CN111952552A - Glass state coated positive electrode material and preparation method thereof - Google Patents
Glass state coated positive electrode material and preparation method thereof Download PDFInfo
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Abstract
A glass state coated anode material comprises an anode material matrix and a glass state substance Li coated on the surface of the anode material matrix3‑3fAlfBO3Wherein f is more than 0 and less than 1. The preparation method comprises the following steps: according to Li3‑3fAlfBO3Weighing raw materials according to a ratio, dissolving a weighed Al source in an ethanol solvent, adding a B source, and stirring to obtain a coating solution; then adding Li source into the coating solution, stirring to obtain glass stateA viscous, gelatinous coating material; adding the glassy state colloidal coating material into a positive electrode material matrix to be coated, stirring, drying, screening, sintering, crushing and screening to obtain the glassy state coated positive electrode material. The coating adopted in the invention is a compact glassy substance, has strong adhesive capacity, can fill the void on the surface of the anode material particles after coating, effectively reduce the specific surface area, reduce the side reaction of the electrolyte and the anode material, prevent the structure from collapsing and improve the long-circulating performance.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a glassy state coated positive electrode material and a preparation method thereof.
Background
In recent years, new energy electric vehicles are more and more concerned and rapidly developed under the strong support of governments at home and abroad. As a core technology of electric vehicles, research on power batteries is critical. The lithium ion battery is recognized as the most potential power battery for the electric vehicle by virtue of the advantages of high specific capacity, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like. The performance of the power battery is mainly determined by the anode material.
The ideal positive electrode material of the power lithium battery has the most basic requirement of long cycle life, the current requirement is at least matched with half of the service life of the whole vehicle (8-10 years), the cycle frequency is more than 3000 times, and the safety performance is the second, which are one of the technical problems restricting the application of the positive electrode material in the field of power batteries. At present, in order to solve the problems of long cycle life and safety performance of the anode material, inorganic electrochemical active metal oxide is generally adopted for doping or cladding, the doped metal element replaces the position of the main metal element of the anode material, and the bond energy is enhanced, but the cladding material enables the anode material particles not to directly detect the electrolyte, prevents the dissolution of the main element, shortens the cycle life due to lattice collapse, influences the safety performance and the like; moreover, the coating of the metal oxide is generally a particle coating, so that a uniform and compact coating layer is difficult to form, and the metal oxide is still partially contacted with the electrolyte, so that the corrosion of the electrolyte cannot be well prevented.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology and provide a glassy state coated cathode material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a glass state coated anode material comprises an anode material matrix and a glass state substance Li coated on the surface of the anode material matrix3-3fAlfBO3Wherein f is more than 0 and less than 1.
Boron is an important element for synthesizing glass, and at high temperature, oxide or borate compound of boron can form molten glassy substance which is combined with Al and Li, and the reaction at high temperature can generate the glassy substance Li3-3fAlfBO3Therefore, a compact glassy coating layer can be formed on the surface of the matrix of the anode material, and side reactions caused by contact with the electrolyte in the circulation process of the anode material are effectively eliminated; meanwhile, the coefficient of Li is more than 0 and less than 3-3f and less than 3, at the moment, the coating material is in a Li-lacking state, and when the coating material is coated on the surface of the positive electrode material, residual Li on the surface of the positive electrode material is diffused into the glassy coating material, so that the residual Li is reduced, and the high-temperature storage performance is improved.
In the positive electrode material of the present invention, Li having a colloidal glassy state is used3-3fAlfBO3As a coating of the anode material matrix, the coating can be in good contact with the anode material to be tightly adhered to form a compact coating layer, and the defect of conventional particle coating is perfectly overcome.
In the above coated cathode material, preferably, the glassy substance Li3-3fAlfBO3The weight of (a) is 0.01-2% of the weight of the positive electrode material.
Preferably, the coated positive electrode material has a specific surface area of 0.2 to 0.9m2(ii)/g; the tap density is 1.5-2.5 g/cm3。
In the above coated cathode material, preferably, the molecular formula of the matrix of the cathode material is Li1+a(NixCoyMn1-x-y)1-b(M)bO2(ii) a Wherein M is any one or more of doped metal elements Al, Mg, Zr, Ti, Sr, Y, Nb, W, Bi and La, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 0.9, Y is more than or equal to 0 and less than or equal to 0.334, and x + Y is more than or equal to 0 and less than or equal to 1.
