CN115528340A - Regeneration method of waste lithium ion battery anode material - Google Patents
Regeneration method of waste lithium ion battery anode material Download PDFInfo
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- CN115528340A CN115528340A CN202211296287.8A CN202211296287A CN115528340A CN 115528340 A CN115528340 A CN 115528340A CN 202211296287 A CN202211296287 A CN 202211296287A CN 115528340 A CN115528340 A CN 115528340A
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- 239000002699 waste material Substances 0.000 title claims abstract description 163
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 162
- 239000010405 anode material Substances 0.000 title claims abstract description 90
- 238000011069 regeneration method Methods 0.000 title description 28
- 239000000843 powder Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 46
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- 238000002156 mixing Methods 0.000 claims abstract description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 30
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 6
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- 239000007788 liquid Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- 230000008929 regeneration Effects 0.000 description 12
- 230000008439 repair process Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 238000000498 ball milling Methods 0.000 description 4
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- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
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Images
Classifications
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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
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for regenerating a waste lithium ion battery anode material, which comprises the following steps: discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative electrode material, and pretreating the waste lithium ion battery positive plate to obtain waste lithium ion battery positive electrode material powder; mixing a waste lithium ion battery negative electrode material with a NaCl solution and an accelerant to obtain a first solution, carrying out hydrothermal reaction, and carrying out evaporative crystallization to obtain LiCl powder; mixing LiCl powder with an organic solvent and an activating agent, and performing saponification reaction to obtain a second solution; mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution; drying the third solution to obtain anode material powder; and quenching the anode material powder to obtain the regenerated lithium ion battery anode material. The method can efficiently regenerate the anode material of the waste lithium ion battery and recover the excellent electrochemical performance of the anode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery regeneration, in particular to a regeneration method of a waste lithium ion battery anode material.
Background
China is faced with the constant rising of the dependence of fossil energy on the outside, the engine technology is limited by people, the triple pressure of serious pollution of automobile exhaust is realized, sustainable development new energy is developed, the establishment of a low-carbon society becomes a urgent task, the development of new energy automobiles is a necessary choice for 'lane change and overtaking' in China, and the lithium ion battery is also concerned as a novel high-energy green battery by virtue of the advantages of high specific capacity, small self-discharge, long service life and the like. The dramatic increase in the production of lithium ion batteries necessarily results in a large consumption of manufacturing resources. Particularly, in the case of metal minerals, a heavy burden is imposed on the supply of rare metals such as lithium (Li) and cobalt (Co). Lithium, cobalt and nickel are the focus of resource competition in various countries, and the cobalt and nickel are deficient in China, and the dependency on foreign resources exceeds 70%. The extraction and extraction of lithium metal is very complicated and expensive. Therefore, the waste lithium ion battery can be regarded as an "artificial mineral" from which metals are extracted. The recycling of the waste lithium ion battery can reduce environmental pollution and effectively relieve the requirements of metal resources such as lithium, cobalt and the like. The resource utilization of the waste lithium ion battery can realize the resource utilization of limited resources, drive the development of circular economy, avoid potential threats to human health and ecological environment, and have multiple benefits of resources, economy, society and the like, so the resource utilization technology of the waste lithium ion battery has important significance and practical value.
With the rapid development of the global new energy industry, currently commercialized lithium ion battery positive electrode materials include lithium cobaltate, lithium manganate, lithium iron phosphate, ternary materials and the like. At present, the recovery method of the anode material of the waste lithium ion battery mainly comprises pyrometallurgy, hydrometallurgy and direct regeneration. The direct regeneration technology repairs and regenerates a new lithium ion battery anode material by the lithium ion battery anode material, can effectively avoid the problem that the anode material with complex components is difficult to separate and purify in the later period, not only can shorten the recovery process, but also has greater economic benefit and wider application prospect.
In the prior art, a high-temperature solid-phase sintering method is used for directly repairing a ternary cathode material, or a waste lithium iron phosphate battery cathode material is heated at a high temperature, carbon and a binder are removed to obtain solid powder, a lithium source compound and a carbon source are added into the solid mixture, the mixture is subjected to ball milling by a high-energy wet method, and finally the powder subjected to ball milling is placed in a non-oxidizing atmosphere and is roasted at a high temperature to obtain the qualified lithium iron phosphate battery cathode material. However, although the two methods can regenerate the anode material of the waste lithium ion battery, the method adopts high temperature and the high-temperature roasting time is long, so that the anode material of the waste lithium ion battery cannot be efficiently regenerated.
