CN115140722B - Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery - Google Patents
Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery Download PDFInfo
- Publication number
- CN115140722B CN115140722B CN202210650984.2A CN202210650984A CN115140722B CN 115140722 B CN115140722 B CN 115140722B CN 202210650984 A CN202210650984 A CN 202210650984A CN 115140722 B CN115140722 B CN 115140722B
- Authority
- CN
- China
- Prior art keywords
- lithium
- vanadyl phosphate
- waste
- positive electrode
- vanadium
- 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.)
- Active
Links
- -1 vanadyl phosphate lithium Chemical compound 0.000 title claims abstract description 35
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- 239000010452 phosphate Substances 0.000 claims abstract description 19
- 125000005287 vanadyl group Chemical group 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 7
- 230000001502 supplementing effect Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- AGFJBJZWQNDDPA-UHFFFAOYSA-K [O-2].[V+5].[Li+].P(=O)([O-])([O-])[O-] Chemical compound [O-2].[V+5].[Li+].P(=O)([O-])([O-])[O-] AGFJBJZWQNDDPA-UHFFFAOYSA-K 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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 invention discloses a method for preparing a positive electrode material by using a waste vanadyl phosphate lithium battery, which comprises the following steps: (1) Disassembling the waste vanadyl phosphate lithium battery to obtain a positive electrode, and crushing to obtain powder; (2) Roasting the powder, mixing the powder with an alkaline solution, and carrying out solid-liquid separation after reaction to obtain a solid; (3) Oxidizing the solid to obtain an oxidized product; (4) Detecting the content of lithium, vanadium and phosphorus elements in the oxidation product obtained in the step (3), supplementing a lithium source, a vanadium source or a phosphorus source according to the detection result, and mixing with the oxidation product to obtain a mixture, wherein the molar ratio of the lithium, vanadium and phosphorus elements in the mixture is (1-1.5): (1-1.5): 1; (5) calcining the mixture obtained in the step (4), crushing and sieving to obtain the lithium vanadyl phosphate anode material. The method can directly recover and prepare the lithium vanadyl phosphate anode material from the waste lithium vanadyl phosphate battery, and has simple process.
Description
Technical Field
The invention belongs to the technical field of recycling of battery materials, and particularly relates to a method for preparing a positive electrode material by using a waste vanadyl phosphate lithium battery.
Background
Lithium vanadyl phosphate (LiVOPO) 4 ) Is a polyanion compound lithium ion battery anode material, and the vanadyl phosphate lithium has better structural stability and better Li + And (3) the release performance. The lithium vanadyl phosphate has a higher discharge platform (3.9V vs Li/Li) + ) And a higher theoretical energy density (616 Wh/Kg), and therefore, are widely applied to the vanadyl phosphate lithium battery, thereby bringing a large amount of waste vanadyl phosphate lithium batteries.
In the existing recovery method for the positive electrode material in the waste vanadyl phosphate lithium battery, only vanadium-containing compounds and lithium-containing compounds can be recovered, extraction, impurity removal, concentration, crystallization and other processes are needed in the recovery process, the process is complex, a large amount of solvents are needed, and a large amount of wastes are generated.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a method for preparing the anode material by using the waste vanadyl phosphate lithium battery, the method can directly recover and prepare the vanadyl phosphate lithium anode material from the waste vanadyl phosphate lithium battery, the process is simple, and the obtained vanadyl phosphate lithium anode material can be directly used for preparing the vanadyl phosphate lithium battery.
The technical aim of the invention is realized by the following technical scheme:
a method for preparing a positive electrode material by using a waste vanadyl phosphate lithium battery comprises the following steps:
(1) Disassembling the waste vanadyl phosphate lithium battery to obtain a positive electrode, and crushing to obtain powder;
(2) Roasting the powder in the step (1), mixing with an alkaline solution, and carrying out solid-liquid separation after reaction to obtain a solid;
(3) Oxidizing the solid obtained in the step (2) to obtain an oxidized product;
(4) Detecting the content of lithium, vanadium and phosphorus elements in the oxidation product obtained in the step (3), supplementing a lithium source, a vanadium source or a phosphorus source according to the detection result, and mixing with the oxidation product to obtain a mixture, wherein the molar ratio of the lithium, vanadium and phosphorus elements in the mixture is (1-1.5): (1-1.5): 1;
(5) And (3) calcining the mixture obtained in the step (4), crushing and sieving to obtain the lithium vanadyl phosphate anode material.
