CN114388923A - Method for repairing and regenerating waste lithium iron phosphate anode material and lithium iron phosphate anode material - Google Patents
Method for repairing and regenerating waste lithium iron phosphate anode material and lithium iron phosphate anode material Download PDFInfo
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 93
- 239000002699 waste material Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000010405 anode material Substances 0.000 title claims abstract description 30
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 44
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 20
- 239000010406 cathode material Substances 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- GMKDNCQTOAHUQG-UHFFFAOYSA-L dilithium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=S GMKDNCQTOAHUQG-UHFFFAOYSA-L 0.000 claims description 2
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001383 lithium hypophosphite Inorganic materials 0.000 claims description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a method for repairing and regenerating a waste lithium iron phosphate anode material and a lithium iron phosphate anode material, wherein the method comprises the following steps: 1) preparing a reducing lithium salt solution by using an organic solvent; 2) mixing waste lithium iron phosphate powder with a reducing lithium salt solution, and placing the mixture in a constant temperature device for heating, stirring and reacting, wherein the reaction atmosphere is inert atmosphere; 3) collecting the solid powder in the step 2), and sequentially washing and drying the solid powder; 4) and annealing the solid powder obtained in the step 3) in an inert atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material. In the method, lithium salt is a main consumable, the organic solvent can be recycled, the steps are simple, secondary pollution is avoided, and the cost is low. In the regeneration process, waste LiFePO4The metal ions in the anode cannot be leached out, so that the metal resources in the waste anode are utilized to the maximum extent. The regenerated lithium iron phosphate anode material has higher crystallinity,and exhibits excellent electrochemical properties.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a method for repairing and regenerating a waste lithium iron phosphate anode material and a lithium iron phosphate anode material.
Background
The large-scale use of lithium ion batteries has gradually led to the development of resourcesThe worry of insufficient supply can solve the contradiction of resource supply and demand by effectively recycling the retired lithium ion battery. The current method for recovering the anode of the waste lithium ion battery mainly comprises two methods: fire and wet processes. Both processes aim to separate the valuable metallic elements from the spent anodes individually, but generally involve high energy consumption and the use of large amounts of chemical raw materials, and therefore high recovery costs. On the other hand, the recovery processes of the two methods generate toxic gas or discharge excessive pollution liquid, so that the risk of secondary pollution exists. For waste lithium iron phosphate (LiFePO)4) The element with higher value in the cathode material is only lithium, and the content of the lithium element is also less, so that the traditional method for recycling the lithium iron phosphate cathode material is irrevocable in economic benefit. Lithium deficiency and FePO can occur in the lithium iron phosphate anode material in the charge-discharge cycle process4The performance of the battery is poor due to the mixed phases, and if the defects can be directly repaired in a targeted mode, the use of excessive chemical reagents is avoided, so that the method has important significance for recycling the retired lithium iron phosphate battery.
The repair of the waste lithium iron phosphate anode material generally needs two reagents: a lithium salt and a reducing agent. The existing repair method has the defect that the ratio of lithium salt to reducing agent needs to be strictly controlled, so that a method for simply and effectively regenerating the waste lithium iron phosphate cathode material is necessary.
Disclosure of Invention
In view of the problems in the prior art, the present application aims to provide a method for repairing and regenerating a waste lithium iron phosphate positive electrode material, which uses a reducing lithium salt to repair and regenerate FePO in the waste lithium iron phosphate positive electrode material4Conversion of impurities into LiFePO4Wherein the reducing lithium salt acts as both a lithium source and a reducing agent. The method makes full use of valuable metal elements in the waste lithium iron phosphate anode material, avoids the use of an additional reducing agent, and has the advantages of less consumption of reducing lithium salt, economy, high efficiency and no pollution. After regeneration, the lithium source missing in the waste lithium iron phosphate anode material is supplemented, and simultaneously FePO is added4The impure phase is repaired to LiFePO4Waste lithium iron phosphateThe discharge capacity of the positive electrode material can be recovered. In addition, the invention obviously improves the crystallinity of the waste lithium iron phosphate anode material by implementing the regeneration step, and the cycle performance of the waste lithium iron phosphate anode material can also be obviously improved.
