CN114335488B - Coating modified lithium-rich manganese-based cathode material and preparation method thereof - Google Patents
Coating modified lithium-rich manganese-based cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a coating modified lithium-rich manganese-based positive electrode material with a molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (1) is a composite coating structure with a matrix, lithium aluminate as a secondary outer layer and alumina as an outer layer; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1. Compared with the prior art, the coating modified lithium-rich manganese-based positive electrode material provided by the invention takes the compound with the specific general formula as a matrix, and is subjected to composite coating by using nano aluminum oxide and nano lithium aluminate to obtain a composite coating layer with stable chemical properties, so that the thickness of the coating layer can be effectively controlled, the stability of the coating layer is improved, and the evaporation of lithium oxide and oxygen in the positive electrode material during high-temperature roasting is effectively inhibited, thereby improving the cycle performance and the rate capability of the lithium-rich manganese-based positive electrode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a coated and modified lithium-rich manganese-based positive electrode material and a preparation method thereof.
Background
The lithium ion battery, one of the most successful mobile energy storage devices for commercialization, has the advantages of high working voltage, high energy density, long service life, environmental friendliness and the like, and is widely applied to the fields of mobile communication, electronic equipment, electric tools, electric automobiles and the like.
The positive electrode material is one of the key factors determining the performance of the lithium ion battery, and the coating modification of the surface of the lithium ion positive electrode material can improve the conductivity of the positive electrode material and improve the compatibility of the material and an electrolyte, so that the first coulombic efficiency, the rate capability and the cycle performance of the lithium ion battery are improved. For example, chinese patent publication No. CN103441252A discloses a method for preparing a lithium-rich manganese-based anode material of a nano-oxide-coated lithium ion battery, which comprises mixing a nano-metal oxide and a lithium-rich manganese-based anode material uniformly, drying, and keeping the temperature at 400-1000 ℃ for 2-20 h to obtain a lithium-rich manganese-based anode material coated with a nano-metal oxide; the method reduces the first irreversible capacity of the lithium-rich cathode material, and improves the cycling stability and rate capability of the material. For example, chinese patent publication No. CN105932251A discloses a method for preparing a metal oxide coated lithium ion positive electrode material and an application thereof, wherein nanoscale metal powder and a positive electrode material are ball-milled and mixed, water is added to the obtained mixture to react, so as to obtain a positive electrode material with a surface coated with metal hydroxide colloid, and then the positive electrode material is calcined at a high temperature of 200 to 900 ℃ for 5 to 20 hours, so as to obtain a layer of a dense, uniform and stable metal oxide coated lithium ion battery positive electrode material with a surface formed thereon. For example, chinese patent publication No. CN107068995A discloses an in-situ precipitated oxide coated lithium ion battery positive electrode material, a preparation method, a preparation apparatus and an application thereof, wherein a raw material of a coating material is added in the preparation process of an oxide positive electrode material precursor, and then in the high-temperature heat treatment process, the coating material is oxidized and decomposed on the surface of an oxide positive electrode material substrate and precipitated in situ, and is subjected to coating modification to obtain an oxide coated oxide composite positive electrode material; the heat treatment temperature is 600-1000 ℃, and the heat treatment time is 5-48 h. For example, chinese patent publication No. CN109360969A discloses an alumina-coated lithium ion battery positive electrode material, a preparation method and a preparation apparatus thereof, the positive electrode material of a lithium ion battery, a solvent, carbonate/bicarbonate and an aluminum salt are mixed and subjected to an ultrasonic reaction to generate a precipitate; microwave heating the precipitate to obtain a product; the sintering temperature is 700-1100 ℃, and the roasting time is 0.5-5 h.
