Wet recovery is the most common method. The separated LiFePO is usually decomposed4The positive electrode material is leached by acid-base solution to obtain solution containing metal ions, relevant precipitating agent is added into the solution to selectively precipitate the metal ions to separate Li, Fe and P elements, and the obtained elements are recovered in a salt form or synthesized into the LFP positive electrode material again. These processes are widely used but still suffer from some unavoidable disadvantages. For example, a large amount of chemical reagents are used in the wet recovery process, so that a large amount of salt-containing wastewater is discharged, and secondary pollution is caused; the harmful materials in the electrolyte are not well recovered or disposed.
Disclosure of Invention
Aiming at the defects of the prior art, the present disclosure aims to provide a regeneration method of a lithium iron phosphate positive electrode material, a lithium iron phosphate positive electrode material and an application thereof, which are used for LiFePO4And (4) recycling the cathode material. The direct regeneration method in the invention does not involve the use of substances such as acid, alkali and the like, and does not produce secondary pollution.
The purpose of the disclosure can be realized by the following technical scheme:
in a first aspect, the present disclosure discloses a lithium iron phosphate positive electrode material comprising a carbon nanotube and lithium iron phosphate powder using a 1:1 ethanol aqueous solution as a solventA dispersant prepared by mixing 2-10% (wt) of carbon nanotubes, 5-30% (wt) of glucose and 10% (at) of Li2CO3Adding the mixture into lithium iron phosphate powder, and completely mixing;
drying the mixture at 80 deg.C, grinding and refining;
and keeping the ground powder at 200-600 ℃ for 2h under the condition of argon, and then heating to 400-800 ℃ for 12h to obtain the lithium iron phosphate cathode material.
In some disclosures, the carbon nanotube content is 5% (wt), the glucose content is 15% (wt); or, the carbon nano tube content is 3% (wt), the glucose content is 9% (wt); alternatively, the carbon nanotube content is 10% (wt) and the glucose content is 30% (wt).
In some disclosures, the lithium iron phosphate powder preparation includes the following steps:
fully discharging the lithium iron phosphate battery to below 0.6V, then disassembling, and carrying out the whole process in an environment filled with argon (the water oxygen index is less than 0.01 ppm);
soaking the anode plate obtained by disassembly in ionized water, and performing ultrasonic separation to obtain LFP powder;
after drying at 80 ℃, the powder obtained was a lithium iron phosphate powder.
In some disclosures, the carbon nano tube is modified, and the carbon nano tube is heated for 1h at the temperature of 300-800 ℃;
after heating, adding concentrated nitric acid, heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate; washing with deionized water and drying at 100 ℃ for 2h to obtain the modified carbon nano tube.
In a second aspect, the present disclosure discloses a regeneration method of a lithium iron phosphate positive electrode material, comprising the following steps:
using 1:1 ethanol water solution as dispersant, 2-10% (wt) of carbon nano tube, 5-30% (wt) of glucose and 10% (at) of Li2CO3Adding into lithium iron phosphate powder, and mixing completely;
drying the mixture at 80 deg.C, grinding and refining;
and maintaining the ground powder at 200-600 ℃ for 2 hours under the condition of argon, and then heating to 400-800 ℃ for 12 hours to obtain the lithium iron phosphate cathode material.
In some disclosures, the carbon nanotube content is 5% (wt), the glucose content is 15% (wt); or, the carbon nano tube content is 3% (wt), the glucose content is 9% (wt); alternatively, the carbon nanotube content is 10% (wt) and the glucose content is 30% (wt).
In some disclosures, the lithium iron phosphate powder preparation includes the following steps:
fully discharging the lithium iron phosphate battery to below 0.6V, then disassembling, and carrying out the whole process in an environment filled with argon (the water oxygen index is less than 0.01 ppm);
soaking the anode plate obtained by disassembly in ionized water, and performing ultrasonic separation to obtain LFP powder;
after drying at 80 ℃, the powder obtained was a lithium iron phosphate powder.
In some disclosures, the carbon nano tube is modified, and the carbon nano tube is heated for 1h at the temperature of 300-800 ℃;
after heating, adding concentrated nitric acid, and heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate the nitric acid; washing with deionized water and drying at 100 ℃ for 2h to obtain the modified carbon nano tube.