It is further preferred that the molar ratio of lithium, vanadium and phosphorus elements in the mixture after mixing in step (4) is (1-1.1): 1:1.
Preferably, the roasting temperature in the step (2) is 300-400 ℃, and the roasting time is 4-8 hours.
Further preferably, the roasting temperature in the step (2) is 300-350 ℃ and the roasting time is 5-7h.
Preferably, the alkaline solution in step (2) is sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the oxidation treatment in the step (3) is to subject the solid matter to oxidation at 50-300 ℃ in an oxygen atmosphere for 4-8 hours.
It is further preferred that the oxidation treatment in step (3) is to oxidize the solid under an oxygen atmosphere at 150 to 250 ℃ for 5 to 7 hours.
Preferably, in step (4), the content of the element in the oxidation product is detected using an ICP detection method.
Preferably, the mode of mixing in the step (4) is ball milling.
Preferably, the calcination temperature in step (5) is 700-900 ℃ and the calcination time is 6-12h.
It is further preferred that the calcination temperature in step (5) is 700-800 ℃ and the calcination time is 8-12 hours.
Preferably, the atmosphere of calcination in step (5) is an aerobic atmosphere.
Preferably, the method for preparing the positive electrode material by using the waste vanadyl phosphate lithium battery comprises the following steps:
s1, disassembling a waste vanadyl phosphate lithium battery to obtain a positive electrode, and then crushing to obtain powder containing vanadyl phosphate lithium, aluminum and graphite;
s2, roasting the powder obtained in the step S1 for 4-8 hours at the temperature of 300-400 ℃ in air or in a reducing atmosphere;
s3, mixing the powder obtained after the S2 roasting with a sodium hydroxide solution, dissolving aluminum in the powder, and filtering to obtain filter mud;
s4, drying the filter mud obtained in the step S3, and then placing the filter mud into oxygen to oxidize the filter mud at 50-300 ℃ for 4-8 hours to obtain an oxidation product;
s5, detecting the content of lithium, vanadium and phosphorus elements in the oxidation product obtained in the step S4 through ICP, supplementing a lithium source, a vanadium source or a phosphorus source according to a detection result, mixing and ball milling for 5-9 hours to obtain a mixture, and enabling the molar ratio of the lithium, the vanadium and the phosphorus elements in the mixture to be (1-1.1): 1:1;
s6, calcining the mixture obtained in the step S5 for 6-12 hours in a non-reducing atmosphere at 700-900 ℃, crushing and sieving to obtain the lithium vanadium oxide phosphate anode material, wherein the non-reducing atmosphere is air, argon, helium, nitrogen and the like.
Use of a method as described above in the preparation of an electrode.
Use of a method as described above in the preparation of a battery.
The beneficial effects of the invention are as follows:
(1) According to the method for preparing the anode material by utilizing the waste vanadyl phosphate lithium battery, lithium, vanadium and phosphorus in the waste vanadyl phosphate lithium battery anode material are not separated after being respectively dissolved and precipitated by a solvent, but the waste vanadyl phosphate lithium battery anode material is directly treated simply, and then a lithium source, a vanadium source or a phosphorus source is supplemented according to an element detection result and is calcined to obtain the vanadyl phosphate lithium anode material, so that the process is simple, a large amount of solvents are not needed, a large amount of wastes are not generated, and the process is simple and easy to implement;
(2) According to the method for preparing the positive electrode material by utilizing the waste vanadyl phosphate lithium battery, the positive electrode material of the waste vanadyl phosphate lithium battery is firstly crushed into powder, then roasting is carried out, then the powder is mixed with an alkaline solution for reaction, the graphite in the powder is utilized to reduce positive tetravalent vanadium (neutral oxide) in the powder into positive trivalent or lower valent (alkaline oxide) so as to avoid the loss of vanadium ions caused by the reaction of the alkaline solution, meanwhile, aluminum in the powder can react with the alkaline solution to generate metaaluminate, after solid-liquid separation, aluminum in the powder is removed, the solid is subjected to oxidation treatment at a specific temperature, so that the positive trivalent or lower valent vanadium in the solid is oxidized into tetravalent vanadium so as to avoid further oxidation into pentavalent vanadium, and then the lithium source, the vanadium source and the phosphorus source are supplemented according to element detection results, and then the powder is calcined at the specific temperature, so that the vanadyl phosphate lithium positive electrode material is prepared.