In the technical scheme, the coated anode material is obtained by roasting at 200-1000 ℃ for 2-48 h. Taking alumina as an example of the coating, alpha-Al 2 O 3 The material has the optimal conductive performance and chemical property stability, and is the optimal inorganic metal oxide coating material of the lithium ion battery anode material; but the aluminum-containing precipitate, suspension, aluminum-containing hydroxide and aluminum oxide are roasted at 200-1000 ℃ to synthesize the alpha-Al 2 O 3 、γ-Al 2 O 3 、δ-Al 2 O 3 、η-Al 2 O 3 、θ-Al 2 O 3 When the roasting temperature is higher than 1200 ℃, the alpha-Al can be completely synthesized by roasting the alumina with the same crystal form or a plurality of mixed crystal forms 2 O 3 Therefore, the above invention has not fully realized the α -Al 2 O 3 And (4) optimal scheme of coating. Taking titanium dioxide as an example of a coating, rutile type titanium dioxide has the most stable crystal structure, anatase type titanium dioxide begins to be converted into rutile type at 610 ℃, brookite type titanium dioxide is completely converted into rutile type at 915 ℃, so that rutile type titanium dioxide can be completely synthesized by roasting at the roasting temperature of more than 915 ℃. Therefore, the above technical solutions cannot fully realize the optimal solution of titanium dioxide coating.
In addition, during the long-time high-temperature roasting process of the lithium ion battery anode material, the evaporation of lithium oxide and oxygen can occur, so that the crystal structure on the surface of the lithium-rich manganese-based anode material is converted from a lamellar phase to a spinel phase, and the specific capacity of the material is reduced.
Disclosure of Invention
In view of the above, the invention aims to provide a coating modified lithium-rich manganese-based cathode material and a preparation method thereof, and the coating modified lithium-rich manganese-based cathode material provided by the invention is compositely coated by nano aluminum oxide and nano lithium aluminate, so that the cycle performance and rate capability of the lithium-rich manganese-based cathode material are improved.
The invention provides a coating modified lithium-rich manganese-based positive electrode material with a molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (A) is a composite coating structure with a matrix, lithium aluminate as a secondary outer layer and alumina as an outer layer; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1.
Preferably, the lithium aluminate is a nanocrystal with the size of 2-10 nm and is continuously coated on the surface of the matrix.
Preferably, the aluminum oxide is a nanocrystal, the size of the crystal is 50 nm-300 nm, and the crystal is discontinuously coated on the surface of the secondary outer layer.
The invention also provides a preparation method of the coating modified lithium-rich manganese-based positive electrode material, which comprises the following steps:
a) Preparing an aluminum source solution of 0.1 to 10mol/L of an aluminum source and water, and adding Li to the matrix 1+a Ni x Co y Mn z O 2 Adding into water to prepare suspension;
b) According to the molar ratio of the matrix to the aluminum element of 1: (0.0005-0.2), adding an aluminum source solution into the suspension, soaking for 1-30 min, stirring for 1-30 min, filtering, and drying to obtain an intermediate;
c) Conveying the intermediate into a heat treatment device by using airflow, burning and heating the intermediate by using combustible gas, wherein the pressure of the combustible gas is 0.15-2 MPa, the heating temperature is 1200-2500 ℃, the heating time is 1-300 s, and cooling to obtain the coated modified lithium-rich manganese-based positive electrode material.
Preferably, the aluminum source in step a) is aluminum nitrate; the concentration of the aluminum source solution is 0.2-5 mol/L.
Preferably, the molar ratio of the matrix to the aluminum element in step b) is 1: (0.01-0.08).
Preferably, the dipping time in the step b) is 1min to 20min, and the stirring time is 5min to 30min.
Preferably, said combustible gas in step c) is selected from the group consisting of 20MJ/Nm in heating value 3 ～180MJ/Nm 3 The combustible gas of (1).
Preferably, the pressure of the combustible gas in step c) is 0.15MPa to 2MPa.
Preferably, the heating temperature in the step c) is 1300-2200 ℃ and the heating time is 5-100 s.
The invention provides a coating modified lithium-rich manganese-based positive electrode material with a molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (A) is a composite coating structure with a matrix, lithium aluminate as a secondary outer layer and alumina as an outer layer; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1. Compared with the prior art, the invention providesThe coating modified lithium-rich manganese-based positive electrode material takes the compound with the specific general formula as a matrix, and is subjected to composite coating by using nano aluminum oxide and nano lithium aluminate to obtain a composite coating layer with stable chemical properties, so that the thickness of the coating layer can be effectively controlled, the stability of the coating layer is improved, and the evaporation of lithium oxide and oxygen in the positive electrode material during high-temperature roasting is effectively inhibited, thereby improving the cycle performance and the rate capability of the lithium-rich manganese-based positive electrode material.