In order to achieve the above purpose, the present application provides a method for repairing and regenerating a waste lithium iron phosphate positive electrode material, which includes the following steps:
1) preparing a reducing lithium salt solution by using an organic solvent;
2) mixing waste lithium iron phosphate powder with a reducing lithium salt solution, and placing the mixture in a constant temperature device for heating, stirring and reacting, wherein the reaction atmosphere is inert atmosphere;
3) collecting the solid powder in the step 2), and sequentially washing and drying the solid powder;
4) and annealing the solid powder obtained in the step 3) in an inert atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
Preferably, in step 1), the reducing lithium salt includes lithium iodide (LiI), lithium borohydride (LiBH)4) Lithium aluminum hydride (LiAlH)4) Lithium sulfite (Li)2SO3) Lithium thiosulfate (Li)2S2O3) Lithium sulfide (Li)2S), lithium hypophosphite (LiH)2PO2) And lithium amide (LiNH)2) And the like, at least one kind of reducing lithium salt.
Preferably, in the step 1), the concentration of the reducing lithium salt solution is 0.03-0.3M, and more preferably 0.05-0.1M.
Preferably, in the step 1), the organic solvent is at least one of acetonitrile, diethyl ether, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dioxane, hexamethyl phosphoramide benzene and carbon tetrachloride.
Preferably, the solid-to-liquid ratio in the step 2) is 10-300 g/L, and more preferably 50-200 g/L; the stirring speed is 100-2000 rpm, the reaction temperature is 25-100 ℃, and the reaction time is 2-50 h.
Preferably, the washing solvent in step 3) is at least one of water, ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dioxane and hexamethylphosphoramide.
Preferably, the drying temperature in the step 3) is 60-120 ℃, and more preferably 80-100 ℃.
Preferably, the annealing temperature in the step 4) is 500-900 ℃, and more preferably 600-700 ℃; the annealing time is 1 to 18 hours, and more preferably 5 to 10 hours.
Preferably, in the step 2) and the step 4), the inert atmosphere is at least one of argon, nitrogen and neon.
In addition, the application also provides a lithium iron phosphate positive electrode material which is prepared by the method for repairing and regenerating the waste lithium iron phosphate positive electrode material.
The technical scheme provided by the application can achieve the following beneficial effects:
1) the waste lithium iron phosphate anode material treated by the repairing and regenerating method has higher crystallinity, and has more excellent electrochemical performance compared with the waste lithium iron phosphate anode material. Under the current density of 1C, the specific capacity of the regenerated lithium iron phosphate anode material is improved to be more than 151mAh/g, and the capacity retention rate after 100 cycles is improved to be more than 97%.
2) According to the method for directly supplementing lithium to the waste lithium iron phosphate positive electrode material by using the reductive lithium salt, the lithium salt is a main consumable material, and an additional reducing agent is not needed, so that the organic solvent can be recycled, the using amount of a reagent is reduced, secondary pollution is avoided, the recovery cost is reduced, the steps are simple, and the method is suitable for industrial popularization and application. In addition, during the regeneration process, waste LiFePO is used4The metal ions in the anode cannot be lost, so that the metal resources in the waste anode are utilized to the maximum extent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is an XRD spectrum of the waste lithium iron phosphate powder and the lithium iron phosphate cathode material regenerated in example 1.
Fig. 2 is a graph showing the first discharge capacity of the lithium iron phosphate cathode material regenerated in example 1 and the waste lithium iron phosphate powder.
Fig. 3 is a cycle performance diagram of the waste lithium iron phosphate powder and the regenerated lithium iron phosphate positive electrode of example 1 at 1C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
Example 1
A method for repairing and regenerating a waste lithium iron phosphate anode material comprises the following specific steps:
(1) preparing 100ml of LiI solution with the concentration of 0.1M by taking acetonitrile as a solvent;
(2) adding waste lithium iron phosphate powder into the solution obtained in the step (1), wherein the solid-to-liquid ratio is 50g/L, the stirring speed is 400rpm, reacting for 12 hours at 60 ℃, and introducing argon gas as a protective gas;
(3) centrifuging the suspension obtained in the step (2) to obtain lithium-supplemented lithium iron phosphate positive electrode powder, washing the lithium iron phosphate positive electrode powder with acetonitrile for 3 times, collecting the positive electrode powder through centrifugation, and drying the positive electrode powder at 100 ℃ for 12 hours;
(4) and (4) annealing the lithium iron phosphate powder obtained in the step (3) in a tubular furnace in an argon atmosphere at 700 ℃ for 5h to obtain the repaired and regenerated lithium iron phosphate cathode material.
