CN113265704B - Method for preparing flake single crystal ternary electrode material with exposed {010} crystal face by regenerating waste lithium ion battery - Google Patents
Method for preparing flake single crystal ternary electrode material with exposed {010} crystal face by regenerating waste lithium ion battery Download PDFInfo
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Abstract
The invention discloses a method for preparing a flaky single crystal ternary electrode material with an exposed {010} crystal face by regenerating a waste lithium ion battery, which comprises the steps of discharging and disassembling a recovered waste ternary lithium ion battery, separating to obtain a positive plate, carrying out alkaline leaching pretreatment and the like to obtain ternary electrode material powder, carrying out mechanical crushing or electrochemical crushing on the electrode material, mixing the collected crushed ternary material powder with lithium-containing molten salt for lithium supplement and calcination, and finally obtaining the regenerated flaky single crystal ternary electrode material with the exposed {010} crystal face. The sheet-shaped single crystal with the exposed {010} crystal face has ordered internal atom arrangement, is beneficial to the diffusion of lithium ions in the crystal, and improves the stability of the structure of the single crystal ternary electrode material. The flaky single crystal ternary electrode material with the exposed {010} crystal face, which is prepared from the ternary electrode material of the waste lithium ion battery, has excellent electrochemical performance, and provides an economic and effective way for recycling and reusing the ternary electrode material of the waste lithium ion battery.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a method for preparing a flaky single crystal ternary electrode material with an exposed {010} crystal face by regenerating a waste lithium ion battery.
Background
The lithium ion battery has high energyDensity, high coulombic efficiency, long cycle life and the like, so that the composite material becomes a main power source for portable electronic products and electric automobiles. Thanks to the push and vigorous subsidization of new energy vehicles by government policies, the new energy vehicle market is growing rapidly, and it is expected that the global manufacturing capacity of lithium ion batteries will increase substantially at a rate of hundreds of GWh per year in the next 5 years. Wherein the LiNi is used for vehicles 1-x-y Mn x Co y O 2 Compared with other anode materials such as lithium iron phosphate, lithium manganate and lithium cobaltate, the ternary anode material has great advantages in the aspects of energy density, cycle stability and the like, so that the market share of the ternary anode material is larger and larger. However, the number of retired lithium ion batteries is increased sharply after the lithium ion batteries reach a service life of 3 to 5 years. With the decommissioning of a large number of ternary lithium ion batteries, LiNi scrapped in the ternary lithium ion batteries 1-x-y Mn x Co y O 2 Under the background that a ternary cathode material contains a large amount of Li, Co, Ni and Mn resources, the recovery and reutilization of waste lithium ion batteries to recover lithium and transition metal resources and the elimination of pollution caused by the disposal of the waste batteries become an urgent task.
The recovery method widely applied at present mainly comprises pyrometallurgy, hydrometallurgy and direct recovery and regeneration method to recover the lithium ion battery anode material. Pyrometallurgy requires high-temperature smelting and multi-stage purification and separation processes, and consumes a large amount of energy; wet metallurgy, however, requires acid leaching followed by a complicated precipitation step to recover valuable metal elements, and has a large amount of wastewater treatment problems. The direct recovery method combines the physical separation process to separate and collect the anode material and the subsequent process of lithium supplement to repair the components and structural defects of the electrode material particles, but broken particles in the waste electrode material powder always exist in the recovered product, so that the morphology, size and structural uniformity of the material are influenced, and the electrochemical performance of the regenerated material is influenced. The existing commercial ternary cathode material is usually in the form of spherical secondary particles composed of aggregated polycrystalline primary particles, and the single crystal ternary cathode material is composed of single crystal particles, and has attracted much attention due to its excellent stability. However, the morphology uniformity and the size of the single crystal ternary cathode material are difficult to control, the morphology of single crystal-like particles is easily formed in the synthesis process, and the crystal structure orientation is not uniform, which seriously affects the electrochemical performance of the material and hinders the development of the single crystal ternary cathode material.
Therefore, a new technology for recycling the waste ternary cathode material is developed, the waste ternary cathode material is regenerated to prepare the single crystal ternary cathode material with uniform appearance and size and highly oriented crystal structure, and the method has great significance and is expected to promote recycling and cyclic utilization of the waste ternary cathode material and development of the single crystal ternary cathode material.