The reaction principle is as follows:
and (3) reduction roasting: liVOPO 4 +nC＝LiVO (1-2n) PO 4 +nCO 2 ；
Alkali dissolution: 2Al+2NaOH+6H 2 O＝2Na[Al(OH) 4 ]+3H 2 ；
And (3) oxidation treatment: liVO (LiVO) (1-2n) PO 4 +mO 2 (excess) =livopo 4 +(m-1+2n)O 2 。
Drawings
Fig. 1 is an XRD pattern of the lithium vanadyl phosphate cathode material prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
a method for preparing a lithium vanadyl phosphate anode material by using a waste lithium vanadyl phosphate battery comprises the following steps:
s1, disassembling a waste vanadyl phosphate lithium battery A to obtain a positive electrode, crushing the positive electrode by using a vertical high-speed rotary crusher for 10 minutes, and screening the crushed material by using an 80-mesh standard sieve to obtain powder;
s2, weighing the powder, and roasting for 6 hours at 300 ℃ in an air atmosphere to obtain roasted powder;
s3, adding the roasted powder into 200ml of sodium hydroxide solution with the mass fraction of 5%, continuously stirring for 1h at 65 ℃ to dissolve aluminum, and filtering to obtain filter mud;
s4, drying the filter mud, and then placing the filter mud in oxygen to oxidize the filter mud at 200 ℃ for 6 hours to obtain an oxidized product;
s5, detecting the molar ratio of lithium, vanadium and phosphorus elements in the oxidation product to be 2.6:2.7:3.2 through ICP, finding that the content of lithium and vanadium is low, supplementing lithium hydroxide and vanadium pentoxide, and then performing mixing ball milling for 6 hours to obtain a mixture, wherein the molar ratio of the lithium, vanadium and phosphorus elements in the mixture is as follows: 1.1:1:1;
s6, calcining the mixture for 8 hours in a non-reducing atmosphere at 800 ℃, crushing and sieving to obtain the lithium vanadium oxide phosphate anode material A. As can be seen from the figure 1, compared with the standard card (PDF # 85-2438) spectrogram, the XRD chart of the lithium vanadyl phosphate anode material A is identical in characteristic peak one by one, no other impurity peak exists, the diffraction peak is sharp, the characteristic peak is obvious, and the prepared lithium vanadyl phosphate is high in purity and good in crystallinity.
Example 2:
a method for preparing a lithium vanadyl phosphate anode material by using a waste lithium vanadyl phosphate battery comprises the following steps:
s1, disassembling a waste vanadyl phosphate lithium battery B to obtain a positive electrode, crushing the positive electrode by using a vertical high-speed rotary crusher for 10 minutes, and screening the crushed material by using an 80-mesh standard sieve to obtain powder;
s2, weighing the powder, and roasting for 6 hours at 300 ℃ in an air atmosphere to obtain roasted powder;
s3, adding the roasted powder into 200ml of sodium hydroxide solution with the mass fraction of 5%, continuously stirring for 1h at 65 ℃ to dissolve aluminum, and filtering to obtain filter mud;
s4, drying the filter mud, and then placing the filter mud in oxygen to oxidize the filter mud at 200 ℃ for 6 hours to obtain an oxidized product;
s5, detecting the molar ratio of lithium, vanadium and phosphorus elements in the oxidation product to be 2.6:2.7:3.2 through ICP, finding that the content of lithium and vanadium is low, supplementing lithium hydroxide and vanadium pentoxide, and then performing mixing ball milling for 6 hours to obtain a mixture, wherein the molar ratio of the lithium, vanadium and phosphorus elements in the mixture is as follows: 1:1:1;
s6, calcining the mixture for 8 hours in a non-reducing atmosphere at 800 ℃, crushing and sieving to obtain the lithium vanadium oxide phosphate anode material B.