Example 2
A method for repairing and regenerating a waste lithium iron phosphate anode material comprises the following specific steps:
(1) preparing 100ml LiBH with concentration of 0.05M by taking tetrahydrofuran as solvent4A solution;
(2) adding waste lithium iron phosphate powder into the solution obtained in the step (1), wherein the solid-to-liquid ratio is 200g/L, the stirring speed is 600rpm, reacting for 6 hours at 40 ℃, and introducing nitrogen as a protective gas;
(3) centrifuging the suspension obtained in the step (2) to obtain lithium-supplemented lithium iron phosphate positive electrode powder, washing the lithium iron phosphate positive electrode powder with tetrahydrofuran for 3 times, collecting the positive electrode powder through centrifugation, and drying the positive electrode powder at 80 ℃ for 6 hours;
(4) and (4) annealing the lithium iron phosphate powder obtained in the step (3) in a tubular furnace in an argon atmosphere at 600 ℃ for 10h to obtain the repaired and regenerated lithium iron phosphate cathode material.
Example 3
A method for repairing and regenerating a waste lithium iron phosphate anode material comprises the following specific steps:
(1) preparing 100ml LiAlH with concentration of 0.03M by using diethyl ether as solvent4A solution;
(2) adding waste lithium iron phosphate powder into the solution obtained in the step (1), wherein the solid-to-liquid ratio is 100g/L, the stirring speed is 300rpm, reacting for 6 hours at 40 ℃, and introducing argon gas as a protective gas;
(3) centrifuging the suspension obtained in the step (2) to obtain lithium-supplemented lithium iron phosphate positive electrode powder, washing with diethyl ether for 3 times, collecting the positive electrode powder through centrifugation, and drying at 60 ℃ for 12 hours;
(4) and (4) annealing the lithium iron phosphate powder obtained in the step (3) in a tubular furnace in an argon atmosphere at 800 ℃ for 6h to obtain the repaired and regenerated lithium iron phosphate cathode material.
Example 4
A method for repairing and regenerating a waste lithium iron phosphate anode material comprises the following specific steps:
(1) ethanol is used as solvent to prepare 100ml of Li with the concentration of 0.1M2SO3A solution;
(2) adding waste lithium iron phosphate powder into the solution obtained in the step (1), wherein the solid-to-liquid ratio is 150g/L, the stirring speed is 500rpm, reacting for 10 hours at 60 ℃, and introducing nitrogen as a protective gas;
(3) centrifuging the suspension obtained in the step (2) to obtain lithium-supplemented lithium iron phosphate positive electrode powder, washing the lithium iron phosphate positive electrode powder with ethanol for 3 times, collecting the positive electrode powder through centrifugation, and drying the positive electrode powder at 70 ℃ for 10 hours;
(4) and (4) annealing the lithium iron phosphate powder obtained in the step (3) in a tubular furnace in an argon atmosphere at 600 ℃ for 8h to obtain the repaired and regenerated lithium iron phosphate cathode material.
Example 5
A method for repairing and regenerating a waste lithium iron phosphate anode material comprises the following specific steps:
(1) ethanol is used as solvent to prepare 100ml of Li with the concentration of 0.08M2S solution;
(2) adding waste lithium iron phosphate powder into the solution prepared in the step (1), wherein the solid-to-liquid ratio is 150g/L, the stirring speed is 1000rpm, reacting for 5 hours at 70 ℃, and introducing argon as a protective gas;
(3) centrifuging the suspension obtained in the step (2) to obtain lithium-supplemented lithium iron phosphate positive electrode powder, washing the lithium iron phosphate positive electrode powder with ethanol for 3 times, collecting the positive electrode powder through centrifugation, and drying the positive electrode powder at 70 ℃ for 10 hours;
(4) and (4) annealing the lithium iron phosphate powder obtained in the step (3) in a tubular furnace in an argon atmosphere at 700 ℃ for 5h to obtain the repaired and regenerated lithium iron phosphate cathode material.
And respectively carrying out performance test and analysis on the lithium iron phosphate cathode material obtained in the embodiment.
Elemental analysis:
by utilizing an Inductively Coupled Plasma (ICP) test, the element compositions of the waste lithium iron phosphate anode powder and the regenerated anode material obtained in each embodiment are shown in the table I, and it can be seen that the regeneration method provided by the invention can effectively supplement the missing lithium in the waste lithium iron phosphate anode, and the molar ratio of the lithium to the phosphate radical in the regenerated anode material after lithium salt is supplemented is close to 1: 1.
Table one shows the elemental compositions of the regenerated positive electrode and the waste lithium iron phosphate material obtained in the embodiments of the present invention
| Molar ratio of | Li/P | Fe/P | P/P |
| Waste lithium iron phosphate | 0.81 | 1.04 | 1 |
| Example 1 | 0.99 | 1.03 | 1 |
| Example 2 | 1.02 | 0.98 | 1 |
| Example 3 | 0.97 | 1.01 | 1 |
| Example 4 | 1.01 | 0.98 | 1 |
| Example 5 | 0.98 | 0.97 | 1 |
Structural analysis:
referring to fig. 1, XRD comparison was performed on the waste lithium iron phosphate positive electrode and the regenerated positive electrode material collected in example 1 using an X-ray diffractometerIt can be observed that the impurity FePO is added after the lithium source is replenished4The corresponding diffraction peak disappears completely, and the regenerated anode material shows single LiFePO4Pure phase and higher crystallinity, indicating FePO4The impurities are completely converted into LiFePO4And (4) phase(s).