As a general inventive concept, the present invention also provides a method for preparing the above coated cathode material, comprising the steps of:
(1) according to Li3-3fAlfBO3Weighing raw materials according to a ratio, dissolving a weighed Al source in an ethanol solvent, adding a B source, and stirring to obtain a coating solution;
adding a Li source into the coating solution, and stirring to obtain a glassy viscous colloidal coating substance;
(2) adding the glassy colloidal coating substance into a positive electrode material matrix to be coated, stirring, drying and screening;
(3) sintering, crushing and screening the material screened in the step (2) to obtain the glassy state coated anode material.
In the preparation method, preferably, in the step (1), the viscosity of the glassy viscous colloidal coating material is controlled to 3000-10000Pa · s. Too thin of a package viscosity will result in delamination of the coating material; excessive stickiness will result in an uneven coating.
In the above preparation method, preferably, in the step (1), the Al source is at least one of aluminum carbonate, aluminum nitrate, aluminum chloride and aluminum hydroxide; the B source is one of boron oxide and boric acid; the Li source is any one of lithium carbonate, lithium hydroxide, lithium oxide, lithium halide, lithium phosphate, lithium acetate and lithium oxalate; the particle diameters of the Li source and the B source are preferably on the order of nanometers.
In the preparation method, preferably, in the step (2), the temperature is raised to 60-100 ℃ while stirring, and ethanol is evaporated to avoid danger; then putting the mixture into drying equipment, wherein the drying temperature is 100-200 ℃; the water bath heating and stirring can prevent the coating slurry from layering, and the dynamic primary drying process ensures that the coating can be uniformly coated and attached on the particles.
In the step (3), the sintering temperature is 300-700 ℃, and the sintering time is 5-10 h.
In the preparation method, preferably, the cathode material matrix is mainly prepared according to the following preparation method:
(a) weighing Ni according to stoichiometric ratioxCoyMn1-x-yAdding the precursor, the lithium source and the dopant M raw material into a high-speed mixer for mixing to obtain a mixture;
(b) placing the mixture into sintering equipment, heating to 450-550 ℃ in air or oxygen atmosphere, keeping the temperature constant for 5-15h, continuing to heat to 800-1000 ℃, keeping the temperature constant for 5-15h, naturally cooling to 100 ℃, and discharging; the invention adopts a segmentation method to sinter, and promotes Li firstly2CO3Melting is beneficial to Li to fully react, and then the formation of the crystal lattice of the anode material is controlled;
(c) crushing the product sintered in the step (b), and sieving with a 200-400-mesh sieve to obtain a positive electrode material matrix Li1+a(NixCoyMn1-x-y)1-b(M)bO2。
In the above production method, preferably, in the step (a), NixCoyMn1-x-yThe precursor is selected from at least one of oxide, hydroxide and carbonate corresponding to the precursor; the lithium source is at least one of lithium carbonate, lithium hydroxide and lithium chloride; the dopant M raw material refers to one or more of oxide, hydroxide, phosphate and acetate containing the doping element M.
In the above preparation method, preferably, in the step (b), the rate of introducing the air or oxygen atmosphere into the sintering equipment is 1-10m3H, controlling the temperature rise speed to be 1-5 ℃/min. The temperature rise speed is too fast, which is not beneficial to the complete growth of crystal lattices and causes crystal lattice defects, and the temperature rise speed is too slow, which leads to overlong sintering time, large energy consumption and low efficiency.
Compared with the prior art, the invention has the advantages that:
(1) the invention is formed by coating Li with glass3-3fAlfBO3The coating is a compact glassy substance with strong adhesion capability, can fill the surface void holes of the anode material particles after coating, effectively reduces the specific surface area, reduces the side reaction of the electrolyte and the anode material, prevents structural collapse, and promotes long-circulation propertyCan be used.