Disclosure of Invention
The invention aims to provide a waste lithium ion battery LiNi 1-x-y Mn x Co y O 2 Regeneration of ternary electrode material to prepare flaky monocrystal LiNi with uniform appearance and size and exposed {010} crystal face 1-x-y Mn x Co y O 2 A method of ternary electrode materials. Due to the uniform appearance and size of the prepared flaky single crystal ternary electrode material, and the {010} crystal face beneficial to promoting lithium ion transmission is exposed, the electrode material has excellent electrochemical performance, and particularly the cycle performance and the stability of the electrode material are obviously improved. The technology provides an economic and effective way for recycling and reusing the waste ternary electrode material.
The invention relates to a method for preparing a flaky single crystal ternary electrode material with an exposed {010} crystal face by regenerating a waste lithium ion battery, which comprises the steps of firstly discharging, disassembling and separating the recovered waste ternary lithium ion battery to obtain a positive plate, and carrying out alkaline leaching pretreatment and the like to obtain ternary electrode material powder; according to the feature that the ternary electrode material of the waste lithium ion battery is a spherical secondary particle composed of primary particles, crushing the spherical secondary particles by adopting a mechanical crushing or electrochemical crushing method to obtain the primary particles; then mixing the collected crushed ternary material powder with lithium-containing molten salt for lithium supplement and calcination to finally obtain regenerated flaky monocrystal LiNi 1-x-y Mn x Co y O 2 A ternary electrode material.
The invention relates to a method for preparing a flaky single crystal ternary electrode material with an exposed {010} crystal face by regenerating a waste lithium ion battery, which specifically comprises the following steps:
step 1: using 0.1 to 1mol of L -1 The alkaline leaching pretreatment of the positive plate by the sodium hydroxide solution achieves the purpose of separating the waste ternary electrode material and the aluminum foil, the waste ternary electrode material powder is obtained after washing and drying, and then the secondary particles are crushed by adopting a mechanical crushing or electrochemical crushing method to obtain primary particles.
Step 2: uniformly mixing the primary particle powder obtained in the step 1 with lithium salt, and then roasting in air or oxygen atmosphere in two steps at 2-5 ℃ for min -1 Heating to 400- -1 Heating to 750-950 ℃, continuing heat preservation for 8-15h, cooling to room temperature along with the furnace to obtain a mixture of the flaky single crystal ternary electrode material and the lithium salt, and washing the soluble lithium salt in the mixture by using deionized water to obtain the flaky single crystal ternary electrode material. Because the surface structure of the flaky monocrystalline ternary electrode material is damaged to a certain extent in the washing impurity removal process, the dried flaky monocrystalline ternary electrode material needs to be heated for 2-5 ℃ min at a heating rate in the air or oxygen atmosphere -1 Heating to 650 plus 850 ℃, carrying out heat preservation treatment for 5-10h, and then cooling to room temperature along with the furnace to obtain the flaky single crystal ternary electrode material with an intact structure. And finally, performing electrochemical test by taking the regenerated flaky monocrystalline ternary electrode material as a lithium ion battery anode material to evaluate the electrochemical performance of the lithium ion battery anode material.
In the step 1, when mechanical crushing is adopted, waste ternary anode material powder and ball milling particles are mixed and then placed in a ball milling tank, and the set rotating speed is 500-1000r min -1 And performing solid-phase ball milling for 2-24h, and crushing secondary particles to obtain primary particles.
In the step 1, when electrochemical crushing is adopted, waste ternary positive electrode material powder and polyvinylidene fluoride are mixed and dispersed in an N-methyl pyrrolidone solvent, stirred into paste and coated on a conductive substrate, and a working electrode coated with the waste ternary positive electrode material is obtained after drying; connecting a working electrode with a positive electrode of a power supply, connecting an inert electrode with a negative electrode of the power supply, and constructing an electrolysis device by taking inorganic salt or organic salt compound solution as supporting electrolyte solution; and then, turning on a power supply, maintaining the current at 0.01-1A, and controllably crushing the waste ternary electrode material into uniform primary particles.
In the step 1, the secondary particles of the waste ternary cathode material are crushed into primary particles by the mechanical method or the electrochemical method, and the particle size is controlled to be below 5 microns.
In step 2, the lithium salt is one or more of lithium chloride, lithium hydroxide, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium oxalate, lithium bicarbonate, and the like, for example, the lithium salt is a mixture of lithium hydroxide and lithium nitrate in a molar ratio of 2: 3, mixing; the mass ratio of the primary particle powder to the lithium salt is 1: 1-1: 10, preferably 1: 3.8.
the inert electrode is one of non-metal electrodes such as graphite, carbon cloth and carbon paper or metal electrodes such as titanium foil, titanium mesh and stainless steel foil.