Meanwhile, preparing an aluminum source solution and a lithium-rich manganese-based positive electrode material matrix suspension, adding the aluminum source solution into the suspension, stirring, and performing full impregnation or liquid phase precipitation, filtration and drying to obtain an intermediate; then, carrying out high-temperature rapid treatment on the intermediate by using combustible gas to obtain a lithium ion battery anode material compositely coated by nano aluminum oxide and nano lithium aluminate; the preparation method has the advantages of simple production process, high energy utilization efficiency, short sintering time, high production efficiency and the like, and is suitable for large-scale industrial application.
Drawings
Fig. 1 is an SEM image of the uncoated lithium-rich manganese-based positive electrode material obtained in comparative example 1;
FIG. 2 is an SEM image of a lithium-rich manganese-based cathode material compositely coated with nano-alumina and nano-lithium aluminate obtained in example 1;
FIG. 3 is a plot of the acyclic AC impedance of example 11 and comparative examples 3-4;
FIG. 4 is an AC impedance profile after 3 weeks of cycling for example 11 and comparative examples 3-4;
FIG. 5 is a graph showing cycle performance of example 11 and comparative examples 3 to 4.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention providesProvides a coating modified lithium-rich manganese-based cathode material with the molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (A) is a composite coating structure with a matrix, lithium aluminate as a secondary outer layer and alumina as an outer layer; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1.
In the invention, the coating modified lithium-rich manganese-based cathode material has the molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (1) is a substrate; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1. In a preferred embodiment of the invention, the matrix is Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.3 Ni 0.1 Co 0.1 Mn 0.5 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.4 Ni 0.1 Co 0.1 Mn 0.4 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.2 Ni 0.1 Co 0.1 Mn 0.6 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.1 Ni 0.3 Co 0.3 Mn 0.3 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.25 Ni 0.15 Co 0.05 Mn 0.55 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.1 Ni 0.05 Co 0.05 Mn 0.8 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.5 Mn 0.5 O 2 (ii) a In another preferred embodiment of the present invention, the matrix is Li 1.2 Ni 0.4 Mn 0.4 O 2 。
In the present invention, the lithium aluminate is preferably a nanocrystal, and the size of the crystal is preferably 2nm to 10nm, more preferably 2nm to 5nm, and is continuously coated on the surface of the substrate.
In the present invention, the alumina is preferably a nanocrystal, specifically an α -type nanocrystal, the size of the crystal is preferably 50nm to 300nm, more preferably 50nm to 200nm, more preferably 50nm to 100nm, and the crystal is discontinuously coated on the surface of the secondary outer layer.
The invention provides a lithium-rich manganese-based anode material compositely coated by nano alumina and nano lithium aluminate and a preparation method thereof, and relates to a lithium ion battery anode material and a surface modification treatment technology thereof. The coating modified lithium-rich manganese-based positive electrode material provided by the invention takes the compound with the specific general formula as a matrix, and is subjected to composite coating through nano aluminum oxide and nano lithium aluminate to obtain a composite coating layer with stable chemical properties, so that the thickness of the coating layer can be effectively controlled, the stability of the coating layer is improved, and the evaporation of lithium oxide and oxygen in the positive electrode material during high-temperature roasting is effectively inhibited, thereby improving the cycle performance and the rate capability of the lithium-rich manganese-based positive electrode material.
The invention also provides a preparation method of the coating modified lithium-rich manganese-based positive electrode material, which comprises the following steps:
a) Preparing an aluminum source solution of 0.1 to 10mol/L from an aluminum source and water, and adding Li as a matrix 1+a Ni x Co y Mn z O 2 Adding the mixture into water to prepare suspension;
b) According to the molar ratio of the matrix to the aluminum element of 1: (0.0005-0.2), adding an aluminum source solution into the suspension, soaking for 1-30 min, stirring for 1-30 min, filtering, and drying to obtain an intermediate;
c) Conveying the intermediate into a heat treatment device by using airflow, burning and heating the intermediate by using combustible gas, wherein the pressure of the combustible gas is 0.15-2 MPa, the heating temperature is 1200-2500 ℃, the heating time is 1-300 s, and cooling to obtain the coated modified lithium-rich manganese-based positive electrode material.