And (3) analyzing electrochemical properties:
1. preparing a battery pole piece: mixing waste or regenerated cathode material, ketjen black and polyvinylidene fluoride binder according to the weight ratio of 8: 1:1, adding N-methyl pyrrolidone solvent to prepare positive electrode slurry, coating the positive electrode slurry on an aluminum foil, drying the aluminum foil in vacuum at 100 ℃ for 24 hours to prepare a pole piece with a regular shape, and recording the quality of the pole piece.
2. And (3) electrochemical performance testing: and assembling the obtained pole piece, a lithium piece, an elastic piece, a gasket and a Celgard diaphragm in a glove box to obtain the button cell. And (3) carrying out electrochemical test on the assembled battery by using the Wuhan blue battery test system, wherein the voltage window is 2.5-4.0V, and carrying out charge and discharge tests under different multiplying powers (Table II). Under the current density of 1C, the first discharge specific capacity of the button cell prepared from the waste lithium iron phosphate material is only 111.2mAh/g (figure 2), and the capacity retention rate of 100 cycles is 90% (figure 3); the initial discharge specific capacity of the button cell assembled by the regenerated lithium iron phosphate anode material prepared in the embodiment 1 of the invention is improved to 151mAh/g (figure 2), and the capacity retention rate of 100 cycles is improved to 97% (figure 3), which shows that the regeneration method provided by the invention obviously improves the electrochemical performance of the waste lithium iron phosphate anode.
TABLE II electrochemical properties of the regenerated positive electrode and the waste lithium iron phosphate material obtained in the embodiment of the invention
In conclusion, by implementing the repairing and regenerating steps on the waste lithium iron phosphate positive electrode, impurities do not exist in the repaired and regenerated positive electrode material, and LiFePO is represented4A single pure phase. And collecting the positive electrode materials in different regeneration stages to assemble the button cell, and carrying out charge and discharge tests under the current of 1C.Compared with the waste lithium iron phosphate anode material before regeneration, the discharge specific capacity of the regenerated material is remarkably improved, and the capacity retention rate is improved from 90% to 97% after the material is circulated for 100 weeks under 1C current. Therefore, the regeneration method provided by the invention can obviously improve the electrochemical performance of the waste lithium iron phosphate anode material, and is simple, effective, energy-saving and environment-friendly.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. A method for repairing and regenerating a waste lithium iron phosphate positive electrode material is characterized by comprising the following steps:
1) preparing a reducing lithium salt solution by using an organic solvent;
2) mixing waste lithium iron phosphate powder with a reducing lithium salt solution, and placing the mixture in a constant temperature device for heating, stirring and reacting, wherein the reaction atmosphere is inert atmosphere;
3) collecting the solid powder in the step 2), and sequentially washing and drying the solid powder;
4) and annealing the solid powder obtained in the step 3) in an inert atmosphere to obtain the repaired and regenerated lithium iron phosphate cathode material.
2. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the reducing lithium salt includes at least one of lithium iodide, lithium borohydride, lithium aluminum hydride, lithium sulfite, lithium thiosulfate, lithium sulfide, lithium hypophosphite and lithium amide.
3. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1 or 2, wherein the method comprises the following steps: in the step 1), the concentration of the reducing lithium salt solution is 0.03-0.3M.
4. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step 1), the organic solvent is at least one of acetonitrile, diethyl ether, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dioxane, hexamethyl phosphoramide benzene and carbon tetrachloride.
5. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: the solid-liquid ratio in the step 2) is 10-300 g/L, the stirring speed is 100-2000 rpm, the reaction temperature is 25-100 ℃, and the reaction time is 2-50 h.
6. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: the washing solvent in the step 3) is at least one of water, ethanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dioxane and hexamethylphosphoramide.
7. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: the drying temperature in the step 3) is 60-120 ℃.
8. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: the annealing temperature in the step 4) is 500-900 ℃, and the annealing time is 1-18 h.
9. The method for repairing and regenerating the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the method comprises the following steps: in the step 2) and the step 4), the inert atmosphere is at least one of argon, nitrogen and neon.
10. A lithium iron phosphate anode material is characterized in that: the method for repairing and regenerating the waste lithium iron phosphate positive electrode material according to any one of claims 1 to 9.
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