The conductive substrate is one of non-metal electrodes such as graphite, carbon cloth and carbon paper or metal electrodes such as titanium foil, titanium mesh and stainless steel foil.
The supporting electrolyte solution comprises one or more of inorganic salt or organic salt compound solutions such as sodium chloride, lithium chloride, sodium sulfate, lithium sulfate, potassium sulfate, ammonium acetate, sodium dodecyl sulfate and the like; the concentration range of the supporting electrolyte solution is 0.01-10 mol L -1 。
The ternary electrode material of the waste lithium ion battery is LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiNi 0.4 Co 0.2 Mn 0.4 O 2 、 LiNi 0.5 Co 0.2 Mn 0.3 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.7 Co 0.1 Mn 0.2 O 2 、LiNi 0.8 Co 0.1 Mn 0.1 O 2 One or more of the following; also included are LiNiO 2 、LiNi 0.9 Mn 0.1 O 2 、LiNi 0.9 Co 0.1 O 2 Electrode material with higher nickel contentMaterial (considering LiNi) 1-x-y Mn x Co y O 2 The values of x and y are both zero); also included are cases of elemental substitution or doping, e.g. LiNi 1-x-y Co x M y O 2 And LiNi 1-x-y Mn x M y O 2 (wherein M represents a metal element such as Fe, Mg, Al, Ti, etc.) or the like can be recovered and regenerated by the method. The process is likewise suitable for delta Li 2 MnO 3 ·(1-δ)LiNi 1-x-y Mn x Co y O 2 (δ 0-1) recovering the lithium-rich electrode material.
The morphology of the ternary electrode material of the waste lithium ion battery comprises, but is not limited to, a sphere, a rod, irregular particles and the like.
The strategy of recovering and preparing the flaky single crystal ternary electrode material by adopting a mechanical crushing or electrochemical crushing auxiliary molten salt method is adopted, the crushed primary particles are prepared into the flaky single crystal ternary electrode material with the crystal face exposed out of the {010} crystal face again by utilizing the high-temperature molten salt condition, the shape structure of the material is reformed by effectively utilizing high-temperature energy, the complex step of producing a precursor by dissolving and precipitating firstly in a hydrometallurgy method is avoided, the problem that the shape, the size and the structure of the recovered product are not uniform in a direct recovery method is solved, the electrochemical performance of the material can be effectively improved by exposing the {010} crystal face beneficial to lithium ion transmission, and the flaky single crystal ternary electrode material recovered and prepared by the method has excellent electrochemical performance, and particularly the cycle performance of the electrode material is obviously improved.
Compared with the prior art, the invention has the beneficial effects that:
the flaky single crystal ternary electrode material with the exposed {010} crystal face is prepared by a mechanical crushing or electrochemical crushing auxiliary molten salt recovery strategy. The existing single crystal preparation technology is mainly to synthesize Ni with proper grain diameter by adopting battery-grade chemical raw materials x Co y Mn 1-x-y (OH) 2 Preparing a single crystal ternary electrode material by a molten salt method, wherein the obtained single crystal ternary electrode material generally has an irregular particle morphology; existing molten salt repairThe recovery of the waste ternary cathode material by the lithium technology focuses more on the defect of lithium in the waste ternary cathode material and the repair of a non-lamellar phase structure, and the design of the morphology and size uniformity of crushed particles in the waste ternary cathode material and the orientation control of a crystal structure are not related; the technical report that the ternary anode material of the waste lithium ion battery is regenerated by adopting an electrochemical crushing or mechanical crushing auxiliary molten salt method to prepare the flaky single crystal ternary electrode material with the exposed {010} crystal face is not available. The flaky single crystal ternary electrode material with the exposed {010} crystal face, prepared by the recovery strategy provided by the invention, has excellent electrochemical performance, and particularly remarkably improves the cycling stability of the material. For example, at 1C current density, waste ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 The discharge capacity of the electrode material is only 34.8mAh g -1 And the regenerated and prepared flaky single crystal ternary LiNi exposing a {010} crystal face 0.6 Co 0.2 Mn 0.2 O 2 The discharge capacity of the electrode material is up to 153.0mAh g -1 Circulating 200 circles under the current density of 1C, and obtaining the flaky single crystal ternary LiNi 0.6 Co 0.2 Mn 0.2 O 2 The capacity retention of the electrode material was as high as 96.6% (see fig. 4). The method not only provides an effective new way for recycling the ternary cathode material of the waste lithium ion battery, but also provides a new method for preparing the flaky single crystal ternary electrode material with the exposed {010} crystal face and excellent electrochemical performance.