(2) The coating Li on the surface of the cathode material3-3fAlfBO3The coating is a glassy compound, the coefficient of Li is more than 0 and less than 3f, so that the coating is in a certain Li-deficient state, and when the coating is coated on the surface of the anode material, residual Li on the surface of the anode material is diffused into the coating under the action of chemical kinetics to form a finished product of the coating, the residual Li on the surface is absorbed, and the high-temperature storage performance of the anode material is favorably improved.
(3) The glassy coating Li on the surface of the cathode material3-3fAlfBO3The adhesive has viscosity, micro powder particles or fine particles can be enriched on the surface of large particles, and after low-temperature calcination treatment, an adhesive coating is formed on the surface of a matrix of the positive electrode material, so that the positive electrode material has mechanical adhesive force, therefore, micro powder fine powder is fixed, the quantity of the fine powder micro powder particles is reduced, the particle size concentration is high, the direct contact between the positive electrode material and electrolyte is reduced, and the structural stability of the material in a long-circulating process is facilitated.
(4) The invention coats glassy cladding material Li on the surface of the anode material substrate3-3fAlfBO3So that Li remains on the surface of the positive electrode material2CO3The content of the residual LiOH on the surface is reduced from about 6000ppm without coating to 4000ppm from 2000ppm without coating, and therefore, the high-temperature storage performance is greatly improved.
(5) The synthetic process of the coating is simple, the raw materials are common substances, and the coating has the advantages of low cost and simple process.
In conclusion, the glassy substance is coated on the surface of the matrix of the positive electrode material, so that the high-temperature cycle and storage performance of the positive electrode material are obviously improved, and the product can be better applied to power battery systems in the fields of electric bicycles, EVs, PHEVs and the like.
Drawings
FIG. 1 is an XRD spectrum of a glassy state coated cathode material synthesized in example 1;
FIG. 2 is an SEM image of the glassy state coated cathode material synthesized in example 1;
FIG. 3 is a graph showing a particle size distribution of the glassy state coated cathode material synthesized in example 1;
FIG. 4 is a normal temperature (25 ℃) cycle decay curve chart before and after coating of the glassy state coated cathode material synthesized in example 1;
fig. 5 is a high temperature (45 ℃) cycle decay curve of the glassy state coated cathode material synthesized in example 1 before and after coating.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the glassy state coated cathode material of the embodiment comprises a cathode material matrix Li1.04Ni0.6Mn0.2Co0.2Al0.01O2And glassy substance Li coated on the surface of the matrix of the cathode material1.5Al0.5BO3。
The preparation method of the glassy state coated cathode material of the embodiment comprises the following steps:
(1) according to the matrix Li of the positive electrode material1.04Ni0.6Mn0.2Co0.2Al0.01O2Designing the mixture ratio, weighing 10kg of precursor Ni0.6Mn0.2Co0.2(OH)24.18kg of battery-grade lithium carbonate and 84.78g of aluminum hydroxide (the purity is 100 percent) are added into a high-speed mixer together, the materials are mixed for 30min at 1000rpm, and no white point is observed visually after the materials are mixed, so that a mixture is obtained;
(2) loading the mixture obtained in the step (1) into a sagger by adopting a bell jar furnace, and putting the sagger into a sintering device at a distance of 10m3Introducing air at a speed of/h, heating to 500 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 5h, then heating to 860 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 10h, naturally cooling to 100 ℃, and discharging;
(3) primarily crushing the mixture sintered in the step (2) by using a double-roller machine, finely crushing by using an airflow mill, screening by using a 300-mesh sieve, and removing oversize materials to obtain powder of 6-20um, namely the anode material Li to be coated1.04Ni0.6Mn0.2Co0.2Al0.01O2；
(4) According to the glassy substance Li1.5Al0.5BO3In an amount of 0.2% by weight based on the weight of the positive electrode material, LiOH3.593g, Al (OH)3 3.900g、H3BO36.183g, 274g of absolute ethanol, Al (OH) first3Adding into anhydrous ethanol, stirring to dissolve completely, adding LiOH and H3BO3Stirring until the glass state coating slurry is fully dissolved to obtain glass state coating slurry with the viscosity of 8000 Pa.s;
(5) adding 4.13kg of the to-be-coated positive electrode material prepared in the step (3) into the glassy state coating slurry prepared in the step (4), heating to 80 ℃ while stirring, stirring to be sufficiently uniform to enable the material not to be sticky and not to be layered, then placing the material into a forced air drying oven, baking for 2h at 120 ℃ under the condition of ensuring sufficient safety, and sieving by using a 300-mesh sieve;
(6) and (4) calcining the material obtained by screening in the step (5) at 500 ℃ for 8h, and screening to obtain the glassy state coated cathode material.