Accordingly, there is a need for improvements and developments in the art.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for regenerating a waste lithium ion battery cathode material, and aims to solve the problem that the conventional method for regenerating the waste lithium ion battery cathode material cannot efficiently regenerate the waste lithium ion battery cathode material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for regenerating a waste lithium ion battery anode material comprises the following steps:
discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative material, and pretreating the waste lithium ion battery positive plate to obtain waste lithium ion battery positive material powder;
mixing the waste lithium ion battery negative electrode material with a NaCl solution and an accelerant to obtain a first solution, carrying out hydrothermal reaction, and carrying out evaporative crystallization to obtain LiCl powder;
mixing the LiCl powder with an organic solvent and an activating agent, and performing saponification reaction to obtain a second solution;
mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution;
drying the third solution to obtain anode material powder;
and quenching the anode material powder to obtain the regenerated lithium ion battery anode material.
The regeneration method of the anode material of the waste lithium ion battery comprises the step of mixing the first solution and the second solution, wherein the solid-liquid mass ratio of the first solution to the second solution is 1 (5-10).
The regeneration method of the anode material of the waste lithium ion battery is characterized in that the temperature of the hydrothermal reaction is 200-240 ℃ and the time is 10-30min.
The regeneration method of the anode material of the waste lithium ion battery comprises the step of carrying out regeneration on the anode material of the waste lithium ion battery by using an organic solvent, wherein the organic solvent is one or more of urea, acetamide and thiourea.
The regeneration method of the waste lithium ion battery anode material comprises the step of preparing an activating agent, wherein the activating agent is ethyl acetate or 2-ethylhexyl phosphate mono-2-ethylhexyl ester.
The method for regenerating the anode material of the waste lithium ion battery comprises the following steps of mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution, and specifically comprises the following steps:
mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a mixed solution;
and (3) introducing direct current to the mixed solution as an anode for electrolysis.
The regeneration method of the anode material of the waste lithium ion battery is characterized in that in the electrolysis process, the voltage drop between a cathode and an anode is 8-10V.
The regeneration method of the anode material of the waste lithium ion battery comprises the following steps of: heating to 500-700 deg.c at room temperature in the heating rate of 10 deg.c/min, maintaining for 4 hr, cooling to 100 deg.c in the cooling rate of 8 deg.c/min and natural cooling.
The regeneration method of the waste lithium ion battery anode material comprises the following steps of discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery anode plate and a waste lithium ion battery cathode material, and pretreating the waste lithium ion battery anode plate to obtain waste lithium ion battery anode material powder, wherein the steps specifically comprise:
soaking the waste lithium ion battery in 3M NaCl solution for 24-48h to enable the SOC value to reach below 20%, and disassembling to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative material;
placing the waste lithium ion battery positive plate in a 3M NaOH solution, stirring and reacting for 10 hours, washing and filtering to obtain a waste lithium ion battery positive material;
and calcining the waste lithium ion battery anode material at 650 ℃ for 5h to obtain waste lithium ion battery anode material powder.
The regeneration method of the anode material of the waste lithium ion battery is characterized in that the waste lithium ion battery is a waste lithium iron phosphate battery or a waste lithium ion ternary battery.
Has the beneficial effects that: the invention discloses a method for regenerating a waste lithium ion battery anode material, which comprises the steps of mixing a cathode material obtained by discharging and disassembling a waste lithium ion battery with NaCl to perform hydrothermal treatment to obtain LiCl serving as a lithium source, mixing the LiCl with an organic solvent and an activating agent to perform saponification reaction to obtain a medium with various binding sites, reacting the lithium source with the waste lithium ion battery anode material in the medium to repair the waste lithium ion battery anode material, and drying and quenching to obtain the regenerated lithium ion battery anode material.
Drawings
Fig. 1 is a flowchart of a preferred embodiment of a method for regenerating a positive electrode material of a waste lithium ion battery according to an embodiment of the present invention.
FIG. 2 is an XRD pattern of RNCM-622 and SNCM-622 from example 1.
FIG. 3 is an SEM photograph of RNCM-622 and SNCM-622 obtained in example 1.
FIG. 4 is a graph of the electrochemical performance of RNCM-622 and SNCM-622 in example 1.