Drawings
FIG. 1 is a diagram showing (a) waste LiNi in example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material morphology picture, (b) waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 Primary particle morphology picture obtained by mechanically crushing ternary cathode material, (c) flaky single crystal LiNi obtained by regenerating after mechanical crushing 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material morphology picture, (d) waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 A primary particle morphology photo obtained by electrochemical crushing of the ternary cathode material, (e-f) a flaky single crystal LiNi obtained by regeneration after electrochemical crushing 0.6 Co 0.2 Mn 0.2 O 2 Scanning Electron Microscope (SEM) morphology photographs of the ternary cathode material.
FIG. 2 is a diagram showing (a) waste LiNi in example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material, and (b) sheet-like single crystal LiNi prepared by regeneration after mechanical crushing 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material, and (c) sheet-like single crystal LiNi prepared by electrochemical crushing and regeneration 0.6 Co 0.2 Mn 0.2 O 2 X-ray diffraction (XRD) pattern of the ternary cathode material.
FIG. 3 is a sheet-like single crystal LiNi which was regenerated after electrochemical crushing in example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 The images of Transmission Electron Microscope (TEM), High Resolution Transmission Electron Microscope (HRTEM) and Selected Area Electron Diffraction (SAED) of the ternary cathode material in different directions are as follows: (a-c) a front surface, and (d-f) a side surface.
FIG. 4 shows (a) waste LiNi in example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material, (b) regenerating and preparing sheet monocrystal LiNi after mechanical crushing 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material, and (c) sheet-shaped single crystal LiNi obtained by electrochemical crushing and regeneration 0.6 Co 0.2 Mn 0.2 O 2 And (3) a charge-discharge cycle performance diagram of the ternary cathode material.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1: from waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 Method for preparing sheet-shaped single crystal LiNi by regenerating ternary electrode material 0.6 Co 0.2 Mn 0.2 O 2 Ternary electrode material method
Using 0.1mol L -1 Separating waste LiNi from the anode plate pretreated by the sodium hydroxide solution 0.6 Co 0.2 Mn 0.2 O 2 Washing and drying the ternary electrode material and aluminum foil to obtain waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material powder. If mechanical crushing is adopted, the waste LiNi is crushed 0.6 Co 0.2 Mn 0.2 O 2 Mixing ternary anode material powder and ball milling particles, placing the mixture in a ball milling tank, and setting the rotating speed to be 1000r min -1 And carrying out solid-phase ball milling for 4h, and crushing secondary particles to obtain primary particles. If electrochemical crushing is used, waste LiNi is crushed 0.6 Co 0.2 Mn 0.2 O 2 Mixing the ternary positive electrode material powder and polyvinylidene fluoride according to the weight ratio of 150: 1 in N-methyl pyrrolidone solvent, mixing and stirring into paste, coating on a titanium mesh, and placing in a vacuum oven for drying to obtain the working electrode. Connecting the working electrode with the positive electrode of a direct current power supply, and connecting the blank titanium net with the negative electrode of the direct current power supply to obtain a titanium net with the concentration of 0.5mol L -1 The lithium nitrate solution is used as electrolyte to construct an electrolytic cell. The power was turned on and the current was maintained steady at 500mA for 2 h. Collecting primary particles obtained by electrochemical crushing at the bottom of the electrolytic cell, washing and drying.
Mixing the primary particle powder obtained above with a lithium salt (the molar ratio of lithium hydroxide to lithium nitrate is 2: 3) according to a mass ratio of 1: 3.8 mixing and grinding, roasting in air atmosphere in two steps, at first 3 deg.C for min -1 Heating to 500 deg.C, maintaining for 5 hr, and heating at 3 deg.C for 3 min -1 Heating to 850 ℃, continuing heat preservation treatment for 11h, and cooling to room temperature along with the furnace to obtain the flaky single crystal LiNi 0.6 Co 0.2 Mn 0.2 O 2 Ternary electrode material and lithium salt mixture.