Wherein, the glass state coating slurry in the testing step (4) is calcined at 500 ℃ for 8h after being dried at 80 ℃, and then sampling and testing XRD are carried out to obtain Li1.5Al0.5BO3The compound phase and XRD pattern are shown in figure 1.
The sample of the glassy state coated cathode material prepared in this example was SEM scanned with a microscope scanner, and the result is shown in fig. 2, where the surface of the morphology is attached with a layer of obvious coating, and the density is uniform, and the tap density is 2.5g/cm3The specific surface area is lower,at 0.2-0.7m2Within a lower numerical range between the concentration of the electrolyte and the concentration of the anode material particles, the contact area between the anode material particles and the electrolyte is greatly reduced.
Particle size tests are performed on the glassy state coated cathode material sample prepared in the embodiment, as shown in fig. 3, the volume distribution D10 is more than 4um, D50 is between 9 and 10um, and Dmax is within 35um, which further indicates that the glassy state coated cathode material has less fine particles.
The glassy state coated cathode material sample prepared in the embodiment is used for testing the content of residual Li by adopting a potentiometric titration method, and the Li is tested after coating2CO3The content is 0.310%, the LiOH content is 0.079%, and the content of residual Li is greatly reduced after coating.
The glassy state coated cathode material prepared in the embodiment is used as a cathode, and a CR2032 button cell is assembled and subjected to first charge and discharge capacity evaluation. Glass state coated positive electrode material: SP (conductive carbon black): mixing PVDF (binder) in a mass ratio of 92.5:0.5:0.25, uniformly coating the mixture on an aluminum foil, drying, rolling and cutting into pieces to prepare a positive plate, wherein the negative plate is a metal lithium plate. Assembling and sealing the assembly in a glove box, standing and activating for 10 hours, testing by adopting a Xinwei 5V and 5mA test cabinet, testing the voltage range of 2.8-4.25V, testing the first-time capacity by charging and discharging 0.1C, wherein the first-time discharge capacity of the battery reaches 174.6mAh/g, and the first-time efficiency reaches 89%.
The positive electrode material to be coated and the glassy state coated positive electrode material manufactured by the embodiment are respectively used as positive electrodes to be assembled into a 4060C0 type soft package battery, and the positive electrode: SP (conductive carbon black): HSV900 (binder) is 95:3:2, and the negative electrode comprises the following components: preparing anode slurry and cathode slurry by FSN-1 (Shanghai fir artificial graphite), SP (conductive carbon black), CMC, SBR, H2O, 95.2:1.0:1.50:2.30:120.0, uniformly coating the anode slurry on an aluminum foil, uniformly coating the cathode slurry on a copper foil, carrying out sheet making, assembly, liquid injection and formation, testing by using a Xinwei test cabinet, and testing the voltage with a voltage test range of 3.0-4.2V. The capacity, normal temperature and high temperature 45 ℃ cycle performance of the two were tested and are shown in fig. 4 and fig. 5, respectively. Fig. 4 is a graph of a charge-discharge cycle curve of a coated positive electrode material and an uncoated positive electrode material at a normal temperature of 25 ℃, and the result shows that the coated positive electrode material enables the cycle retention rate of the battery at 500 weeks and 1C to be 91.8%; fig. 4 is a graph of a cycle curve of the coated cathode material at a high temperature of 45 ℃, and the result shows that the coated cathode material of the invention enables the cycle retention rate of 500 weeks and 1C of the battery to be 80.1%.