In some disclosures, the carbon nanotube is heated at 360 ℃, 480 ℃, or 600 ℃.
In a third aspect, the present disclosure discloses the material of the first aspect or the material prepared by the material preparation method of the second aspect, which is applied to a lithium battery as a positive electrode material.
The beneficial effect of this disclosure:
according to the method, the positive electrode plate is obtained by disassembling the waste battery after pre-discharging. And then heating the positive electrode powder in the air to remove carbon components and electrolytes such as polyvinylidene fluoride (PVDF), and washing and drying to obtain the waste LFP material. And (3) performing one-step high-temperature calcination regeneration to obtain the regenerated LFP. Meanwhile, the carbon nano tube is doped in the regeneration process, and the regenerated LFP material shows higher rate performance and capacity retention rate.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present disclosure, the drawings used in the embodiments or technical solutions of the present disclosure will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a scanning electron microscope image, wherein (a) is waste lithium iron phosphate (W-LFP) which is not subjected to regeneration treatment, and (b) is waste lithium iron phosphate (W-LFP) which is subjected to regeneration treatment;
FIG. 2 shows the complete XPS spectra of N-LFP, W-LFP, and R-LFP.
Detailed Description
The technical solutions in the embodiments of the present disclosure will be described clearly and completely with reference to the drawings in the embodiments of the present disclosure, and it is obvious that the embodiments described are only some embodiments of the present disclosure, rather than all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
Example 1A method for modifying carbon nanotubes
The carbon nano tube is placed in a high temperature furnace and heated for 1h at 480 ℃ under the air condition so as to oxidize and calcine and remove impurities with poor crystallinity. After heating, adding concentrated nitric acid, heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate; washing the carbon nano tube to be neutral by deionized water and drying the carbon nano tube at 100 ℃ for 2h to obtain the modified carbon nano tube.
Example 2A method for modifying carbon nanotubes
Placing the carbon nano tube in a high-temperature furnace, and heating for 1h at 360 ℃ under the air condition to perform oxidation calcination and remove impurities. After heating, adding concentrated nitric acid, and heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate the nitric acid; washing with deionized water and drying at 100 deg.c for 2 hr to obtain modified carbon nanotube.
Example 3A method for modifying carbon nanotubes
The carbon nano tube is placed in a high-temperature furnace and heated for 1h at 600 ℃ under the air condition to be oxidized and calcined and remove impurities. After heating, adding concentrated nitric acid, and heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate the nitric acid; washing with deionized water and drying at 100 deg.c for 2 hr to obtain modified carbon nanotube.
Example 4 treatment of waste lithium iron phosphate (W-LFP) without regeneration treatment
Fully discharging the waste lithium iron phosphate battery (20Ah soft package battery) to below 0.6V, then disassembling, and carrying out the whole process in a glove box filled with argon (the water oxygen index is less than 0.01 ppm). And (4) moving the anode plate obtained by disassembly out of the glove box, and soaking the anode plate in ionized water so as to ultrasonically separate the waste LFP powder from the aluminum foil. After drying at 80 ℃ the powder obtained is marked as waste LiFePO4I.e. "W-LFP".
Certainly, for convenience of display, what is described in this application is a soft package battery of 20Ah waste lithium iron phosphate, and in other cases, of course, other specifications may also be adopted.
Embodiment 5. composite regeneration method of waste lithium iron phosphate doped with carbon nanotubes in embodiment 1
Using a 1:1 ethanol aqueous solution as a dispersant, 5% wt of modified carbon nanotubes (sample in example 1), 15% (wt) glucose and 10% (at) Li2CO3Added to the W-LFP powder and the mixture was then ball milled to complete mixing. Drying the mixture at 80 deg.C, and grinding the dried powder uniformly. The powder is placed in a tube furnace and is kept for 2h at 350 ℃ under the condition of argon, and then is heated to 650 ℃ and kept for 12 h. The regenerated LiFePO obtained4Labeled "R-LFP".