Washing soluble lithium salt in the mixture by deionized water to obtain the sheet-shaped single crystal LiNi 0.6 Co 0.2 Mn 0.2 O 2 And (3) placing the ternary electrode material in a constant-temperature drying box for drying.
The dried flaky single crystal ternary electrode material is subjected to heat preservation treatment again at 700 ℃ for 6 hours in the air or oxygen atmosphere, and then is cooled to room temperature along with the furnace to obtain the flaky single crystal LiNi with an intact structure 0.6 Co 0.2 Mn 0.2 O 2 A ternary electrode material.
Example 2: from waste LiNi 0.5 Co 0.2 Mn 0.3 O 2 Method for preparing sheet-shaped single crystal LiNi by regenerating ternary electrode material 0.5 Co 0.2 Mn 0.3 O 2 Ternary electrode material method
Using 0.1mol L -1 Separating waste LiNi from the anode plate pretreated by the sodium hydroxide solution 0.5 Co 0.2 Mn 0.3 O 2 Washing and drying the ternary electrode material and aluminum foil to obtain waste LiNi 0.5 Co 0.2 Mn 0.3 O 2 Ternary positive electrode material powder. If mechanical crushing is adopted, the waste LiNi is crushed 0.5 Co 0.2 Mn 0.3 O 2 Mixing ternary anode material powder and ball milling particles, placing the mixture in a ball milling tank, and setting the rotating speed to be 1000r min -1 And carrying out solid-phase ball milling for 4h, and crushing secondary particles to obtain primary particles. If electrochemical crushing is used, waste LiNi is crushed 0.5 Co 0.2 Mn 0.3 O 2 Mixing the ternary anode material powder and polyvinylidene fluoride according to the weight ratio of 150: dispersing the mixture in N-methyl pyrrolidone solvent according to the mass ratio of 1, mixing the mixture into paste, coating the paste on a titanium mesh, and placing the paste in a vacuum oven for drying to obtain the working electrode. Connecting the working electrode with the positive electrode of a direct current power supply, and connecting the blank titanium net with the negative electrode of the direct current power supply to obtain a titanium net with the concentration of 0.5mol L -1 The lithium nitrate solution is used as an electrolyte to construct an electrolytic cell. The power was turned on and the current was maintained steady at 500mA for 2 h. Collecting primary particles obtained by electrochemical crushing at the bottom of the electrolytic cell, washing and drying.
Mixing the primary particles obtained above with a lithium salt (the molar ratio of lithium hydroxide to lithium nitrate is 2: 3) in a mass ratio of 1: 3.8 mix-grind evenly, calcine in air atmosphere in two steps, first at 3 deg.C for min -1 Heating to 500 deg.C, holding for 5 hr, and heating at 3 deg.C for 3 min -1 Heating to 850 ℃, continuing heat preservation treatment for 11h, and cooling to room temperature along with the furnace to obtain the sheet-shaped single crystal LiNi 0.5 Co 0.2 Mn 0.3 O 2 Ternary electrode material and lithium salt mixture.
Washing soluble lithium salt in the mixture by deionized water to obtain the flaky single crystal LiNi 0.5 Co 0.2 Mn 0.3 O 2 And (3) placing the ternary electrode material in a constant-temperature drying box for drying.
Preserving the heat of the dried flaky single crystal ternary electrode material for 6 hours at 700 ℃ in air atmosphere, and then cooling the dried flaky single crystal ternary electrode material to room temperature along with a furnace to obtain the flaky single crystal LiNi with a good structure 0.5 Co 0.2 Mn 0.3 O 2 A ternary electrode material.