Firstly, preparing an aluminum source solution with the concentration of 0.1-10 mol/L from an aluminum source and water, and adding Li to a matrix 1+ a Ni x Co y Mn z O 2 Adding into water to obtain suspension. In the present invention, the aluminum source is preferably aluminum nitrate; the invention is directed to its sourceThere is no particular limitation, and commercially available products known to those skilled in the art may be used.
In the present invention, the concentration of the aluminum source solution is preferably 0.2 to 5mol/L, and more preferably 0.5 to 2mol/L.
Then, according to the invention, the molar ratio of the matrix to the aluminum element is 1: (0.0005-0.2), adding an aluminum source solution into the suspension, soaking for 1-30 min, stirring for 1-30 min, filtering, and drying to obtain an intermediate.
In the invention, the prepared aluminum source (aluminum nitrate) solution is an acidic solution, and the water immersion liquid of the lithium-rich manganese-based positive electrode material matrix is alkaline; the matrix is immersed in the salt solution, and aluminum ions and free hydroxide ions in the mixed solution are subjected to precipitation reaction to generate neutral aluminum hydroxide nano-precipitates which are adsorbed on the surface or in pores of the matrix to form an aluminum hydroxide coating. The invention can regulate the thickness of the aluminum hydroxide nanometer coating layer by regulating the concentration of the aluminum nitrate solution, the molar ratio of the matrix to the aluminum element and the dipping time; the uniformity of the surface coating of the cathode material can be improved by stirring.
In the present invention, the molar ratio of the matrix to the aluminum element is preferably 1: (0.01-0.08).
In the present invention, the time for the immersion is preferably 1min to 20min, more preferably 1min to 10min, and the time for the stirring is preferably 5min to 30min.
In the preparation method of the invention, the intermediate is a substrate with the surface attached with an aluminum nitrate solution, and the intermediate includes but is not limited to an intermediate formed by attaching (adsorbing, precipitating, polymerizing, complexing, and electrostatic self-assembling) other kinds of metal salts, metal hydroxides, metal carbonates, organic metal salts, and nano metal oxides on the surface of the substrate; the synthesis method of the intermediate includes, but is not limited to, a salt solution impregnation coating method, a coprecipitation coating method, a nano powder dispersion coating method, and an organic metal salt polymerization coating method.
After the intermediate is obtained, the intermediate is conveyed to a heat treatment device by airflow, the intermediate is burnt and heated by combustible gas, the pressure of the combustible gas is 0.15 MPa-2 MPa, the heating temperature is 1200-2500 ℃, the heating time is 1-300 s, and the coated and modified lithium-rich manganese-based positive electrode material is obtained after cooling.
The method uses combustible gas to rapidly heat the intermediate, so that the surface temperature of the intermediate can reach 1200-2500 ℃ instantly, and aluminum hydroxide coated on the surface reacts with lithium salt remained on the surface of the intermediate to obtain a nano lithium aluminate coating layer on the inner layer; volatilizing and oxidizing the aluminum nitrate solution dipped on the surface to obtain a nano aluminum oxide particle coating layer of the secondary outer layer. Meanwhile, the average grain diameter of the coated nano lithium aluminate crystal is smaller than 10nm and the average grain diameter of the nano alumina is smaller than 300nm by controlling shorter heating time, and the transformation of the material crystal structure caused by the evaporation of lithium oxide and oxygen in the high-temperature roasting process of the conventional method is avoided; the nano lithium aluminate forms an electrolyte coating layer on the surface of the lithium-rich manganese-based anode material, so that the lithium ion mobility of a material surface interface can be improved, and the multiplying power performance of the material is improved; the nano alumina particle coating layer can effectively isolate the contact between the anode material and the electrolyte, and improve the compatibility of the material and the electrolyte under high voltage, thereby improving the cycle performance of the material.