Example 3:
a method for preparing a lithium vanadyl phosphate anode material by using a waste lithium vanadyl phosphate battery comprises the following steps:
s1, disassembling a waste vanadyl phosphate lithium battery C to obtain a positive electrode, crushing the positive electrode by using a vertical high-speed rotary crusher for 10 minutes, and screening the crushed material by using an 80-mesh standard sieve to obtain powder;
s2, weighing the powder, and roasting for 6 hours at 300 ℃ in an air atmosphere to obtain roasted powder;
s3, adding the roasted powder into 200ml of sodium hydroxide solution with the mass fraction of 5%, continuously stirring for 1h at 65 ℃ to dissolve aluminum, and filtering to obtain filter mud;
s4, drying the filter mud, and then placing the filter mud in oxygen to oxidize the filter mud at 200 ℃ for 6 hours to obtain an oxidized product;
s5, detecting the molar ratio of lithium, vanadium and phosphorus in the oxidation product to be 2.6:3:2.9 by ICP, finding that the content of lithium and phosphorus is lower, supplementing lithium hydroxide and phosphoric acid, and then performing mixing ball milling for 6 hours to obtain a mixture, wherein the molar ratio of lithium, vanadium and phosphorus in the mixture is as follows: 1:1:1;
s6, calcining the mixture for 12 hours in a non-reducing atmosphere at 700 ℃, crushing and sieving to obtain the lithium vanadium oxide phosphate anode material C.
Test example:
the positive electrode materials A, B and C obtained in the examples 1-3 are used for preparing button cells for testing the electrochemical performance of lithium ion batteries, and the specific steps are as follows: n-methyl pyrrolidone is used as a solvent, the anode material, acetylene black and PVDF are uniformly mixed according to the mass ratio of 9.2:0.5:0.3, the mixture is coated on an aluminum foil, and the mixture is dried for 8 hours by blowing at 80 ℃ and then is dried for 12 hours in vacuum at 120 ℃. The battery is assembled in a glove box protected by argon, the negative electrode is a metal lithium sheet, the diaphragm is a polypropylene film, and the electrolyte is 1M LiPF 6 (lithium hexafluorophosphate) -EC (ethylene carbonate)/DMC (dimethyl carbonate) (1:1, V/V), a 2032-type button cell case was assembled into a button cell in an argon-protected glove box, and then electrochemical performance test was performed at 25 ℃ at 3.0-4.5V. The results are shown in Table 1.