Comparative example 1:
in the coated positive electrode material of the present comparative example, the matrix of the positive electrode material was Li1.04Ni0.6Mn0.2Co0.2Al0.01O2The coating is Li3.0Al0.5BO3。
The preparation method of the coated cathode material of the embodiment comprises the following steps:
(1) according to the matrix Li of the positive electrode material1.04Ni0.6Mn0.2Co0.2Al0.01O2Designing the mixture ratio, weighing 10kg of precursor Ni0.6Mn0.2Co0.2(OH)24.18kg of battery-grade lithium carbonate and 84.78g of aluminum hydroxide (the purity is 100 percent) are added into a high-speed mixer together, the materials are mixed for 30min at 1000rpm, and no white point is observed visually after the materials are mixed, so that a mixture is obtained;
(2) loading the mixture obtained in the step (1) into a sagger by adopting a bell jar furnace, and putting the sagger into a sintering device at a distance of 10m3Introducing air at a speed of/h, heating to 500 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 5h, then heating to 860 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 10h, naturally cooling to 100 ℃, and discharging;
(3) primarily crushing the mixture sintered in the step (2) by using a double-roller machine, finely crushing by using an airflow mill, screening by using a 300-mesh sieve, and removing oversize materials to obtain powder of 6-20um, namely the anode material Li to be coated1.04Ni0.6Mn0.2Co0.2Al0.01O2；
(4) According to the coating substance Li3.0Al0.5BO3In an amount of 0.2% by weight based on the weight of the positive electrode material, 7.186g of LiOH and Al (OH) were weighed3 3.900g、H3BO3 6.183g、274g of absolute ethanol, Al (OH) first3Adding into anhydrous ethanol, stirring to dissolve completely, adding LiOH and H3BO3Stirring until the mixture is fully dissolved to obtain coating slurry with the viscosity of 8000 Pa.s;
(5) adding 4.13kg of the to-be-coated positive electrode material prepared in the step (3) into the coating slurry prepared in the step (4), heating to 80 ℃ while stirring, stirring until the material is fully and uniformly stirred to be non-sticky and non-layered, then placing the material into a forced air drying oven, baking for 2h at 120 ℃ under the condition of ensuring sufficient safety, and sieving by using a 300-mesh sieve;
(6) and (4) calcining the material obtained by screening in the step (5) at 500 ℃ for 8h, and screening to obtain the glassy state coated cathode material.
The positive electrode material sample prepared in comparative example 1 was subjected to a potentiometric titration method to measure the content of residual Li2CO3The content was 2.236% and the LiOH content was 0.541%.
According to the electricity-saving manufacturing method and the test method of the embodiment 1, the anode material obtained in the comparative example is tested, the first discharge capacity is 168.3mAh/g at 2.8-4.25V and 0.1C, and the first efficiency is 84%.
The positive electrode material obtained in comparative example 1 was tested according to the manufacturing method and the testing method of the soft pouch battery model 4060C0 in example 1, and is shown in fig. 4 and fig. 5, respectively. The cycle retention rate of the battery at 25 ℃ under normal temperature for 500 weeks and 1C is 82.0 percent; the cycle retention rate of the 500-week and 1-C cycle curve at the high temperature of 45 ℃ is 73.2 percent.