In the present invention, the combustible gas is preferably selected from among those having a heating value of 20MJ/Nm 3 ～180MJ/Nm 3 Including but not limited to one or more of ethane, propane, n-butane, isobutane, ethylene, propylene, butylenes, acetylene, propyne, butyne, coal gas, natural gas, liquefied petroleum gas, more preferably having a heating value of 35MJ/Nm 3 ～150MJ/Nm 3 Including but not limited to one or more of ethane, isobutane, butylenes, acetylene, propyne, butyne, natural gas, liquefied petroleum gas, and more preferably with a heating value of 50MJ/Nm 3 ～140MJ/Nm 3 Including but not limited to one or more of isobutane, ethane, natural gas, liquefied petroleum gas.
In the present invention, the pressure of the combustible gas is preferably 0.15 to 2MPa, more preferably 0.15 to 1MPa, and still more preferably 0.2 to 0.5MPa.
In the present invention, the heating temperature is preferably 1300 to 2200 ℃, more preferably 1300 to 2000 ℃, more preferably 1300 to 1500 ℃, and the heating time is preferably 5 to 100 seconds, more preferably 5 to 60 seconds.
In the invention, the waste heat of the heating temperature can be used for drying the intermediate in the step b), so that the utilization efficiency of energy is improved, and the consumption of energy is reduced.
Preparing an aluminum source solution and a lithium-rich manganese-based positive electrode material matrix suspension, adding the aluminum source solution into the suspension, stirring, and performing full impregnation or liquid phase precipitation, filtration and drying to obtain an intermediate; then, carrying out high-temperature rapid treatment on the intermediate by using combustible gas to obtain a lithium ion battery anode material compositely coated by nano alumina and nano lithium aluminate; the preparation method obtains the composite coating layer with stable chemical properties on the surface of the lithium-rich manganese-based positive electrode material, can effectively control the thickness of the coating layer, improve the stability of the coating layer, and effectively inhibit the evaporation of lithium oxide and oxygen in the positive electrode material during high-temperature roasting, so that the rate performance and the cycle performance of the positive electrode material are improved, and the preparation method has the advantages of simple production process, high energy utilization efficiency, short sintering time, high production efficiency and the like, and is suitable for large-scale industrial application.
The preparation method provided by the invention can be used for surface coating modification of other lithium/sodium ion battery anode materials known by those skilled in the art, such as lithium-rich ternary anode materials, lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate, lithium nickel manganese aluminate, lithium-rich anode materials, lithium iron silicate, lithium manganese silicate, lithium cobalt silicate, lithium vanadate, lithium titanate, lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate, sodium cobaltate, sodium nickelate, sodium manganate, sodium nickel cobalt manganate, sodium titanium phosphate, sodium vanadium phosphate and the like.
The invention provides a coating modified lithium-rich manganese-based positive electrode material with a molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (A) is a composite coating structure with a matrix, lithium aluminate as a secondary outer layer and alumina as an outer layer; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1. He-ShiCompared with the prior art, the coating modified lithium-rich manganese-based positive electrode material provided by the invention has the advantages that the compound with the specific general formula is used as the matrix, the composite coating layer with stable chemical properties is obtained by the composite coating of the nano alumina and the nano lithium aluminate, the thickness of the coating layer can be effectively controlled, the stability of the coating layer is improved, the evaporation of lithium oxide and oxygen in the positive electrode material during high-temperature roasting is effectively inhibited, and the cycle performance and the rate capability of the lithium-rich manganese-based positive electrode material are improved.
Meanwhile, firstly preparing an aluminum source solution and a lithium-rich manganese-based anode material matrix suspension, then adding the aluminum source solution into the suspension, stirring, and obtaining an intermediate after full immersion or liquid phase precipitation, filtration and drying; then, carrying out high-temperature rapid treatment on the intermediate by using combustible gas to obtain a lithium ion battery anode material compositely coated by nano aluminum oxide and nano lithium aluminate; the preparation method has the advantages of simple production process, high energy utilization efficiency, short sintering time, high production efficiency and the like, and is suitable for large-scale industrial application.
In order to further illustrate the present invention, the following examples are provided for illustrative purposes.