TABLE 1 results of electrochemical Performance test of cells
As can be seen from Table 1, after the lithium vanadyl phosphate anode material prepared by the invention is prepared into a button cell, the specific charge and discharge capacity of the battery 0.1C is more than 132.7mAh/g, the specific charge and discharge capacity of the battery 0.1C after 100 circles is more than 113.7mAh/g, and the capacity retention rate of 100 circles is more than 85.46%, which indicates that the lithium vanadyl phosphate anode material prepared by the invention has relatively stable electrochemical performance and can be used for preparing the lithium vanadyl phosphate battery.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. A method for preparing a positive electrode material by using a waste vanadyl phosphate lithium battery is characterized by comprising the following steps: the method comprises the following steps:
(1) Disassembling the waste vanadyl phosphate lithium battery to obtain a positive electrode, and crushing to obtain powder;
(2) Roasting the powder in the step (1), mixing with an alkaline solution, and carrying out solid-liquid separation after reaction to obtain a solid;
(3) Oxidizing the solid obtained in the step (2) to obtain an oxidized product;
(4) Detecting the content of lithium, vanadium and phosphorus elements in the oxidation product obtained in the step (3), supplementing a lithium source, a vanadium source or a phosphorus source according to the detection result, and mixing with the oxidation product to obtain a mixture, wherein the molar ratio of the lithium, vanadium and phosphorus elements in the mixture is (1-1.5): (1-1.5): 1;
(5) Calcining the mixture obtained in the step (4), crushing and sieving to obtain a lithium vanadyl phosphate anode material;
the roasting temperature in the step (2) is 300-400 ℃, the roasting time is 4-8 hours, and the alkaline solution in the step (2) is sodium hydroxide solution and/or potassium hydroxide solution; the oxidation treatment in the step (3) is to put the solid in an oxygen atmosphere, and oxidize the solid at 50-300 ℃ for 4-8 hours; the calcination temperature in the step (5) is 700-900 ℃, the calcination time is 6-12h, and the calcination atmosphere is an aerobic atmosphere.
2. The method for preparing the positive electrode material by using the waste vanadyl phosphate lithium battery as claimed in claim 1, which is characterized in that: detecting the element content in the oxidation product in the step (4) by using an ICP detection method.
3. The method for preparing the positive electrode material by using the waste vanadyl phosphate lithium battery as claimed in claim 1, which is characterized in that: the mode of mixing materials in the step (4) is ball milling.
4. Use of the method of any one of claims 1-3 for the preparation of an electrode.
5. Use of the method of any one of claims 1-3 in the preparation of a battery.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210650984.2A CN115140722B (en) | 2022-06-10 | 2022-06-10 | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery |
| PCT/CN2023/078764 WO2023236595A1 (en) | 2022-06-10 | 2023-02-28 | Method for preparing positive electrode material from waste livopo4 battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210650984.2A CN115140722B (en) | 2022-06-10 | 2022-06-10 | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115140722A CN115140722A (en) | 2022-10-04 |
| CN115140722B true CN115140722B (en) | 2024-02-09 |
Family
ID=83408852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210650984.2A Active CN115140722B (en) | 2022-06-10 | 2022-06-10 | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115140722B (en) |
| WO (1) | WO2023236595A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115140722B (en) * | 2022-06-10 | 2024-02-09 | 广东邦普循环科技有限公司 | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107579304A (en) * | 2017-09-06 | 2018-01-12 | 湖南省正源储能材料与器件研究所 | A kind of method that phosphoric acid vanadium iron lithium is prepared in the anode pole piece from waste lithium iron phosphate |
| CN110331288A (en) * | 2019-06-28 | 2019-10-15 | 湖南邦普循环科技有限公司 | A kind of method that waste lithium iron phosphate material selectivity mentions lithium |
| CN110581323A (en) * | 2019-09-25 | 2019-12-17 | 深圳清华大学研究院 | In-situ regeneration method of waste lithium iron phosphate battery positive electrode material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7901810B2 (en) * | 2003-06-03 | 2011-03-08 | Valence Technology, Inc. | Battery active materials and methods for synthesis |
| CN102646857A (en) * | 2012-05-17 | 2012-08-22 | 哈尔滨工业大学 | Method for recycling and regenerating waste Li3V2(PO4)3 positive pole material |