Embodiment 6. composite regeneration method of waste lithium iron phosphate doped with carbon nanotubes of embodiment 1
Using a 1:1 ethanol aqueous solution as a dispersant, 3% wt of modified carbon nanotubes (sample in example 1), 9% (wt) glucose and 10% (at) Li2CO3Added to the W-LFP powder and the mixture was then ball milled to complete mixing. Drying the mixture at 80 deg.C, and grinding the dried powderAnd further refining. The powder is placed in a tube furnace and is kept for 2h at 350 ℃ under the condition of argon, and then is heated to 650 ℃ and kept for 12 h. The regenerated LiFePO obtained4Labeled "R-LFP".
Embodiment 7. composite regeneration method of waste lithium iron phosphate doped with carbon nanotubes of embodiment 1
Using a 1:1 ethanol aqueous solution as a dispersant, 10% wt of modified carbon nanotubes (sample in example 1), 30% (wt) glucose and 10% (at) Li2CO3Added to the W-LFP powder and the mixture was then ball milled to complete mixing. The mixture was dried at 80 c and the dried powder was ground and further refined. The powder is placed in a tube furnace and is kept for 2h at 350 ℃ under the condition of argon, and then is heated to 650 ℃ and kept for 12 h. The regenerated LiFePO obtained4Labeled "R-LFP".
Example 8 SEM scanning analysis of Material Structure before and after regeneration
To evaluate the effect of the recycled material, SEM scan analysis was performed on the material before and after recycling. FIG. 1 shows the results of SEM analysis of W-LFP and R-LFP. As can be seen from FIG. 1(a), due to the residual PVDF as the binder, there was serious agglomeration among the W-LFP particles, and the particle size was not uniform, indicating that the microstructure of the W-LFP was destroyed. FIG. 1(b) shows the SEM analysis result of R-LFP, from which it can be seen that the modified carbon nanotubes are crosslinked with R-LFP, and the particle size of R-LFP is relatively uniform, which indicates that the structure of the regenerated material is recovered.
Example 9 elemental analysis of materials before and after regeneration
To further verify the regeneration effect, elemental analysis before and after regeneration was performed. FIG. 2 shows the results of X-ray photoelectron spectroscopy (XPS) analysis to further characterize N-LFP (New LiFePO)4) W-LFP and R-LFP. The C, O, P and Fe element contents are listed in Table 1. Compared with W-LFP, the O, P, Fe molar concentration ratio in R-LFP is 6.07: 1.51: 1.00, which is close to that of N-LFP. The regeneration was successful as evidenced by the elemental content.
TABLE 1 contents of C, O, P, Fe elements of N-LFP, W-LFP, R-LFP
Example 10 analysis of electrochemical Properties of materials before and after regeneration
To verify the rate performance of the material before and after regeneration, the material was first cycled twice through active charge and discharge at a rate of 0.05C, and then cycled at different rates up to 2C. Compared with W-LFP, R-LFP has specific discharge capacity of about 151.43, 148.67, 141.27, 131.83 and 119.50mAh/g at 0.1, 0.2, 0.5, 1 and 2C respectively, and has remarkable regeneration effect at high rate. When the rate is reduced to 0.1C, the discharge capacity of the R-LFP is still kept at a higher specific discharge capacity of 150.12mAh/g, and the excellent stability of the regeneration electrode material and the SEI film thereof in the circulation process is revealed. In addition, the cycling stability of N-LFP, W-LFP and R-LFP in the range of 0.1 to 1C was also investigated. As shown in Table 2, R-LFP shows excellent long-term cycling performance close to that of N-LFP as the number of cycles increases.
TABLE 2 Cyclic stability of N-LFP, W-LFP and R-LFP materials
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the disclosure. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing illustrates and describes the general principles, principal features, and advantages of the present disclosure. It will be understood by those skilled in the art that the present disclosure is not limited to the embodiments described above, which are presented solely for purposes of illustrating the principles of the disclosure, and that various changes and modifications may be made to the disclosure without departing from the spirit and scope of the disclosure, which is intended to be covered by the claims.