Example 3: from waste LiNi 0.8 Co 0.1 Mn 0.1 O 2 Preparation of sheet-shaped single crystal LiNi by regeneration of ternary electrode material 0.8 Co 0.1 Mn 0.1 O 2 Ternary electrode material method
With 0.1mol L -1 Separating waste LiNi from the anode plate pretreated by the sodium hydroxide solution 0.8 Co 0.1 Mn 0.1 O 2 Washing and drying the ternary electrode material and aluminum foil to obtain waste LiNi 0.8 Co 0.1 Mn 0.1 O 2 Ternary positive electrode material powder. If mechanical crushing is adopted, the waste LiNi is crushed 0.8 Co 0.1 Mn 0.1 O 2 Mixing the ternary anode material powder and the ball mill, placing the mixture in a ball milling tank, and setting the rotating speed to be 1000r min -1 And performing solid-phase ball milling for 4 hours, and crushing secondary particles to obtain primary particles. If electrochemical crushing is used, waste LiNi is crushed 0.8 Co 0.1 Mn 0.1 O 2 Mixing the ternary positive electrode material powder and polyvinylidene fluoride according to the weight ratio of 150: dispersing the mixture in N-methyl pyrrolidone solvent according to the mass ratio of 1, mixing the mixture into paste, coating the paste on a titanium mesh, and placing the paste in a vacuum oven for drying to obtain the working electrode. Connecting the working electrode with the positive electrode of a direct current power supply, and connecting the blank titanium net with the negative electrode of the direct current power supply to obtain a titanium net with the concentration of 0.5mol L -1 The lithium nitrate solution is used as an electrolyte to construct an electrolytic cell. The power was turned on and the current was maintained steady at 500mA for 2 h. Collecting primary particles obtained by electrochemical crushing at the bottom of the electrolytic cell, washing and drying.
Mixing the above obtained primary particles with lithium salt (hydrogen and oxygen)The molar ratio of lithium fluoride to lithium nitrate is 2: 3) according to the mass ratio of 1: 3.8 mix-grind evenly, then calcine in oxygen atmosphere in two steps, first at 3 deg.C for min -1 Heating to 500 deg.C, holding for 5 hr, and heating at 3 deg.C for 3 min -1 Heating to 850 ℃, continuing heat preservation treatment for 11h, and cooling to room temperature along with the furnace to obtain the sheet-shaped single crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 Ternary electrode material and lithium salt mixture.
Washing soluble lithium salt in the mixture by deionized water to obtain the flaky single crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 And (3) placing the ternary electrode material in a constant-temperature drying box for drying.
The dried flaky single crystal ternary electrode material is subjected to heat preservation treatment for 6 hours again at 700 ℃ in an oxygen atmosphere, and then is cooled to room temperature along with a furnace to obtain the flaky single crystal LiNi with an intact structure 0.8 Co 0.1 Mn 0.1 O 2 A ternary electrode material.
Table 1 shows the results of X-ray spectroscopy before and after the recovery of the sample of example 1. From the table, it can be seen that the Ni obtained from the test: mn: the atomic ratio of Co is close to 6: 2: 2, indicating that the elemental composition of the sample did not substantially change before and after recovery.
Table 2 shows the results of calculation of the unit cell parameters obtained from X-ray diffraction (XRD) patterns before and after the recovery of the sample of example 1. As can be seen from the table, I before and after recovery (003) /I (104) 1.187, 2.485 and 2.699, respectively, indicating waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 The material LiNi is seriously mixed and discharged, and the flaky single crystal LiNi obtained by mechanical crushing or electrochemical crushing assisted molten salt recovery and regeneration 0.6 Co 0.2 Mn 0.2 O 2 The material has very low lithium-nickel mixing degree. The values of the lattice constant c/a of the recovered samples are close, which indicates that the two materials have relatively complete laminated structures.
TABLE 1
TABLE 2
FIG. 1 includes a Scanning Electron Microscope (SEM) photograph of a sample of example 1 of the present invention. (a) Waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material morphology picture, (b) waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 Primary particle morphology picture of ternary anode material after mechanical crushing, (c) sheet-shaped single crystal LiNi obtained by regeneration after mechanical crushing 0.6 Co 0.2 Mn 0.2 O 2 Morphology picture of ternary anode material, (d) waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 Primary particle morphology picture of ternary anode material after electrochemical crushing, (e-f) sheet monocrystal LiNi obtained by regeneration after electrochemical crushing 0.6 Co 0.2 Mn 0.2 O 2 And (4) a morphology picture of the ternary cathode material. It is apparent from the figure that waste LiNi 0.6 Co 0.2 Mn 0.2 O 2 The ternary anode material is in the shape of spherical secondary particles consisting of primary particles, the spherical particles are converted into primary particles after mechanical crushing or electrochemical crushing, and finally the material is converted into a flaky single crystal shape from the primary particles through regeneration treatment by a molten salt method.
FIGS. 2(a), (b) and (c) are respectively waste LiNi of example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material and sheet-shaped single crystal LiNi obtained by recycling and regenerating 0.6 Co 0.2 Mn 0.2 O 2 X-ray diffraction (XRD) pattern of the ternary cathode material. The diffraction peaks of the three samples are clear and sharp and are all equal to the alpha-NaFeO 2 The layered structures correspond to and belong to
The space groups, and the diffraction peaks of (006)/(012) and (018)/(110) are all obviously split, which shows that the materials have typical laminated structures before and after recycling.