Example 2:
the glassy state coated cathode material of the embodiment comprises a cathode material matrix Li1.08Ni0.5Mn0.3Co0.2Mn0.02Mg0.02O2And glassy substance Li coated on the surface of the matrix of the cathode material2.4Al0.2BO3。
The preparation method of the glassy state coated cathode material of the embodiment comprises the following steps:
(1) according to Li1.08Ni0.5Mn0.3Co0.2Mn0.02Mg0.02O2The mixture ratio is measured before 10kgDriver Ni0.5Mn0.3Co0.2(OH)24.35kg of battery-grade lithium carbonate and 87.97g of magnesium oxide (the purity is 100%), adding the materials into a high-speed mixer, mixing for 5min at the speed of 800rpm, mixing for 30min at the speed of 1000rpm, and observing without white spots visually after the materials are mixed to obtain a mixture;
(2) loading the mixture obtained in the step (1) into a sagger by adopting a bell jar furnace, and putting the sagger into a sintering device at a distance of 10m3Introducing air at a speed of/h, heating to 500 ℃ at a speed of 2.5 ℃/min, keeping the temperature for 7h, then heating to 910 ℃, sintering at the constant temperature for 12 h, naturally cooling to 100 ℃, and discharging; obtaining a positive electrode material to be coated after crushing and screening;
(3) coating in the glassy state Li2.4Al0.2BO3Weighing Li2CO3 17.7g、Al(OH)3 1.6g、B2O33.5g of absolute ethanol 69g, first Al (OH)3Adding into anhydrous alcohol, stirring to dissolve completely, adding Li2CO3、B2O3Stirring until the mixture is fully dissolved and completely reacted to obtain glassy state coating slurry with the viscosity of 5000 Pa.s;
(4) according to the glassy substance Li2.4Al0.2BO3In an amount of 0.3% by weight based on the weight of the positive electrode material, is added to the Li obtained in the step (2)1.08Ni0.5Mn0.3Co0.2Mn0.02Mg0.02O22.7kg of positive electrode material is stirred and heated to 80 ℃ so that the material is not sticky and not layered, then the material is placed into a blast drying oven, is baked for 2 hours in an open state at 150 ℃ under the condition of ensuring enough safety, and is sieved by a 300-mesh sieve;
(5) and (4) calcining the positive electrode material obtained in the step (4) at 500 ℃ for 8h, and screening to obtain the glassy state coated positive electrode material.
The glassy state coated cathode material prepared in example 2 was tested, and the specific surface area was 0.30m2The particle size volume distribution shows that D10 is more than 4.5um, D50 is 11um, Dmax is more than 40, and the comprehensive result shows that the fine powder is less.
The positive electrode material obtained in example 2 was tested by potentiometric titrationResidual Li content of the material, residual Li before coating2CO3The content is 0.652%, the LiOH content is 0.036%, and Li is tested after coating2CO3The content is 0.330 percent, the LiOH content is 0.020 percent, and the content of residual Li is greatly reduced after coating.
According to the electricity-saving manufacturing method and the test method in the embodiment 1, when the anode material obtained in the embodiment 2 is tested, the first discharge capacity of 2.8-4.25V and 0.1C reaches 162.1mAh/g, and the first efficiency reaches 89%.
According to the manufacturing method and the testing method of the 4060C0 type soft package battery in the embodiment 1, the 500-week and 1C cycle retention rate of the coated positive electrode material battery is 85% at the normal temperature of 25 ℃ when the positive electrode material obtained in the embodiment 2 is tested; the cycle retention rate of the coated positive electrode material is 74% at a high temperature of 45 ℃ under the 1C cycle retention rate of 500 weeks.
Comparative example 2:
the only difference from example 2 is that: step (3) according to the coating being Li5Al0.2BO3Weighing Li2CO3 36.9g、Al(OH)3 1.6g、B2O33.5g of absolute ethanol 69g, first Al (OH)3Adding into anhydrous alcohol, stirring to dissolve completely, adding Li2CO3、B2O3Stirring until the mixture is fully dissolved and completely reacted to obtain coating slurry with the viscosity of 8000 Pa.s; the other steps and their parameters are the same.
The positive electrode material sample prepared in the comparative example 2 was subjected to a potentiometric titration method to measure the content of residual Li2CO3The content is 0.836% and the LiOH content is 0.541%.
According to the electricity-saving manufacturing method and the test method of the embodiment 1, the anode material obtained in the comparative example is tested, the first discharge capacity is 157.3mAh/g at 2.8-4.25V and 0.1C, and the first efficiency is 84%.
The positive electrode material obtained in this comparative example was tested according to the manufacturing method and the testing method of the soft pouch battery model 4060C0 in example 1, and is shown in fig. 4 and fig. 5, respectively. The cycle retention rate of the battery at 25 ℃ under normal temperature for 500 weeks and 1C is 82.0 percent; the cycle retention rate of the 500-week and 1-C cycle curve at the high temperature of 45 ℃ is 73.2 percent.
Example 3-example 7:
examples 3 to 7 are different from example 1 only in that the positive electrode material substrate, the coating material, the substrate calcination temperature and the constant temperature time, and the coating material treatment temperature and time are different, and other parameters are the same, as shown in table 1.