Claims (10)
1. The lithium iron phosphate positive electrode material is characterized by comprising a carbon nano tube and lithium iron phosphate powder, wherein a 1:1 ethanol water solution is used as a dispersing agent, and 2-10% (wt) of the carbon nano tube, 5-30% (wt) of glucose and 10% (at) of Li are added2CO3Adding the mixture into lithium iron phosphate powder, and completely mixing;
drying the mixture at 80 deg.C, grinding and refining;
and keeping the ground powder at 200-600 ℃ for 2h under the condition of argon, and then heating to 400-800 ℃ for 12h to obtain the lithium iron phosphate cathode material.
2. The lithium iron phosphate positive electrode material according to claim 1, wherein the content of the carbon nanotubes is 5% (wt), and the content of glucose is 15% (wt); or, the carbon nano tube content is 3% (wt), the glucose content is 9% (wt); alternatively, the carbon nanotube content is 10% (wt) and the glucose content is 30% (wt).
3. The lithium iron phosphate positive electrode material according to claim 1, wherein the preparation of the lithium iron phosphate powder comprises the following steps:
fully discharging the lithium iron phosphate battery to below 0.6V, then disassembling, and carrying out the whole process in an environment filled with argon (the water oxygen index is less than 0.01 ppm);
soaking the anode plate obtained by disassembly in ionized water, and performing ultrasonic separation to obtain LFP powder;
after drying at 80 ℃, the powder obtained was a lithium iron phosphate powder.
4. The lithium iron phosphate positive electrode material according to any one of claims 1 to 3, wherein the carbon nanotubes are modified by heating the carbon nanotubes at 300 to 800 ℃ for 1 hour;
after heating, adding concentrated nitric acid, heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate; washing with deionized water and drying at 100 ℃ for 2h to obtain the modified carbon nano tube.
5. A regeneration method of a lithium iron phosphate positive electrode material is characterized by comprising the following steps:
using 1:1 ethanol water solution as dispersant, 2-10% (wt) of carbon nano tube, 5-30% (wt) of glucose and 10% (at) of Li2CO3Adding the mixture into lithium iron phosphate powder, and completely mixing;
drying the mixture at 80 deg.C, grinding and refining;
and maintaining the ground powder at 200-600 ℃ for 2 hours under the condition of argon, and then heating to 400-800 ℃ for 12 hours to obtain the lithium iron phosphate cathode material.
6. The method for regenerating a lithium iron phosphate positive electrode material according to claim 5, wherein the content of the carbon nanotubes is 5% (wt), and the content of glucose is 15% (wt); or, the carbon nano tube content is 3% (wt), the glucose content is 9% (wt); alternatively, the carbon nanotube content is 10% (wt) and the glucose content is 30% (wt).
7. The method for regenerating a lithium iron phosphate positive electrode material according to claim 5, wherein the preparation of the lithium iron phosphate powder comprises the following steps:
fully discharging the lithium iron phosphate battery to below 0.6V, then disassembling, and carrying out the whole process in an environment filled with argon (the water oxygen index is less than 0.01 ppm);
soaking the anode plate obtained by disassembly in ionized water, and performing ultrasonic separation to obtain LFP powder;
after drying at 80 ℃, the powder obtained was a lithium iron phosphate powder.
8. The method for regenerating the lithium iron phosphate positive electrode material as claimed in any one of claims 5 to 7, wherein the carbon nanotubes are modified by heating the carbon nanotubes at 300 to 800 ℃ for 1 hour;
after heating, adding concentrated nitric acid, and heating and refluxing for 10h at 100 ℃ to hydroxylate and carboxylate the nitric acid; washing with deionized water and drying at 100 ℃ for 2h to obtain the modified carbon nano tube.
9. The method for regenerating a lithium iron phosphate positive electrode material according to claim 8, wherein the carbon nanotube is heated to 360 ℃, 480 ℃ or 600 ℃.