FIG. 3 is a sheet-like single crystal LiNi which was regenerated after electrochemical crushing in example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 And (c) images of the ternary cathode material on the front surface (a-c) and the side surface (d-f) of the ternary cathode material respectively correspond to a Transmission Electron Microscope (TEM), a high-resolution transmission electron microscope (HRTEM) and a Selected Area Electron Diffraction (SAED) photograph. FIG. 3b shows a reproducibly prepared, sheet-like, single-crystal LiNi 0.6 Co 0.2 Mn 0.2 O 2 The ternary cathode material has good crystallinity, and a layered structure is formed in a bulk phase and a surface region; the lattice fringe spacing is 0.246nm and corresponds to a (100) crystal face in the layered structure; fig. 3c reflects that the sheet-like front structure corresponds to the 001 plane of the layered structure. If the front surface of the sheet is a {001} surface, since the {010} surface is perpendicular to the {001} surface, the side surface is highly likely to belong to the {010} surface. High Resolution Transmission Electron Microscopy (HRTEM) images of the facets (fig. 3b) show a lattice spacing of 0.47nm, corresponding to the (003) plane, indicating that the facets are parallel to the c-axis direction. The Selected Area Electron Diffraction (SAED) pattern of the plate-like side surfaces (FIG. 3f) further reveals that the side surfaces are 010 planes. The combination of the flaky morphology can indicate the regenerated flaky single crystal LiNi 0.6 Co 0.2 Mn 0.2 O 2 The ternary positive electrode material has an exposed 010 crystal plane. To facilitate calculation of the exposure rate of the {010} crystal plane, according to the feature size of fig. 1(e-f), it can be assumed that the flaky single crystal particle is a cylinder with a diameter of 1.5 μm and a height of 0.73 μm, and by calculating the ratio of the side surface area to the total area of the cylinder, the exposure rate of the {010} crystal plane is 49.3%.
The three materials in the example 1 are mixed with conductive carbon black and polyvinylidene fluoride respectively in a mass ratio of 8: 1: 1 proportion is dispersed in N-methyl pyrrolidone solvent for mixing, after size mixing, a scraper is used for evenly coating on an aluminum foil, after drying in a drying box at 80 ℃, the aluminum foil is rolled and compacted, and the aluminum foil is cut into a positive plate with the diameter of 12 mm. Assembling the positive plate, the metal lithium plate and a Cellgard 2400 type polypropylene film into a 2032 button cell in a glove box filled with argon, and then carrying out electrochemical performance test on the cell under the constant temperature condition of 25 ℃.
FIGS. 4(a), (b) and (c) are respectively the waste LiNi in example 1 of the present invention 0.6 Co 0.2 Mn 0.2 O 2 Ternary positive electrode material and sheet-like single crystal LiNi prepared by regeneration of the method of the present invention 0.6 Co 0.2 Mn 0.2 O 2 And (3) a charge-discharge cycle performance diagram of the ternary cathode material under the current density of 1C. As can be seen from the figure, the waste LiNi in example 1 0.6 Co 0.2 Mn 0.2 O 2 The first discharge capacity of the ternary cathode material under the current density of 1C is only 34.8mAh g -1 After circulating for 100 circles, the capacity is reduced to 20.5mAh g -1 . The method of the invention mechanically breaks the flaky single crystal LiNi prepared by assisting the regeneration of the molten salt 0.6 Co 0.2 Mn 0.2 O 2 The first discharge capacity of the ternary cathode material under the current density of 1C can reach 150.2mAh g -1 The capacity is still 137.9mAh g after 200 cycles of circulation -1 The capacity retention rate reaches 91.8%, and excellent cycle performance is shown. In particular to sheet-shaped single crystal LiNi prepared by electrochemical crushing auxiliary molten salt regeneration 0.6 Co 0.2 Mn 0.2 O 2 The first discharge capacity of the ternary cathode material under the current density of 1C can reach 153.0mAh g -1 The capacity is kept at 147.8mAh g after circulating for 200 circles -1 The capacity retention rate reaches 96.6 percent, compared with the sheet-shaped single crystal LiNi prepared by mechanical crushing auxiliary molten salt regeneration 0.6 Co 0.2 Mn 0.2 O 2 Has better cycle performance.
