CN117239272A - Method for repairing lithium battery anode material - Google Patents
Method for repairing lithium battery anode material Download PDFInfo
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- CN117239272A CN117239272A CN202311205513.1A CN202311205513A CN117239272A CN 117239272 A CN117239272 A CN 117239272A CN 202311205513 A CN202311205513 A CN 202311205513A CN 117239272 A CN117239272 A CN 117239272A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 76
- 238000009832 plasma treatment Methods 0.000 claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- 230000008439 repair process Effects 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- 241000220479 Acacia Species 0.000 claims description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000001502 supplementing effect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002253 acid Substances 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
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium battery regeneration, in particular to a method for repairing a lithium battery anode material. The method comprises the following steps: step 1, disassembling from waste lithium batteries to obtain anode powder before repair; step 2, uniformly mixing the anode powder before restoration with a lithium source, a binder and a dispersing agent to obtain slurry; step 3, centrifugally drying the slurry to obtain powder; and 4, carrying out plasma treatment on the powder to obtain the repaired lithium battery anode material. According to the invention, the recovered invalid positive electrode material is subjected to crystal structure regeneration under the action of plasma jet flow by supplementing a lithium source, so that the electrochemical activity of the positive electrode powder material is recovered, and the direct repair of the invalid positive electrode material can be realized in a short process.
Description
Technical Field
The invention relates to the technical field of lithium battery regeneration, in particular to a method for repairing a lithium battery anode material.
Background
Lithium ion batteries are widely applied in the fields of electric automobiles and energy storage at present, with the high-speed development of new energy industry, the consumption of metal lithium and related rare metals is increased more and more, and meanwhile, a large number of power batteries face retirement, and according to prediction, the number of the globally scrapped lithium ion batteries reaches over 1100 ten thousand tons by 2030, and the development of an effective lithium battery material recycling technology is quite important.
At present, technologies for recycling waste lithium ion batteries at home and abroad mainly comprise hydrometallurgy, pyrometallurgy and physical repair. The wet metallurgy method has the advantages that the element recovery rate is high, the purity is high, the application is the widest, a large amount of strong acid and strong oxidant are used during recovery, the environmental protection pressure of waste liquid treatment is quite high, meanwhile, the anode and cathode powder obtained after the waste batteries are physically disassembled often contains more aluminum scraps, scrap iron and other impurities, the wet metallurgy cannot achieve high material selectivity, during recovery, impurity elements such as iron, aluminum, phosphate radical and other soluble metals or oxides are often dissolved in the leaching liquid, the subsequent impurity removal cost is increased, and some elements are easy to form colloidal precipitates to adsorb lithium elements so as to reduce the recovery rate of the lithium elements.
The pyrometallurgy is to smelt the disintegrated waste battery materials in a high-temperature furnace and then recover valuable elements therein by a wet method, the process of the method is relatively complex, but the high-temperature smelting needs to consume a large amount of energy, and meanwhile, a large amount of alloy elements still become slag in the form of salt and are difficult to treat. The physical repair regeneration is to carry out lithium supplement and proper post treatment on the recovered and impurity-removed anode and cathode powder so as to realize the repair regeneration of the electrode material. The method can reduce pollution, can obtain the recovered material with high added value to the maximum extent, and the repaired anode and cathode materials can be returned to the battery manufacturing chain again, so that the method has obvious economic benefit. However, the physical repair regeneration method requires long-time high-temperature heat treatment to ensure the repair of the structure of the positive electrode material, and has the advantages of long treatment time, equivalent treatment process and preparation process of new materials, lower production efficiency and reduced economy of the regenerated lithium battery positive electrode material.
Therefore, the method for repairing the lithium battery anode material in a short process is of great significance to the application of power lithium battery regeneration.
Disclosure of Invention
Based on the above, the present invention provides a method for repairing a positive electrode material of a lithium battery.
In order to achieve the above object, the present invention provides the following solutions:
according to one of the technical schemes, the method for repairing the lithium battery anode material comprises the following steps:
step 1, disassembling from waste lithium batteries to obtain anode powder before repair;
step 2, uniformly mixing the anode powder before restoration with a lithium source, a binder and a dispersing agent to obtain slurry;
step 3, centrifugally drying the slurry to obtain powder;
and 4, carrying out plasma treatment on the powder to obtain the repaired lithium battery anode material.
In step 2, ball milling and mixing are carried out in a uniform mixing mode, and the ball milling medium is zirconia balls or agate balls.