10. The material according to any one of claims 1 to 4 or the material prepared by the method for preparing a material according to any one of claims 5 to 9, which is used as a positive electrode material in a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210394871.0A CN114744192A (en) | 2022-04-14 | 2022-04-14 | Regeneration method of lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210394871.0A CN114744192A (en) | 2022-04-14 | 2022-04-14 | Regeneration method of lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode material and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114744192A true CN114744192A (en) | 2022-07-12 |
Family
ID=82281988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210394871.0A Pending CN114744192A (en) | 2022-04-14 | 2022-04-14 | Regeneration method of lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114744192A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634222A (en) * | 2017-09-16 | 2018-01-26 | 兰州理工大学 | A kind of renovation process of waste lithium iron phosphate positive electrode |
| CN111403837A (en) * | 2019-11-11 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Regeneration method of lithium iron phosphate in retired lithium battery |
| CN113582153A (en) * | 2021-09-30 | 2021-11-02 | 中南大学 | Waste lithium iron phosphate cathode material for repairing and regenerating and repairing and regenerating method thereof |
| CN113782857A (en) * | 2021-08-20 | 2021-12-10 | 南京信息工程大学 | Method for repairing and regenerating anode material of waste lithium iron phosphate battery and application |
-
2022
- 2022-04-14 CN CN202210394871.0A patent/CN114744192A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634222A (en) * | 2017-09-16 | 2018-01-26 | 兰州理工大学 | A kind of renovation process of waste lithium iron phosphate positive electrode |
| CN111403837A (en) * | 2019-11-11 | 2020-07-10 | 余姚市鑫和电池材料有限公司 | Regeneration method of lithium iron phosphate in retired lithium battery |
| CN113782857A (en) * | 2021-08-20 | 2021-12-10 | 南京信息工程大学 | Method for repairing and regenerating anode material of waste lithium iron phosphate battery and application |
| CN113582153A (en) * | 2021-09-30 | 2021-11-02 | 中南大学 | Waste lithium iron phosphate cathode material for repairing and regenerating and repairing and regenerating method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3907182B1 (en) | Method for producing lithium iron phosphate precursor by using retired lithium iron phosphate battery as raw material | |
| JP7220360B2 (en) | Method for recovering positive electrode material, obtained positive electrode material and use thereof | |
| Yao et al. | LiMn2O4 prepared from waste lithium ion batteries through sol-gel process | |
| US20210226202A1 (en) | Lithium ion battery negative electrode material and preparation method therefor | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN102751549A (en) | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries | |
| WO2023116018A1 (en) | Recovery method for retired lithium ion battery electrode material and use thereof | |
| CN111048862B (en) | Method for efficiently recovering lithium ion battery anode and cathode materials as supercapacitor electrode materials | |
| Yang et al. | A combined method of leaching and co-precipitation for recycling spent LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode materials: process optimization and performance aspects | |
| CN113072052A (en) | Waste lithium iron phosphate lithium supplement repair method and application | |
| CN112607789A (en) | Process for recovering valuable metals and regenerating anode materials of waste lithium ion batteries | |
| CN114335781A (en) | Method for extracting precious metal from waste lithium battery | |
| Liu et al. | Pyrometallurgically regenerated LiMn2O4 cathode scrap material and its electrochemical properties | |
| CN115347265A (en) | Method for preparing copper-aluminum co-doped modified lithium iron phosphate positive electrode material from waste lithium iron phosphate battery | |
| CN113206227B (en) | Method for preparing carbon-based metal sulfide negative electrode material by simultaneously recycling positive and negative electrode materials of waste nickel-cobalt-manganese lithium ion battery | |
| CN112886084B (en) | Method for repairing layered oxide positive electrode material of sodium ion battery | |
| CN110563046B (en) | Method for recycling waste lithium ion battery anode material | |
| CN117393886A (en) | Method for regenerating and repairing graphite of negative electrode of waste lithium ion battery | |
| CN116845408A (en) | Method for recycling waste lithium cobaltate battery positive electrode material by using water-based eutectic solvent | |
| US20240120566A1 (en) | Method of recycling positive electrode active material and recycled positive electrode active material prepared by the same | |
| CN115472948A (en) | Method for regenerating sodium-electricity positive electrode material by using waste lithium manganate | |
| CN116315219A (en) | Method for preparing carbon-based catalyst by recycling conductive agent from waste lithium iron phosphate battery and application of method | |
| CN114744192A (en) | Regeneration method of lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode material and application | |
| CN112830484B (en) | Modified graphite and preparation method thereof, lithium battery negative electrode material, lithium battery negative electrode sheet and lithium battery | |
| CN114566728A (en) | Recovery method of cobalt-free positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220712 |