Tests show that the flaky single crystal ternary positive electrode materials prepared by recycling in other embodiments have higher charge-discharge specific capacity and stable long cycle performance.
The above description is only a partial example of the present invention and should not be construed as limiting the present invention, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for preparing a flaky single crystal ternary electrode material with an exposed {010} crystal face by regenerating a waste lithium ion battery is characterized by comprising the following steps: firstly, discharging, disassembling and separating the recovered waste ternary lithium ion batterySeparating to obtain a positive plate, and performing alkaline leaching pretreatment and the like to obtain ternary electrode material powder; according to the morphological structure characteristic that the ternary electrode material of the waste lithium ion battery is spherical secondary particles formed by primary particles, crushing the spherical secondary particles by adopting a mechanical crushing or electrochemical crushing method to obtain primary particles; then mixing the collected crushed ternary material powder with lithium-containing molten salt for lithium supplementing calcination to finally obtain regenerated flaky single crystal LiNi 1-x-y Mn x Co y O 2 A ternary electrode material;
the method comprises the following steps:
step 1: using 0.1 to 1mol of L -1 The alkaline leaching pretreatment of the positive plate by the sodium hydroxide solution achieves the purpose of separating the waste ternary electrode material from the aluminum foil, the waste ternary electrode material powder is obtained after washing and drying, and then secondary particles are crushed by adopting a mechanical crushing or electrochemical crushing method to obtain primary particles;
step 2: uniformly mixing the primary particle powder obtained in the step 1 with lithium salt, roasting in air atmosphere in two steps, cooling to room temperature along with a furnace to obtain a flaky single crystal ternary electrode material and a lithium salt mixture, and washing and removing soluble lithium salt in the mixture by using deionized water to obtain the flaky single crystal ternary electrode material;
in the step 2, the lithium salt is one or more of lithium chloride, lithium hydroxide, lithium carbonate, lithium sulfate, lithium nitrate, lithium acetate, lithium oxalate and lithium bicarbonate; the mass ratio of the primary particle powder to the lithium salt is 1: 1-1: 10;
in step 2, the roasting is firstly carried out for 2-5 ℃ min -1 Heating to 400- -1 Heating to 750-950 ℃, continuing heat preservation for 8-15h, and cooling to room temperature along with the furnace to obtain a flaky single crystal ternary electrode material and lithium salt mixture;
in the step 2, the deionized water is used for washing and impurity removal, which can cause the surface structure of the flaky single crystal ternary electrode material to be damaged to a certain extent, so that the dried flaky single crystal ternary electrode material is heated for 2-5 ℃ min at the heating rate in the air or oxygen atmosphere -1 Heating to 650-850 ℃ for secondary protectionAnd (3) performing warm treatment for 5-10h, and then cooling to room temperature along with the furnace to obtain the flaky single crystal ternary electrode material with an intact structure.
2. The method of claim 1, wherein:
in the step 1, when mechanical crushing is adopted, waste ternary anode material powder and ball milling particles are mixed and then placed in a ball milling tank, and the set rotating speed is 500-1000r min -1 And performing solid-phase ball milling for 2-24h, and crushing secondary particles to obtain primary particles.
3. The method of claim 1, wherein:
in the step 1, when electrochemical crushing is adopted, waste ternary positive electrode material powder and polyvinylidene fluoride are mixed and dispersed in an N-methyl pyrrolidone solvent, stirred into paste and coated on a conductive substrate, and a working electrode coated with the waste ternary positive electrode material is obtained after drying; connecting a working electrode with a positive electrode of a power supply, connecting an inert electrode with a negative electrode of the power supply, and constructing an electrolysis device by taking inorganic salt or organic salt compound solution as supporting electrolyte solution; and then, turning on a power supply, maintaining the current at 0.01-1A, and controllably crushing the waste ternary electrode material into uniform primary particles.
4. A method according to claim 2 or 3, characterized in that:
the secondary particles of the waste ternary cathode material are crushed into primary particles by a mechanical method or an electrochemical method, and the particle size is controlled to be below 5 mu m.
5. The method of claim 3, wherein:
the supporting electrolyte solution comprises one or more of inorganic salt or organic salt compound solutions such as sodium chloride, lithium chloride, sodium sulfate, lithium sulfate, potassium sulfate, ammonium acetate, sodium dodecyl sulfate and the like; the concentration range of the supporting electrolyte solution is 0.01-10 mol L -1 。
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