FIG. 5 is an impedance diagram of RNCM-622 and SNCM-622 in example 1.
Detailed Description
The invention provides a method for regenerating a waste lithium ion battery anode material, which is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used merely for convenience in describing the present application and for simplicity in description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present application.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first" and "second" may explicitly or implicitly include one or more of the described features. It will be understood by those skilled in the art that, unless otherwise defined, all terms (including 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. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In the prior art, a high-temperature solid-phase sintering method is used for directly repairing a ternary cathode material, or a waste lithium iron phosphate battery cathode material is heated at a high temperature, carbon and a binder are removed to obtain solid powder, a lithium source compound and a carbon source are added into the solid mixture, the mixture is subjected to ball milling by a high-energy wet method, and finally the powder subjected to ball milling is placed in a non-oxidizing atmosphere and is roasted at a high temperature to obtain the qualified lithium iron phosphate battery cathode material. However, although the two methods can regenerate the anode material of the waste lithium ion battery, the method adopts high temperature and the high-temperature roasting time is long, so that the anode material of the waste lithium ion battery cannot be efficiently regenerated.
Based on this, the present invention provides a method for regenerating a cathode material of a waste lithium ion battery, referring to fig. 1, which comprises the steps of:
s10, discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative electrode material, and pretreating the waste lithium ion battery positive plate to obtain waste lithium ion battery positive electrode material powder;
s20, mixing the waste lithium ion battery negative electrode material with a NaCl solution and an accelerant to obtain a first solution, carrying out hydrothermal reaction, and carrying out evaporative crystallization to obtain LiCl powder;
s30, mixing the LiCl powder with an organic solvent and an activating agent, and performing saponification reaction to obtain a second solution;
s40, mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution;
s50, drying the third solution to obtain anode material powder;
and S60, quenching the anode material powder to obtain the regenerated lithium ion battery anode material.
Specifically, the method comprises the steps of mixing a negative electrode material obtained by discharging and disassembling the waste lithium ion battery with NaCl to perform hydrothermal treatment to obtain LiCl as a lithium source, mixing the LiCl with an organic solvent and an activating agent to perform saponification reaction to obtain a medium with various binding sites, reacting the lithium source with a positive electrode material of the waste lithium ion battery in the medium to repair the positive electrode material of the waste lithium ion battery, and drying and quenching the medium to obtain a regenerated positive electrode material of the lithium ion battery.
The existing method for recycling the anode material of the waste lithium ion battery comprises pyrometallurgical recovery, hydrometallurgical recovery and material regeneration. Although the pyrometallurgy is simple to operate and high in productivity, the pyrometallurgy has the defects of high energy consumption, harmful gas emission and high equipment requirement; hydrometallurgy faces the problem of long flow and the danger of environmental pollution caused by acid and alkali byproducts generated in the smelting process. Regeneration of materials includes both indirect and direct regeneration of materials. Although the indirect regeneration method can control the purity of the precursor, the production process is complex, a corrosive solvent is required to be used, and secondary pollution is easily caused; the direct regeneration directly separates out the anode material through the pretreatment process, and then the attenuated anode material is subjected to lithium supplement treatment. The existing direct regeneration methods include a high-temperature solid phase method, an electrochemical method, a hydrothermal method and a molten salt method. The high-temperature solid phase completes the regeneration process at 800-1000 ℃ by uniformly mixing the waste material and the lithium salt, repairs the crystal structure of the lithium cobalt oxide and realizes the direct regeneration of the waste lithium cobalt oxide anode material, but the high-temperature solid phase method has high requirements on the precursor of the material, the final product is not uniform due to non-uniform lithium mixing, the reaction temperature is higher, the sintering time is long, the energy consumption is high, and the electrochemical performance of the regenerated anode material needs to be improved; electrochemical methods are a promising material separation and regeneration technique that can use electrodeposition or electrochemical insertion to produce useful materials with little waste generation or low reagent requirements, but electrochemical methods have limited recovery of material properties and high requirements for precursor materials; the hydrothermal method is characterized in that in a specially-made closed container (high-pressure kettle), an aqueous solution is used as a reaction medium, and the reaction container is heated to create a high-temperature environment of 100-1000 ℃ and a high-pressure environment of 1-100MPa, so that substances which are usually insoluble or insoluble are dissolved and recrystallized, low energy consumption is realized, and the hydrothermal method has the advantages of compatibility with batteries under different capacity attenuation conditions, short time and good electrochemical performance of a regenerated anode material. Therefore, the waste cathode material is regenerated more efficiently, greener and safer to recover the electrochemical performance by adopting the method of combining the hydrothermal method and the electrochemical method, and the waste cathode material is directly subjected to lithium supplement without knowing the lithium shortage in the original waste cathode material and performing ICP (inductively coupled plasma) test.
In some embodiments, in step S20, the mass ratio of the negative electrode material to the NaCl solution and the accelerator is 1: (5-10): (1-3), the accelerator is an oxidizing substance, and hydrogen peroxide is preferred in the embodiment.
In some embodiments, the mass ratio of solid to liquid (solid refers to the graphite cathode material of the waste lithium ion battery) in the first solution is 1 (5-10), the temperature of the hydrothermal reaction is 200-240 ℃, and the time is 10-30min, because the lithium ions in the cathode of the waste lithium ion battery are Li x C 6 The compound exists in a form, so that lithium ions can be rapidly extracted by adding an accelerant and a NaCl solution to perform a hydrothermal reaction, and LiCl powder can be obtained by removing impurities and performing evaporative crystallization.
In some embodiments, the hydrothermal reaction is specifically: adding the uniformly mixed first solution into the inner liner of the hydrothermal kettle, then placing the hydrothermal kettle into a forced air drying oven, and keeping the temperature at 200-240 ℃ for 10-30min. In the hydrothermal reaction process, the LiC in the graphite is reacted by using the solution as a medium and heating the reaction container to create a high-temperature and high-pressure reaction environment 6 Li in (1) + Extracted, and the promoter promotes Li through oxide substances + This process of extraction occurs.
In some embodiments, the organic solvent is one or more of urea, acetamide, thiourea.
In some embodiments, the activator is ethyl acetate or 2-ethylhexyl phosphate mono 2-ethylhexyl ester.
Specifically, the organic solvent is used as a carrier, the activator is used for activating the organic solvent to carry out saponification, the activator is hydrolyzed under alkaline conditions to generate hydroxyl, the hydroxyl attacks alkoxy, and the alkoxy is separated to generate alcohol and carboxylate (taking the activator as ethyl acetate for example, the ethyl acetate is hydrolyzed into the alcohol and the carboxylate under alkaline conditions), so that the saponified mixed solution becomes a medium with various binding sites, and the LiCl can react with the waste lithium ion battery anode material in the medium, so as to repair the waste lithium ion battery anode material.
In some embodiments, the step of mixing the second solution with the powder of the positive electrode material of the waste lithium ion battery to obtain a third solution specifically includes:
mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a mixed solution;
and introducing direct current into the mixed solution as an anode to perform electrolysis.
In some embodiments, during the electrolysis process, the voltage drop between the cathode and the anode is 8-10V, the cathode is a platinum sheet, the anode is a positive electrode material of a waste lithium ion battery, and the electrolyte is a second solution.
Specifically, lithium ions can be promoted to enter the anode material of the waste lithium ion battery under the action of an external current through an electrolysis mode, so that the lithiation effect is further enhanced, the existing substance in the anode region has certain reducibility, the lithiation process and the synchronous application of voltage are promoted, and the anode material can be better repaired. In the actual production, the above process can be omitted, and the second solution and the waste lithium ion battery anode material powder are mixed to spontaneously generate the lithiation reaction.
In some embodiments, the drying process is achieved using a spray dryer.
In some embodiments, the quenching treatment is specifically: heating to 500-700 ℃ at room temperature at a heating rate of 10 ℃/min, preserving heat for 4h, cooling to 100 ℃ at a cooling rate of 8 ℃/min, and then naturally cooling, wherein the material structure is easier to crack in the rapid heating process, the lithiated lithium reaction is facilitated, and the generation of some adverse impurity phases is avoided.
In some embodiments, the step of discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative electrode material, and preprocessing the waste lithium ion battery positive plate to obtain waste lithium ion battery positive electrode material powder specifically includes:
soaking the waste lithium ion battery in 3M NaCl solution for 24-48h to enable the SOC value to reach below 20%, and disassembling to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative material;
placing the waste lithium ion battery positive plate in a 3M NaOH solution, stirring and reacting for 10 hours, washing and filtering to obtain a waste lithium ion battery positive material;
and calcining the waste lithium ion battery anode material at 650 ℃ for 5h to obtain waste lithium ion battery anode material powder.
In some embodiments, the spent lithium ion battery is a spent lithium iron phosphate battery or a spent lithium ion ternary battery.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is clear that the described embodiments are only a part of the embodiments of the invention, not all embodiments, merely intended to illustrate the invention and in no way limit it. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for regenerating a positive electrode material of a waste NCM-622 (recorded as SNCM-622) battery comprises the following steps:
s10, placing the waste NCM-622 battery in a 3M NaCl solution to be soaked for 24 hours, enabling the SOC value to reach 20%, and disassembling to obtain a waste NCM-622 battery positive plate and a waste NCM-622 battery negative electrode material; placing the waste NCM-622 battery positive plate in a 3M NaOH solution, stirring and reacting for 10 hours, washing and filtering to obtain a waste NCM-622 battery positive material; calcining the anode material of the waste NCM-622 battery for 5 hours at 650 ℃ to obtain anode material powder of the waste NCM-622 battery;
s20, mixing the waste NCM-622 battery negative electrode material, a NaCl solution and hydrogen peroxide in a proportion of 1:8:2 to obtain a first solution, carrying out hydrothermal reaction at 220 ℃ for 15min, removing impurities, and carrying out evaporative crystallization to obtain LiCl powder;
s30, mixing the LiCl powder, thiourea and ethyl acetate according to a mass ratio of 1;
s40, mixing the second solution and the waste NCM-622 battery anode material powder according to a proportion of 100ml:2g of the mixture is mixed, the mixture is used as an anode, direct current is introduced to electrolyze the mixture, and the voltage drop between a cathode and the anode is 10V to obtain a third solution;
s50, drying the third solution at 120 ℃ in a spray dryer to obtain anode material powder;
and S60, heating the anode material powder from normal temperature to 600 ℃ at a heating rate of 10 ℃/min, then preserving heat for 4h, cooling to 100 ℃ at a cooling rate of 8 ℃/min, and then naturally cooling to obtain the regenerated NCM-622 (recorded as RNCM-622) battery anode material.
FIG. 2 shows XRD patterns of RNCM-622 and SNCM-622 in example 1, all regenerated NCM-622 having hexagonal layered alpha-NaFeO pattern in accordance with the pattern of spent NCM-622 2 The structure, belonging to the R-3m space group, indicates that this regeneration method does not destroy the original structure of NCM-622.
FIG. 3 is SEM pictures of RNCM-622 and SNCM-622 in example 1, wherein (a) to (c) are SEM pictures of RNCM-622 and (d) to (f) are SEM pictures of SNCM-622. As can be seen from the figure, the surface of the waste NCM-622 has obvious cracks, and the NCM-622 cathode material after regeneration has no cracks, which indicates that the structure of the cathode material is well repaired by the regeneration method.
Fig. 4 (a) is a 100-turn cycle performance diagram of RNCM-622 and SNCM-622 in example 1, from which it can be seen that SNCM-622 is already 135.7mAh/g in the fourth turn and is only 121.5mAh/g after 100 turns, although the first turn discharge is 160 mAh/g. The discharge specific capacity of the first circle of the RNCM-622 can reach 166.7mAh/g, the coulombic efficiency can reach 94.6%, the discharge specific capacity can still reach 151.5mAh/g after one hundred circles of circulation, and the retention rate of the hundred circles is 90.8%. Fig. 4 (b) shows the discharging conditions of RNCM-622 and SNCM-622 in example 1 at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 0.1C, and the discharging specific capacities of RNCM-622 are 156.9mAh/g, 153.9mAh/g, 151.4mAh/g, 148.1mAh/g, 142.2mAh/g, 131.2mAh/g, 119.1mAh/g, and 157.4mAh/g in this order, which shows that the rate capability is better than that of SNCM-622, and the capacity can be rapidly restored to the initial degree from the high rate of 10C to 0.1C, indicating that it has excellent rate capability, and that the lithium supplement effect is very obvious by using the method of the present invention.
Fig. 5 is an impedance diagram of RNCM-622 and SNCM-622 in example 1, from which it can be seen that both samples of RNCM-622 and SNCM-622 have nyquist diagrams of typical ternary cathode materials, and the surface of SNCM-622 material has higher solid electrolyte resistance and charge transfer resistance due to the blocking of lithium ion transport caused by the destruction of the surface layer structure of the thick DEI film of the cathode surface and the cathode material during cyclic charge and discharge. And the resistance values of the RNCM-622 are all reduced, which shows that the regeneration method repairs the damaged structure to a certain degree and has obvious repairing effect.
In summary, the invention discloses a method for regenerating a waste lithium ion battery anode material, which comprises the following steps: discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative electrode material, and pretreating the waste lithium ion battery positive plate to obtain waste lithium ion battery positive electrode material powder; mixing the waste lithium ion battery negative electrode material with a NaCl solution and an accelerant to obtain a first solution, carrying out hydrothermal reaction, and carrying out evaporative crystallization to obtain LiCl powder; mixing the LiCl powder with an organic solvent and an activating agent, and performing saponification reaction to obtain a second solution; mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution; drying the third solution to obtain anode material powder; and quenching the anode material powder to obtain the regenerated lithium ion battery anode material. According to the invention, a negative electrode material obtained by discharging and disassembling the waste lithium ion battery is mixed with NaCl for hydrothermal treatment to obtain LiCl as a lithium source, then the LiCl is mixed with an organic solvent and an activating agent for saponification reaction to obtain a medium with various binding sites, the lithium source can react with the positive electrode material of the waste lithium ion battery in the medium to repair the positive electrode material of the waste lithium ion battery, and then the regenerated positive electrode material of the lithium ion battery can be obtained through drying and quenching treatment.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for regenerating a waste lithium ion battery anode material is characterized by comprising the following steps:
discharging and disassembling the waste lithium ion battery to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative material, and pretreating the waste lithium ion battery positive plate to obtain waste lithium ion battery positive material powder;
mixing the waste lithium ion battery negative electrode material with a NaCl solution and an accelerant to obtain a first solution, carrying out hydrothermal reaction, and carrying out evaporative crystallization to obtain LiCl powder;
mixing the LiCl powder with an organic solvent and an activating agent, and performing saponification reaction to obtain a second solution;
mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution;
drying the third solution to obtain anode material powder;
and quenching the anode material powder to obtain the regenerated lithium ion battery anode material.
2. The method for regenerating the waste lithium ion battery positive electrode material according to claim 1, wherein the solid-liquid mass ratio in the first solution is 1 (5-10).
3. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein the temperature of the hydrothermal reaction is 200-240 ℃ and the time is 10-30min.
4. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein the organic solvent is one or more of urea, acetamide and thiourea.
5. The method for regenerating the cathode material of the waste lithium ion battery as claimed in claim 1, wherein the activator is ethyl acetate or 2-ethylhexyl mono-2-ethylhexyl phosphate.
6. The method for regenerating the anode material of the waste lithium ion battery according to claim 1, wherein the step of mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a third solution specifically comprises:
mixing the second solution with the anode material powder of the waste lithium ion battery to obtain a mixed solution;
and introducing direct current into the mixed solution as an anode to perform electrolysis.
7. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 6, wherein the voltage drop between the cathode and the anode during the electrolysis process is 8-10V.
8. The method for regenerating the anode material of the waste lithium ion battery according to claim 1, wherein the quenching treatment specifically comprises: heating to 500-700 ℃ at room temperature at a heating rate of 10 ℃/min, preserving heat for 4h, cooling to 100 ℃ at a cooling rate of 8 ℃/min, and naturally cooling.
9. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein the step of discharging and disassembling the waste lithium ion battery to obtain the anode plate of the waste lithium ion battery and the anode material of the waste lithium ion battery, and the step of pretreating the anode plate of the waste lithium ion battery to obtain the anode material powder of the waste lithium ion battery specifically comprises:
soaking the waste lithium ion battery in 3M NaCl solution for 24-48h to enable the SOC value of the waste lithium ion battery to be below 20%, and disassembling to obtain a waste lithium ion battery positive plate and a waste lithium ion battery negative material;
placing the waste lithium ion battery positive plate in a 3M NaOH solution, stirring and reacting for 10 hours, washing and filtering to obtain a waste lithium ion battery positive material;
and calcining the waste lithium ion battery anode material at 650 ℃ for 5 hours to obtain waste lithium ion battery anode material powder.
10. The method for regenerating the anode material of the waste lithium ion battery according to claim 1, wherein the waste lithium ion battery is a waste lithium iron phosphate battery or a waste lithium ion ternary battery.
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