Further, in step 2, the lithium source is Li 2 CO 3 、Li(OH)、LiNO 3 And one or more of the lithium salts.
Further, in the step 2, the binder is one or more of PVA (polyvinyl alcohol), PEG (polyethylene glycol), PVC (polyvinyl chloride) and acacia; the dispersing agent is one or more of PEG, polyacrylamide, cellulose and methyl amyl alcohol.
Further, in the step 2, the slurry contains 40-65% of the positive electrode powder before repair, 1-20% of the binder, 0.1-5% of the dispersing agent and the balance of the lithium source according to mass percentage.
Further, in the step 3, the centrifugal drying temperature is 150-200 ℃ and the rotating speed is 15000-28000 r/min.
The centrifugal drying treatment time of the powder is related to the amount of the material to be treated, and the drying time per kg of powder varies from 5 minutes to 5 hours depending on the capacity of the drying apparatus.
Further, in step 4, the plasma processing parameters specifically include: feeding inert gas which is argon and/or nitrogen into two paths on the cathode side, wherein the flow rate of the single path of gas is 20-60L/min; the single-path plasma power is 10-50kw, the plasma current is 200-500A, the voltage is 30-80V, the carrier gas flow is 2-10L/min, and the powder feeding amount is 20-50g/min; the carrier gas is a mixed gas of argon and oxygen in a volume ratio of 1:1.
The invention proves that the parameter range is the optimal technological parameter, and the parameters such as gas flow, plasma power, plasma current, voltage, carrier gas flow, powder feeding amount and the like exceed the ranges described above, which can influence the plasma treatment effect and further influence the repairing effect of the anode material.
Further, in the step 4, the powder is subjected to plasma treatment, and the step of screening out the powder with the median particle diameter of 0-15 mu m is further included.
According to a second technical scheme, the double-cathode plasma generator for the method for repairing the lithium battery anode material comprises two obliquely opposite cathodes with an included angle smaller than 90 degrees and an anode which is common to the two cathodes; the anode is positioned on the vertical plane of the bisector of the included angle of the two cathodes.
The plasma generator in the prior art is mainly composed of one cathode and one anode which are coaxial, and the plasma generator is composed of two cathodes which are obliquely opposite, powder materials to be treated are fed from the center, so that the uniformity of the powder heating process can be ensured, meanwhile, the powder can be ensured to be heated in the atmosphere after high-temperature oxygen ionization, and the recovery of the components and the structure of the positive electrode powder of the lithium battery in short time and high temperature is facilitated.
Further, the device also comprises a plasma treatment bin; one end of the plasma treatment bin is connected with the feeding port through a plasma torch, and an observation window is arranged on the plasma treatment bin; the other end of the plasma treatment bin is connected with the powder collecting barrel.
The third technical scheme of the invention is that the method for repairing the anode material of the lithium battery by using the double-cathode plasma generator comprises the following steps:
disassembling the waste lithium battery to obtain anode powder before repair;
uniformly mixing the anode powder before restoration with a lithium source, a binder and a dispersing agent to obtain slurry;
centrifugally drying the slurry to obtain powder;
and (3) delivering the powder into a powder delivering device for spray drying, delivering the powder after spray drying from a feeding port, and carrying out plasma treatment in a plasma treatment bin, wherein the powder is collected after the plasma treatment is finished, namely the repaired anode powder.
The invention discloses the following technical effects:
according to the invention, the recovered invalid positive electrode material is subjected to crystal structure regeneration under the action of plasma jet flow by supplementing a lithium source, so that the electrochemical activity of the positive electrode powder material is recovered, and the direct repair of the invalid positive electrode material can be realized in a short process.
For example, ternary lithium cathode materials (LiNi x Co y Mn 1-x-y O 2 Short for NCM), the positive electrode material is generally required to be redissolved and precipitated, and then the positive electrode material is sintered at high temperature after being matched with lithium, so that the process is complex, and a large amount of acid and alkali and water are required to be consumed. The method for repairing the positive electrode material of the lithium battery can greatly shorten the regeneration process of the positive electrode material, and the processing process of kilogram-level positive electrode material powder is completed within 1 hour.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed 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 invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the cathode and anode composition of a dual cathode plasma generator of the present invention.
Fig. 2 is a schematic diagram of a plasma processing chamber of a dual cathode plasma generator according to the present invention.
Fig. 3 is an SEM image of the powder obtained in step 3 of example 1.
Fig. 4 is an SEM image of the repaired cathode powder obtained in step 5 of example 1 at different magnifications, wherein the left image is an SEM image at 250 magnifications and the right image is an SEM image at 1400 magnifications.
Fig. 5 is a graph showing the first charge/discharge specific capacity of the positive electrode powder obtained in step 1 of example 1.
Fig. 6 is a graph showing the first charge-discharge specific capacity of the positive electrode powder after repair obtained in step 5 of example 1.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the embodiments of the present invention, unless otherwise specified, are available from a purchasing route.
The cathode and anode components of the double-cathode plasma generator used in the embodiment of the invention are shown in figure 1, the plasma treatment bin is shown in figure 2, and the plasma treatment bin is a component part of the double-cathode plasma generator and is positioned at the lower part of the double-cathode plasma generator. Other plasma generators commonly used in the art can be used with the present invention as well.
Example 1
And step 1, fully discharging a waste lithium battery with an anode material of NCM523, then physically disassembling, separating to obtain a cathode pole piece, an anode pole piece, a diaphragm and a shell part, calcining at high temperature (500 ℃ for 1 hour) in an argon atmosphere, and irradiating with a short pulse laser with a pulse width of 8ns and a frequency of 10kHz to enable the anode powder to fall off from a current collector.
Step 2, sieving the positive electrode powder obtained in step 1, and mixing with lithium source (lithium carbonate Li) 2 CO 3 ) Mixing binder PVA and dispersing agent PEG, adding into a ball milling tank, ball milling, crushing and mixing uniformly at high speed with zirconia balls (or agate balls) as medium to obtain precursor slurry, wherein the solid content of the positive electrode powder in the precursor slurry is 50%, the binder is 1.5% by weight, the dispersing agent is 3% by weight, and the balance is lithium source.
And 3, feeding the slurry obtained in the step 2 into a centrifugal dryer, setting the temperature of a centrifugal drying chamber to 190 ℃, rotating a centrifugal atomizing disc for 20000 revolutions per minute, and collecting powder obtained after centrifugal drying, wherein the morphology of the powder is shown in figure 3.
Step 4, screening the powder obtained in the step 3, and pouring the screened reconstituted powder with the median particle size of 0-15 mu m into a powder feeder (the powder is spray-dried in the powder feeder); the powder is processed by a double cathode plasma generator (shown in figure 1), which comprises two cathodes with an included angle of 50 degrees and a common anode, the powder after spray drying is fed from the center of a feeding hole, and the powder is processed in a plasma processing bin (shown in figure 2), specifically: argon is filled in the plasma treatment bin, the plasma power is 31kw, two paths of air are fed from two cathode sides, the single path of air is pure argon, the flow is 50L/min, the single path of plasma current is 250A, the voltage is changed between 62V and 63V, the powder carrier air is the mixed air of argon and oxygen (the volume ratio of the argon to the oxygen is 1:1), the carrier air flow is 3.5L/min, and the powder feeding amount is 30g/min.
And 5, collecting the processed powder, namely the repaired anode powder. The morphology is shown in fig. 4 (in the figure, the left image is a picture at 250 magnification, and the right image is a picture at 1400 magnification). As can be seen by comparing fig. 3 and 4, the treated powder still retains the spherical particle morphology, but the original loose structure becomes more dense.
The positive electrode powder after the repair of example 1 was subjected to performance verification, and the specific verification method is as follows:
the positive electrode powder repaired in example 1 was assembled into a button cell for testing performance, the assembly procedure was that the powder was placed in a vacuum drying oven and dried at 120 ℃ for 2 hours to ensure removal of water adsorbed on the surface of the material, then the positive electrode powder, PVDF, acetylene black were placed in an agate mortar in a glove box, the three substances were mixed in a mass ratio of 8:1:1, the mass to volume ratio of PVDF (polyvinylidene fluoride) to NMP (methylpyrrolidone) was 1mg to 30 μl, NMP was added in this ratio, and grinding was performed in an agate mortar for 30 minutes, and the slurry preparation was completed. The smear process was then continued in the glove box with a thickness of the pole piece of 100 μm. After finishing the smearing process, placing the smeared pole piece in a vacuum drying oven in a glove box, drying for 10 hours at 120 ℃, and then cutting to obtain the positive pole piece.
The button cell assembly is completed in a glove box, and the water content and the oxygen content in the glove box are controlled below 0.1 ppm. And placing the concave surface of the positive electrode shell upwards in a tray, placing the electrode plate in the center of the round positive electrode shell, dripping electrolyte until the electrode plate is soaked, then sequentially placing the diaphragm, the lithium plate, the gasket and the elastic sheet into the positive electrode shell, and finally buckling the concave surface of the negative electrode shell downwards into the positive electrode shell to complete battery assembly.