TABLE 1 characteristics of glassy state coated positive electrode materials of examples 3 to 7
Claims (10)
1. The glass state coated positive electrode material is characterized by comprising a positive electrode material matrix and a glass state substance Li coated on the surface of the positive electrode material matrix3-3fAlfBO3Wherein f is more than 0 and less than 1.
2. The coated positive electrode material according to claim 1, wherein the glassy substance Li3-3fAlfBO3The weight of (a) is 0.01-2% of the weight of the positive electrode material.
3. The coated positive electrode material according to claim 1, wherein the matrix of the positive electrode material has a molecular formula of Li1+a(NixCoyMn1-x-y)1-b(M)bO2(ii) a Wherein M is any one or more of doped metal elements Al, Mg, Zr, Ti, Sr, Y, Nb, W, Bi and La, a is more than or equal to 0 and less than or equal to 0.5, b is more than or equal to 0 and less than or equal to 0.4, x is more than or equal to 0 and less than or equal to 0.9, Y is more than or equal to 0 and less than or equal to 0.334, and x + Y is more than or equal to 0 and less than or equal to 1.
4. A method for producing the coated positive electrode material according to any one of claims 1 to 3, comprising the steps of:
(1) according to Li3-3fAlfBO3Weighing raw materials according to a ratio, dissolving a weighed Al source in an ethanol solvent, adding a B source, and stirring to obtain a coating solution;
adding a Li source into the coating solution, and stirring to obtain a glassy viscous colloidal coating substance;
(2) adding the glassy sticky colloidal coating substance into a positive electrode material matrix to be coated, stirring, drying and screening;
(3) sintering, crushing and screening the material screened in the step (2) to obtain the glassy state coated anode material.
5. The method according to claim 4, wherein in the step (1), the viscosity of the glassy viscous colloidal coating material is controlled to 3000-10000 Pa-s.
6. The method according to claim 4, wherein in the step (1), the Al source is at least one of aluminum carbonate, aluminum nitrate, aluminum chloride and aluminum hydroxide; the source B is one of boron oxide and boric acid; the Li source is any one of lithium carbonate, lithium hydroxide, lithium oxide, lithium halide, lithium phosphate, lithium acetate and lithium oxalate.
7. The method according to claim 4, wherein in the step (2), the temperature is raised to 60-100 ℃ while stirring, and then the mixture is placed into a drying device, wherein the drying temperature is 100-200 ℃;
in the step (3), the sintering temperature is 300-700 ℃, and the sintering time is 5-10 h.
8. The method according to any one of claims 4 to 7, wherein the positive electrode material substrate is prepared mainly according to the following preparation method:
(a) weighing Ni according to stoichiometric ratioxCoyMn1-x-yAdding the precursor, the lithium source and the dopant M raw material into a high-speed mixer for mixing to obtain a mixture;
(b) placing the mixture into sintering equipment, heating to 450-550 ℃ in air or oxygen atmosphere, keeping the temperature constant for 5-15h, continuing to heat to 800-1000 ℃, keeping the temperature constant for 5-15h, naturally cooling to 100 ℃, and discharging;
(c) crushing the product sintered in the step (b), and sieving with a 200-400-mesh sieve to obtain a positive electrode material matrix Li1+a(NixCoyMn1-x-y)1-b(M)bO2。
9. The method of claim 8, wherein in step (a), Ni isxCoyMn1-x-yThe precursor is selected from at least one of oxide, hydroxide and carbonate corresponding to the precursor; the lithium source is at least one of lithium carbonate, lithium hydroxide and lithium chloride; the dopant M raw material refers to one or more of oxide, hydroxide, phosphate and acetate containing the doping element M.
10. The method of claim 8, wherein in step (b), the air or oxygen atmosphere is introduced into the sintering apparatus at a rate of 1 to 10m3The heating rate of the sintering equipment is 1-5 ℃/min.
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Address after: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee after: BASF Shanshan battery material Co.,Ltd. Address before: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: Hunan Shanshan Energy Technology Co.,Ltd. Address after: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee after: Hunan Shanshan Energy Technology Co.,Ltd. Address before: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: HUNAN SHANSHAN ENERGY TECHNOLOGY Co.,Ltd. |