| CN103972476A (en) * | 2014-05-16 | 2014-08-06 | 中南大学 | Preparation method of positive electrode material, phosphoric acid oxygen vanadium lithium, of lithium ion battery |
| CN114162796B (en) * | 2021-12-09 | 2023-01-06 | 宁波行殊新能源科技有限公司 | Method for recycling and regenerating phosphate waste |
| CN115140722B (en) * | 2022-06-10 | 2024-02-09 | 广东邦普循环科技有限公司 | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery |
-
2022
- 2022-06-10 CN CN202210650984.2A patent/CN115140722B/en active Active
-
2023
- 2023-02-28 WO PCT/CN2023/078764 patent/WO2023236595A1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107579304A (en) * | 2017-09-06 | 2018-01-12 | 湖南省正源储能材料与器件研究所 | A kind of method that phosphoric acid vanadium iron lithium is prepared in the anode pole piece from waste lithium iron phosphate |
| CN110331288A (en) * | 2019-06-28 | 2019-10-15 | 湖南邦普循环科技有限公司 | A kind of method that waste lithium iron phosphate material selectivity mentions lithium |
| CN110581323A (en) * | 2019-09-25 | 2019-12-17 | 深圳清华大学研究院 | In-situ regeneration method of waste lithium iron phosphate battery positive electrode material |
Non-Patent Citations (3)
| Title |
|---|
| 刘正 等.废旧磷酸钒锂电池材料回收及再利用研究.《电源技术》.2016,第40卷第35-38页. * |
| 废旧磷酸钒锂电池材料回收及再利用研究;刘正 等;《电源技术》;第40卷;第35-38页 * |
| 锂离子电池电极材料磷酸氧钒锂的研究进展;贺冬华 等;《应用化学》;第31卷;第1115-1122页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023236595A1 (en) | 2023-12-14 |
| CN115140722A (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108886181B (en) | Re-lithiation under oxidizing conditions | |
| CN106997975B (en) | method for recycling waste lithium iron phosphate battery and lithium manganate battery | |
| EP2911224B1 (en) | Li-Ni COMPOSITE OXIDE PARTICLE POWDER AND METHOD FOR MANUFACTURING SAME, AND NONAQUEOUS ELECTROLYTE SECONDARY CELL | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| US20110037019A1 (en) | Method for producing cathode active material for lithium ion batteries, cathode active material for lithium ion batteries obtained by the production method, lithium ion battery electrode, and lithium ion battery | |
| CN112897492B (en) | Method for regenerating and recycling high-impurity lithium iron phosphate waste powder | |
| CN108923090A (en) | A method of carbon-coated lithium iron manganese phosphate anode material is prepared from waste lithium iron phosphate battery recycling | |
| US9966599B2 (en) | Process for manufacturing lithium titanium oxides | |
| CN113265704A (en) | Method for preparing flake single crystal ternary electrode material with exposed {010} crystal face by regenerating waste lithium ion battery | |
| WO2023155539A1 (en) | Preparation method for sodium ferrovanadium phosphate material and application thereof | |
| WO2013056541A1 (en) | Method for producing lithium iron phosphate by using lithium ore as lithium source | |
| WO2023155544A1 (en) | Preparation method for polyanionic positive electrode material | |
| CN115140722B (en) | Method for preparing positive electrode material by using waste vanadyl phosphate lithium battery | |
| CN114162877A (en) | Method for preparing cobaltosic oxide by using lithium cobaltate positive electrode material | |
| JP2022542637A (en) | Relithiation under oxidizing conditions | |
| CN113735196A (en) | Recycling method of waste ternary precursor and ternary cathode material obtained by recycling | |
| WO2024021233A1 (en) | Method for preparing lithium iron phosphate by means of comprehensive recovery of lithium-containing wastewater and use thereof | |
| CN115744857B (en) | Method for preparing lithium iron phosphate positive electrode material by directional circulation of waste lithium iron phosphate battery | |
| CN116845408A (en) | Method for recycling waste lithium cobaltate battery positive electrode material by using water-based eutectic solvent | |
| CN109921121A (en) | A kind of method that waste and old saggar recycles anode material of lithium battery automatically | |
| CN112010278B (en) | Method for preparing battery-grade vanadyl fluorophosphate sodium anode material from industrial waste vanadium and prepared anode material | |
| CN117712544B (en) | Resource utilization method of waste lithium iron phosphate battery | |
| CN109354002A (en) | The method of lithium phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore | |
| JP2018041683A (en) | Method for manufacturing olivine type lithium phosphate-based positive electrode material | |
| CN117430109A (en) | Preparation method of lithium iron manganese phosphate material, lithium iron manganese phosphate material and lithium ion battery |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |