CN116093482B - Recycling method and application of waste lithium ion battery anode material - Google Patents
Recycling method and application of waste lithium ion battery anode material Download PDFInfo
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Abstract
The invention discloses a method for recycling a waste lithium ion battery anode material and application thereof, comprising the following steps: A. pretreating a waste lithium ion battery, and separating to obtain waste anode material powder; B. uniformly mixing waste anode material powder with lithium salt, manganese compound and molten salt, and then sintering in an atmosphere containing oxygen to obtain a sintered body; C. grinding, washing and drying the sintered body to obtain the regenerated positive electrode material. According to the invention, the waste lithium ion battery is efficiently recovered by using the molten salt restoration method, and meanwhile, the waste positive electrode material is regenerated into the lithium-rich manganese-based positive electrode material with a monocrystal structure by means of extracting manganese and supplementing lithium, so that the cost of a recovery process is greatly reduced, a product with higher specific capacity and higher commercial value is obtained, considerable economic benefit is brought to enterprises, and large-scale industrial application is facilitated.
Description
Technical Field
The invention relates to the technical field of battery material recovery, in particular to a method for recovering a waste lithium ion battery anode material and application thereof.
Background
The main recovery technologies of the current ternary cathode material include pyrometallurgy, hydrometallurgy, direct regeneration and the like. Pyrometallurgy and hydrometallurgy are relatively mature and have been operated on an industrial scale, but their development has been limited by the disadvantages of high process difficulties, high costs, low recovery rates, secondary pollution and the like. At present, the research of directly recycling the anode material is still in a starting stage, namely, the process of directly recycling the anode material is a reconstruction process of waste materials, the defect of the material can be ideally repaired without damaging the defect, and the degradation of the anode material is related to the lithium loss and the dissolution of transition metal due to the phase change and the body defect of the anode surface and the interface side reaction, and the existing direct recycling method mainly comprises a high-temperature solid-phase method, a hydrothermal-annealing method, an electrochemical lithium intercalation method, a solvent repair method and a molten salt repair method. The high-temperature solid phase method is simple to operate and environment-friendly, but needs to accurately measure the lithium content in the positive electrode material, the designed process is only applicable to one positive electrode material with similar retired degree, and high-temperature sintering also means a large amount of energy consumption and cost. The solvent repair method uses an organic solvent as an ion transmission medium, so that the structure of the material can be well recovered, but the development of the material is hindered by high cost and pollution. The hydrothermal-annealing method has the advantages that waste materials with any retired degree can be treated, but the positive electrode material is difficult to popularize due to the sensitivity and reactivity of the positive electrode material to moisture, and the required high-temperature and high-pressure environment has certain safety problems. The molten salt repairing method is to repair and regenerate the material by providing a low-temperature and molten liquid environment, compared with the high-temperature solid-phase method, the molten salt repairing method does not need long-time high-temperature treatment, saves the cost, can recycle the molten salt, achieves the purpose of closed loop, and has the potential of large-scale application.
The waste ternary positive electrode material is recovered by utilizing a molten salt restoration method, and the structure of the waste ternary positive electrode material is regulated and controlled in a mode of supplementing lithium and nickel, so that the original lithium and the structure are recovered by utilizing reliithiation, and meanwhile, the energy consumption and the carbon emission are reduced, so that the recyclable ternary positive electrode material with high nickel content is produced, and the theoretical specific capacity of the ternary positive electrode material can reach 278 mAh/g. However, the recovery mode not only needs to use expensive nickel, thereby resulting in high recovery cost, but also has small improvement range of electrochemical performance of the ternary positive electrode material obtained by conversion, poor economic benefit and difficult realization of large-scale industrial application.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides a method for recycling the anode material of the waste lithium ion battery and application thereof, which utilizes a molten salt restoration method to recycle the waste lithium ion battery with high efficiency, and regenerates the waste anode material into a lithium-rich manganese-based anode material with a monocrystal structure by extracting manganese and supplementing lithium, thereby not only greatly reducing the cost of a recycling process, but also obtaining a product with higher electrochemical performance and higher commercial value, and overcoming the defects existing in the prior art.
The technical scheme adopted by the invention is as follows: a method for recycling anode materials of waste lithium ion batteries comprises the following steps:
A. pretreating a waste lithium ion battery, and separating to obtain waste anode material powder;
B. uniformly mixing waste anode material powder with lithium salt, manganese compound and molten salt, and then sintering in an atmosphere containing oxygen to obtain a sintered body;
C. grinding, washing and drying the sintered body to obtain the regenerated positive electrode material.
In the prior art, the type of the waste positive electrode material is not changed generally by utilizing a molten salt restoration method to recycle the waste positive electrode material, and when the waste ternary positive electrode material is recycled and regenerated by using the molten salt restoration method, a lithium source and a nickel source are needed to be added for lithium supplementing and nickel supplementing, and the restored ternary positive electrode material is still the ternary positive electrode material with the theoretical specific capacity of about 278mAh/g, and although the obtained ternary positive electrode material has higher capacity (benefit brought by the increase of nickel content) than the former ternary positive electrode material, the recycling process material has high cost and poor economic benefit, and is difficult to realize large-scale industrial application. In the invention, the waste ternary anode material is taken as an example, and when the waste ternary anode material is recovered and regenerated by a molten salt restoration method, the waste ternary anode material is converted into another alpha-NaFeO with a space group of R-3m type under the condition of low cost by extracting manganese and supplementing lithium due to the existence of excessive lithium ions and manganese ions 2 Li of layered structure 2 MnO 3 Thereby obtaining a ternary layered structure and Li with higher specific capacity 2 MnO 3 The theoretical specific capacity of the lithium-rich manganese-based positive electrode material with the solid solution structure can reach 378mAh/g. In the charge-discharge process of the lithium-rich manganese-based positive electrode material, lithium in the mixed layer can migrate into the lithium layer, and the remained octahedral vacancies are occupied by the transition metal elements of the bulk phase through synergistic diffusion, so that almost all lithium can be separated, high specific capacity is provided, the material advantage of the lithium-rich manganese-based positive electrode material is higher than that of the ternary positive electrode material before conversion, considerable economic benefits are brought to enterprises, and large-scale industrial application is facilitated.
Further, in step B, the lithium salt is selected fromLiCl、Li 2 SO 4 、LiNO 3 、LiOH、Li 2 CO 3 、CH 3 One or more of COOLi; the manganese compound is selected from MnO, mnO 2 、Mn 2 O 3 、Mn 3 O 4 、MnCO 3 、Mn(NO 3 ) 2 、MnCl 2 、MnSO 4 、(CH 3 COO) 2 Mn、MnC 2 O 4 One or more of nickel manganese hydroxide and nickel manganese carbonate.
In the invention, the content of substances such as lithium, nickel, cobalt and the like in the waste anode material can be measured by inductively coupled plasma mass spectrometry (ICP-MS), and the doping amount of the lithium salt and the doping amount of the manganese compound are measured according to the molecular formula xLi of the lithium-rich manganese-based anode material 2 MnO 3 ⋅(1–x)LiTMO 2 And the chemical formula of the measured waste anode material is calculated.
Further, the molten salt contains NaCl, KCl, na 2 SO 4 、K 2 SO 4 、NaNO 3 、KNO 3 、LiOH、NaOH、KOH、Na 2 CO 3 、K 2 CO 3 、CH 3 COONa、CH 3 One or more of COOKs.
Further, in the mixture obtained after the waste positive electrode material powder is mixed with the lithium salt, the manganese compound and the molten salt, the molar ratio of the transition metal to the molten salt is 1:1-1:10, which may be, for example, 1:1, 1:2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8, 1:4, 1:4.5, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., preferably 1:2-1:4. accordingly, the molar ratio of the transition metal ions to the molten salt is not too large or too small, and if the ratio of the molten salt is too small, a molten salt pool is difficult to form in the material sintering process, and the molten salt effect in the method is difficult to be exerted; if the proportion of the molten salt is too large, the sintered body of the material is seriously agglomerated, is not easy to break, and has the problem of wasting resources. Preferably, in some embodiments, the molar ratio of the sum of the amounts of nickel element and cobalt element to the amount of manganese element in the mixture obtained by mixing the waste positive electrode material powder with the lithium salt, the manganese compound and the molten salt is 1:2, i.e., n （Ni+Co） : n Mn =1:2。
Further, the mixture obtained after the positive electrode material powder and the molten salt are mixed is subjected to sectional sintering, the mixture is heated to 400-600 ℃ (the temperature can be 400 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃ and the like) at a heating rate of 5 ℃/min-10 ℃/min (for example, 5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, 10 ℃/min and the like), the mixture is subjected to heat-preserving sintering for 4-6 hours (4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours and the like), and the mixture is further heated to 800 ℃ -950 ℃ (the temperature can be 850 ℃, 920 ℃, 800 ℃, 950 ℃, 10 ℃/min, 930 ℃, 10 ℃/min and the like) at a heating rate of 5 ℃/min-10 ℃/min (for example, 5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 9 ℃/min, 9.5 ℃/min, 10 ℃/min and the like), and the mixture is subjected to heat-preserving sintering for 15 hours (4 hours, 10 hours and the like).
Further, after the sintering is completed, the mixture is cooled to 150 ℃ -250 ℃ (which may be 150 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃ and the like) at a cooling rate of 2 ℃/min-5 ℃/min (which may be 2 ℃/min, 2.5 ℃/min, 2.8 ℃/min, 3 ℃/min, 3.5 ℃/min, 3.8 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min and the like), and then cooled to room temperature with a furnace.
Further, the waste lithium ion battery is disassembled and separated to obtain a positive plate, the positive plate is calcined for 1h to 4h (1 h, 2h, 3h, 4h and the like) at 500 ℃ -600 ℃ (the temperature can be 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃ and the like), and the fallen powder is collected to obtain the waste positive plate material powder.
Further, the waste anode material is nickel cobalt lithium manganate, nickel cobalt lithium aluminate or lithium cobalt oxide anode material.
Furthermore, the invention also comprises application of the recovery method of the waste lithium ion battery anode material in preparing the lithium-rich manganese-based anode material, and the recovery method is adopted to prepare the regenerated lithium-rich manganese-based anode material. The regenerated lithium-rich manganese-based positive electrode material prepared by the recovery method provided by the invention overcomes the defects of complex operation, difficult control of morphology, high cost and the like in the traditional preparation process (such as a high-temperature solid-phase sintering method, a coprecipitation method, a water/solvent thermal method and a spray drying method) of the lithium-rich manganese-based positive electrode material.
Further, the molecular formula of the lithium-rich manganese-based positive electrode material is xLi 2 MnO 3 ⋅(1–x)LiTMO 2 Wherein TM is a transition metal element, x is more than 0 and less than or equal to 1.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. according to the invention, molten salt is adopted as an ion conduction medium, so that diffusion of transition metal ions is facilitated, ni/Li mixed discharge of the material is reduced, ni ions in the surface rock salt structure NiO can enter the anode material again in the high-temperature calcination process, so that the harmful rock salt structure and spinel structure are restored to a layered structure, and a precondition is provided for recycling and regenerating to obtain the high-value anode material;
2. the invention adopts the co-molten salt system to directly repair and regenerate the waste anode material, and the low-temperature co-molten mode reduces the energy consumption, so that the invention has the advantages of simple process, lower energy consumption, environmental friendliness, less three wastes and low environmental protection pressure;
3. the recovery method provided by the invention converts the waste positive electrode material into the lithium-rich manganese-based solid solution with more excellent electrochemical performance, thereby not only providing a more economic way for recovery and recycling of the waste positive electrode material, but also providing a preparation process which is low in cost, easy to operate and easy to control for the preparation of the lithium-rich manganese-based positive electrode material, bringing considerable economic benefit for enterprises and being beneficial to realizing large-scale industrial application.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a spent nickel cobalt manganese cathode material (model NCM 111) of example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the S-LNCM-1 material recovered and regenerated in example 1;
FIG. 3 is an XRD pattern for the S-LNCM-1 material recovered and regenerated in example 1; wherein, "2θ (°)" has the meaning of: the X-ray diffraction spectrum (i.e., XRD pattern) is an XRD diffraction spectrum composed by scanning the whole diffraction region with an angle of 2θ and taking the change of angle of 2θ as the abscissa of the X-ray diffraction spectrum and the intensities of diffraction peaks at different diffraction angles as the ordinate;
FIG. 4 is a charge-discharge plot of the S-LNCM-1 material recovered and regenerated in example 1;
fig. 5 is a charge-discharge graph of a commercially available nickel cobalt manganese positive electrode material (model NCM 811).
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for recycling anode materials of waste lithium ion batteries comprises the following steps:
s1 will contain NCM111 (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) Disassembling the waste battery bags of the anode material under inert atmosphere, and separating to obtain an anode plate;
s2, calcining the positive plate at 550 ℃ for 2 hours to enable powder to fall off from a current collector, collecting the powder, grinding and sieving (200-500 meshes) to obtain pretreated positive powder;
s3, uniformly mixing 0.1mol of pretreated positive electrode powder (about 10 g), 0.25mol of LiOH, 0.1mol of MnO and NaCl molten salt, wherein the molar ratio of transition metal to molten salt is 1:10;
s4, after being uniformly mixed, the mixture is transferred into an aluminum oxide crucible, the temperature is increased to 400 ℃ at 10 ℃/min under the oxygen atmosphere (0.01 standard atmospheric pressure), the heat is preserved for 6 hours, and then the temperature is increased to 900 ℃ at 10 ℃/min, and the heat is preserved for 12 hours;
s5, after sintering, reducing the temperature to 200 ℃ at 3 ℃/min, and naturally cooling to room temperature to obtain a sintered product;
s6, grinding the sinter, washing, drying and sieving to obtain the S-LNCM-1 material.
Respectively observing the waste NCM111 anode material and the S-LNCM-1 material through a scanning electron microscope, wherein as shown in fig. 1 and 2, in fig. 1, the polycrystal ternary anode material has obvious ball cracks after being circulated and has serious failure; in FIG. 2, it can be seen that the uniformly dispersed particles of the regenerated single crystal positive electrode material are obtained in combination with FIG. 3, and that these single crystal positive electrode materials contain not only the original layered structure but also Li 2 MnO 3 The diffraction peaks of (2) indicate the formation of a lithium-rich manganese-based solid solution, and no formation of the remaining impurity phases was found.
Further, the CR2032 coin cell was formed by assembling the S-LNCM-1 material (the assembling process is described below), and the cell was obtained by performing a charge-discharge test (the test conditions are described below) on the cell, and the first discharge capacity of the CR2032 coin cell formed by assembling the S-LNCM-1 material at 0.1C was 282.71mAh/g, and the first charge-discharge efficiency was 91.2%, as shown in fig. 4, and the cell had excellent electrochemical properties.
Example 2
A method for recycling anode materials of waste lithium ion batteries comprises the following steps:
s1 will contain NCM523 (LiNi 0.5 Co 0.2 Mn 0.3 O 2 ) Disassembling the waste battery bags of the anode material under inert atmosphere, and separating to obtain an anode plate;
s2, calcining the positive plate at 550 ℃ for 2 hours to enable powder to fall off from a current collector, collecting the powder, grinding and sieving (200-500 meshes) to obtain pretreated positive powder;
s3, 0.1mol of the pretreated positive electrode powder (about 10 g), 0.125mol of Li 2 CO 3 Mn of 0.055mol 2 O 3 With Na and Na 2 SO 4 The molten salt is uniformly mixed, and the mol ratio of the transition metal to the molten salt is 1:1;
s4, after being uniformly mixed, the mixture is transferred into an aluminum oxide crucible, the temperature is increased to 600 ℃ at 10 ℃/min under the oxygen atmosphere (0.1 standard atmospheric pressure), the heat is preserved for 4 hours, and then the temperature is increased to 950 ℃ at 10 ℃/min, and the heat is preserved for 10 hours;
s5, after sintering, reducing the temperature to 200 ℃ at 3 ℃/min, and naturally cooling to room temperature to obtain a sintered product;
s6, grinding the sinter, washing, drying and sieving to obtain the S-LNCM-2 material with the number of S.
Example 3
A method for recycling anode materials of waste lithium ion batteries comprises the following steps:
s1 will contain NCM622 (LiNi 0.6 Co 0.2 Mn 0.2 O 2 ) Disassembling the waste battery bags of the anode material under inert atmosphere, and separating to obtain an anode plate;
s2, calcining the positive plate at 550 ℃ for 2 hours to enable powder to fall off from a current collector, collecting the powder, grinding and sieving (200-500 meshes) to obtain pretreated positive powder;
s3, 0.1mol of the pretreated positive electrode powder (about 10 g), 0.25mol of LiOH, 0.11mol of MnCO 3 Uniformly mixing with KCl molten salt, wherein the molar ratio of transition metal to molten salt is 1:4;
s4, after being uniformly mixed, the mixture is transferred into an aluminum oxide crucible, the temperature is increased to 500 ℃ at 10 ℃/min under the oxygen atmosphere (1 standard atmospheric pressure), the heat is preserved for 5 hours, and then the temperature is increased to 900 ℃ at 10 ℃/min, and the heat is preserved for 12 hours;
s5, after sintering, reducing the temperature to 200 ℃ at 3 ℃/min, and naturally cooling to room temperature to obtain a sintered product;
s6, grinding the sinter, washing, drying and sieving to obtain the S-LNCM-3 material.
Example 4
A method for recycling anode materials of waste lithium ion batteries comprises the following steps:
s1 will contain NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) Disassembling the waste battery bags of the anode material under inert atmosphere, and separating to obtain an anode plate;
s2, calcining the positive plate at 550 ℃ for 2 hours to enable powder to fall off from a current collector, collecting the powder, grinding and sieving (200-500 meshes) to obtain pretreated positive powder;
s3, 0.1mol of the pretreated positive electrode powder (about 10 g), 0.125mol of Li 2 CO 3 MnCl 0.13mol 2 Uniformly mixing with NaCl-KCl (molar mass ratio 1:1) molten salt, wherein the molar ratio of transition metal to molten salt is 1:4;
s4, after being uniformly mixed, the mixture is transferred into an aluminum oxide crucible, the temperature is increased to 500 ℃ at 10 ℃/min under the oxygen atmosphere (1 standard atmospheric pressure), the heat is preserved for 5 hours, and then the temperature is increased to 900 ℃ at 10 ℃/min, and the heat is preserved for 12 hours;
s5, after sintering, reducing the temperature to 200 ℃ at 3 ℃/min, and naturally cooling to room temperature to obtain a sintered product;
s6, grinding the sinter, washing, drying and sieving to obtain the S-LNCM-4 material.
Example 5
A method for recycling anode materials of waste lithium ion batteries comprises the following steps:
s1 will contain NCA (LiNi 0.8 Co 0.15 Al 0.05 O 2 ) Disassembling the waste battery bags of the anode material under inert atmosphere, and separating to obtain an anode plate;
s2, calcining the positive plate at 550 ℃ for 2 hours to enable powder to fall off from a current collector, collecting the powder, grinding and sieving (200-500 meshes) to obtain pretreated positive powder;
s3, 0.1mol of the pretreated positive electrode powder (about 10 g), 0.25mol of LiOH, 0.14mol of MnC 2 O 4 With NaCl-Na 2 SO 4 Uniformly mixing molten salt in a molar mass ratio of 1:1, wherein the molar ratio of transition metal to molten salt is 1:4;
s4, after being uniformly mixed, the mixture is transferred into an aluminum oxide crucible, the temperature is increased to 500 ℃ at 10 ℃/min under the oxygen atmosphere (1 standard atmospheric pressure), the heat is preserved for 5 hours, and then the temperature is increased to 900 ℃ at 10 ℃/min, and the heat is preserved for 12 hours;
s5, after sintering, reducing the temperature to 200 ℃ at 3 ℃/min, and naturally cooling to room temperature to obtain a sintered product;
s6, grinding the sinter, washing, drying and sieving to obtain the S-LNCM-5 material.
Example 6
A method for recycling anode materials of waste lithium ion batteries comprises the following steps:
s1, to include LCO (LiCoO) 2 ) Disassembling the waste battery bags of the anode material under inert atmosphere, and separating to obtain an anode plate;
s2, calcining the positive plate at 550 ℃ for 2 hours to enable powder to fall off from a current collector, collecting the powder, grinding and sieving (200-500 meshes) to obtain pretreated positive powder;
s3, 0.1mol of the pretreated positive electrode powder (about 2 g), 0.25mol of LiOH, 0.15mol of Mn 0.75 Ni 0.25 CO 3 With NaCl-Na 2 SO 4 Uniformly mixing molten salt in a molar mass ratio of 1:1, wherein the molar ratio of transition metal to molten salt is 1:4;
s4, after being uniformly mixed, the mixture is transferred into an aluminum oxide crucible, the temperature is increased to 500 ℃ at 10 ℃/min under the oxygen atmosphere (1 standard atmospheric pressure), the heat is preserved for 5 hours, and then the temperature is increased to 900 ℃ at 10 ℃/min, and the heat is preserved for 12 hours;
s5, after sintering, reducing the temperature to 200 ℃ at 3 ℃/min, and naturally cooling to room temperature to obtain a sintered product;
s6, grinding the sinter, washing with water, drying and sieving to obtain the S-LNCM-6 material.
Test of Performance experiments
The materials obtained in the examples were mixed with a conductive agent (Super P) and a binder (polyvinylidene fluoride (PVDF) dissolved in N-methylpyrrolidone (NMP) in a mass fraction of 5%) at a ratio of 90:5:5, the materials were weighed into a stirring box, the stirring box was placed into a homogenizer with a set program, the materials were uniformly mixed, and then uniformly coated on a 16 μm aluminum foil by a coater, the coating thickness was controlled at 0.25mm, and a positive plate with a diameter of 14mm was obtained by baking, cutting, weighing and pressing, using metallic lithium as the negative electrode, and LiPF as the negative electrode 6 EC (polytetrafluoroethylene)/EMC (epoxy resin) electrolyteAnd a PE (polyethylene) separator to form a CR2032 button cell.
The positive electrode material was replaced with a commercial ternary positive electrode material C-NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) And then assembled into a CR2032 button cell.
After the button cell was set to 10h, the button cell was set on a blue electric tester (CT 2001C) for charge/discharge cycle performance test. The test conditions of the lithium-rich manganese-based material were set as follows: 25 ℃, 2.0V-4.6V, 1c=280 mAh/g, after 3 weeks activation of the button half cell according to a 0.1C/0.1C cycle, 100 weeks at 1C/1C cycle; the test conditions for the commercially available NCM811 were set as follows: 25 ℃, 2.8V-4.3V, 1 C=210 mAh/g (the charge cut-off voltage of the ternary positive electrode material is generally about 4.3V, and too high can cause serious gas production, unstable structure and the like, while the lithium-rich manganese-based material is required to exert Li 2 MnO 3 The charge cut-off voltage is generally about 4.6V, and the two positive electrode materials are not required to have the same test voltage because the working voltages of the two positive electrode materials are different, so that the specific capacity and the cycle performance of the positive electrode materials are inspected according to the same test mode. The specific electrochemical properties are shown in table 1:
table 1 electrochemical performance table of assembled lithium ion batteries of examples
Note that: S-LNCM-1 sample, S-LNCM-2 sample, S-LNCM-3 sample, S-LNCM-4 sample were prepared in examples 1-4, S-LNCMA-5 sample and S-LNCM-6 sample were prepared in examples 5 and 6, respectively;
the c-NCM811 sample was a commercial ternary positive electrode material NCM811.
As can be seen from Table 1, the charge-discharge curve graph of the commercial ternary cathode material C-NCM811 is shown in FIG. 5, the CR2032 button cell assembled by the commercial ternary cathode material C-NCM is 205.41mAh/g in initial discharge capacity at 0.1C, the initial charge-discharge efficiency is 87.6%, the initial discharge capacity of the single crystal lithium-rich manganese-based material regenerated by the waste NCM can reach 270mAh/g at 0.1C, the initial charge-discharge efficiency can reach about 90%, the capacity and the initial efficiency are obviously improved, and the technical advantage is obvious.
In conclusion, the positive electrode material regenerated by the recovery and regeneration method has high specific capacity, the first discharge capacity of the positive electrode material exceeds 273mAh/g at 0.1 ℃, the first charge-discharge efficiency of the positive electrode material exceeds 88%, the cycle performance of the positive electrode material is good, and the positive electrode material has excellent electrochemical performance, so that a more economic way is provided for recovery and cycle use of the waste positive electrode material, and a preparation process with low cost, easy operation and easy control is provided for preparation of the lithium-rich manganese-based positive electrode material, and large-scale industrial application is facilitated.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The method for recycling the anode material of the waste lithium ion battery is characterized by comprising the following steps of:
A. pretreating a waste lithium ion battery, and separating to obtain waste anode material powder;
B. uniformly mixing waste anode material powder with lithium salt, manganese compound and molten salt, wherein the molar ratio of transition metal to molten salt is 1:1-1:10, then sintering in an atmosphere containing oxygen to obtain a sintered body; the method comprises the steps of mixing positive electrode material powder with molten salt, and performing sectional sintering on the mixture; heating the mixture to 400-600 ℃ at a heating rate of 5-10 ℃/min, preserving heat and sintering for 4-6 h, heating the mixture to 800-950 ℃ at a heating rate of 5-10 ℃/min, and preserving heat and sintering for 10-15 h; after sintering, the mixture is cooled to 150-250 ℃ at a cooling rate of 2-5 ℃/min, and then cooled to room temperature along with a furnace;
C. grinding, washing and drying the sintered body to obtain a regenerated positive electrode material, wherein the regenerated positive electrode material is a lithium-rich manganese-based positive electrode material, and the molecular formula of the lithium-rich manganese-based positive electrode material is xLi 2 MnO 3 ⋅(1–x)LiTMO 2 Wherein TM is a transition metal element, x is more than 0 and less than or equal to 1.
2. The method for recycling anode material of waste lithium ion battery according to claim 1, wherein in the step B, the lithium salt is selected from LiCl, li 2 SO 4 、LiNO 3 、LiOH、Li 2 CO 3 、CH 3 One or more of COOLi; the manganese compound is MnO, mnO 2 、Mn 2 O 3 、Mn 3 O 4 、MnCO 3 、Mn(NO 3 ) 2 、MnCl 2 、MnSO 4 、(CH 3 COO) 2 Mn、MnC 2 O 4 One or more of nickel manganese hydroxide and nickel manganese carbonate.
3. The method for recycling anode material of waste lithium ion battery as claimed in claim 2, wherein the molten salt contains NaCl, KCl, na 2 SO 4 、K 2 SO 4 、NaNO 3 、KNO 3 、NaOH、KOH、Na 2 CO 3 、K 2 CO 3 、CH 3 COONa、CH 3 One or more of COOKs.
4. The method for recycling the positive electrode material of the waste lithium ion battery according to claim 1, wherein in the step A, the waste lithium ion battery is disassembled and separated to obtain a positive electrode plate, the positive electrode plate is calcined at 500-600 ℃ for 1-4 h, and the fallen powder is collected to obtain the waste positive electrode material powder.
5. The method for recycling the waste lithium ion battery positive electrode material according to claim 1, wherein the waste positive electrode material is nickel cobalt lithium manganate, nickel cobalt lithium aluminate or lithium cobaltate positive electrode material.
6. The application of a recovery method of a waste lithium ion battery positive electrode material in preparing a lithium-rich manganese-based positive electrode material is characterized in that the recovery method of any one of claims 1-5 is adopted to prepare a regenerated lithium-rich manganese-based positive electrode material.
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