The assembled battery is put into a sealed bag, taken out from the glove box and sealed by a hydraulic sealing machine to prevent air and moisture from entering. The exterior of the packaged battery was wiped clean and the electrochemical performance was tested after resting for 24 hours.
Fig. 5 shows a graph of the specific capacity of the positive electrode powder obtained in step 1 of example 1.
Fig. 6 shows a graph of the first charge-discharge specific capacity of the positive electrode powder after repair obtained in step 5 of example 1. As can be seen by comparing FIG. 5 with FIG. 6, the discharge capacity after the repair treatment is from 82mAh g -1 Increased to 141mAh g -1 。
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (9)
1. A method of repairing a lithium battery positive electrode material, comprising the steps of:
step 1, disassembling from waste lithium batteries to obtain anode powder before repair;
step 2, uniformly mixing the anode powder before restoration with a lithium source, a binder and a dispersing agent to obtain slurry;
step 3, centrifugally drying the slurry to obtain powder;
and 4, carrying out plasma treatment on the powder to obtain the repaired lithium battery anode material.
2. The method for repairing a positive electrode material of a lithium battery according to claim 1, wherein in step 2, the lithium source is Li 2 CO 3 、Li(OH)、LiNO 3 One or more of the following.
3. The method of repairing a lithium battery positive electrode material according to claim 1, wherein in step 2, the binder is one or more of PVA, PEG, PVC and acacia; the dispersing agent is one or more of PEG, polyacrylamide, cellulose and methyl amyl alcohol.
4. The method for repairing a positive electrode material of a lithium battery according to claim 1, wherein in the step 2, the slurry contains 40-65wt% of the positive electrode powder before repairing, 1-20wt% of a binder, 0.1-5wt% of a dispersing agent, and the balance of a lithium source.
5. The method for repairing a positive electrode material of a lithium battery according to claim 1, wherein in the step 3, the centrifugal drying temperature is 150-200 ℃ and the rotational speed is 15000-28000 rpm.
6. The method for repairing a positive electrode material of a lithium battery according to claim 1, wherein in step 4, the plasma treatment is specifically: two paths of air are supplied to the cathode side, and the air flow is 20-60L/min; argon is delivered from the anode air supply port, and the air flow is 20-200L/min; the power of the plasma is 10-50kw, the current of the plasma is 200-500A, the voltage is 30-80V, the flow rate of carrier gas is 2-10L/min, and the powder feeding amount is 20-50g/min; the carrier gas is a mixed gas of argon and oxygen in a volume ratio of 1:1.
7. A dual cathode plasma generator for use in the method of repairing a lithium battery positive electrode material of claim 1, comprising two diagonally opposite cathodes having an included angle of less than 90 degrees, and an anode common to both; the anode is positioned on the vertical plane of the bisector of the included angle of the two cathodes.
8. The dual cathode plasma generator of claim 7, further comprising a plasma processing chamber; one end of the plasma treatment bin is connected with the feeding port through a plasma torch, and an observation window is arranged on the plasma treatment bin; the other end of the plasma treatment bin is connected with the powder collecting barrel.
9. A method for repairing a positive electrode material of a lithium battery using the double cathode plasma generator of claim 7 or 8, comprising the steps of:
disassembling the waste lithium battery to obtain anode powder before repair;
uniformly mixing the anode powder before restoration with a lithium source, a binder and a dispersing agent to obtain slurry;
centrifugally drying the slurry to obtain powder;
and (3) delivering the powder into a powder delivering device for spray drying, delivering the powder after spray drying from a feeding port, and carrying out plasma treatment in a plasma treatment bin, wherein the powder is collected after the plasma treatment is finished, namely the repaired anode powder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311205513.1A CN117239272A (en) | 2023-09-19 | 2023-09-19 | Method for repairing lithium battery anode material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311205513.1A CN117239272A (en) | 2023-09-19 | 2023-09-19 | Method for repairing lithium battery anode material |
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| CN117239272A true CN117239272A (en) | 2023-12-15 |
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| CN202311205513.1A Pending CN117239272A (en) | 2023-09-19 | 2023-09-19 | Method for repairing lithium battery anode material |
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| CN (1) | CN117239272A (en) |
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2023
- 2023-09-19 CN CN202311205513.1A patent/CN117239272A/en active Pending
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