Example 1
(1) Preparing 1mol/L salt solution of aluminum nitrate and water, and preparing matrix Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Adding the mixture into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.02, adding an aluminum nitrate solution into the suspension, soaking for 5min, stirring for 10min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate body into a heat treatment device by using air flow, burning and heating the intermediate body by using isobutane gas, wherein the pressure of the isobutane gas is 0.3MPa, the heating temperature is 1300 ℃, the heating time is 30 seconds, and cooling to obtain the lithium-rich manganese-based anode material compositely coated by the nano aluminum oxide and the nano lithium aluminate on the surface.
Example 2
(1) Preparing aluminum nitrate and water into a salt solution of 2mol/L, and adding a matrix Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of 1:0.01, adding an aluminum nitrate solution into the suspension, soaking for 2min, stirring for 5min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate body into a heat treatment device by using air flow, burning and heating the intermediate body by using isobutane gas, wherein the pressure of the isobutane gas is 0.2MPa, the heating temperature is 1400 ℃, the heating time is 15 seconds, and cooling to obtain the lithium-rich manganese-based anode material compositely coated by the nano aluminum oxide and the nano lithium aluminate on the surface.
Example 3
(1) Preparing aluminum nitrate and water into a salt solution of 4mol/L, and adding a matrix Li 1.3 Ni 0.1 Co 0.1 Mn 0.5 O 2 Adding the mixture into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.03, adding the aluminum nitrate solution into the suspension, soaking for 1min, stirring for 15min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate body into a heat treatment device by using air flow, burning and heating the intermediate body by using isobutane gas, wherein the pressure of the isobutane gas is 0.15MPa, the heating temperature is 1350 ℃, the heating time is 20 seconds, and cooling to obtain the lithium-rich manganese-based anode material compositely coated by the nano aluminum oxide and the nano lithium aluminate on the surface.
Example 4
(1) Preparing aluminum nitrate and water into a salt solution of 2.5mol/L, and adding a matrix Li 1.4 Ni 0.1 Co 0.1 Mn 0.4 O 2 Adding the mixture into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.02, adding an aluminum nitrate solution into the suspension, soaking for 5min, stirring for 10min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate into a heat treatment device by using air flow, burning and heating the intermediate by using n-butane gas, wherein the pressure is 0.25MPa, the heating temperature is 2000 ℃, the heating time is 5 seconds, and cooling to obtain the lithium-rich manganese-based anode material compositely coated by the nano aluminum oxide and the nano lithium aluminate on the surface.
Example 5
(1) Preparing 5mol/L salt solution of aluminum nitrate and water, and mixing a matrix Li 1.2 Ni 0.1 Co 0.1 Mn 0.6 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.05, adding an aluminum nitrate solution into the suspension, soaking for 2min, stirring for 30min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate into a heat treatment device by using air flow, burning and heating the intermediate by using natural gas under the pressure of 0.22MPa, the heating temperature of 1800 ℃ and the heating time of 100 seconds, and cooling to obtain the lithium-rich manganese-based anode material with the surface being compositely coated by the nano lithium aluminate and the alumina.
Example 6
(1) Preparing aluminum nitrate and water into a salt solution of 4mol/L, and adding a matrix Li 1.1 Ni 0.3 Co 0.3 Mn 0.3 O 2 Adding the mixture into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.08, adding the aluminum nitrate solution into the suspension, soaking for 10min, stirring for 20min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate into a heat treatment device by using air flow, burning and heating the intermediate by using acetylene gas, wherein the pressure is 0.18MPa, the heating temperature is 2200 ℃, the heating time is 5 seconds, and cooling to obtain the lithium-rich manganese-based anode material with the surface being compositely coated by the nano lithium aluminate and the alumina.
Example 7
(1) Preparing aluminum nitrate and water into a salt solution of 0.5mol/L, and adding a matrix Li 1.25 Ni 0.15 Co 0.05 Mn 0.55 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of 1:0.05, adding the aluminum nitrate solution into the suspension, soaking for 5min, stirring for 10min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate body into a heat treatment device by using air flow, burning and heating the intermediate body by using isobutane gas, wherein the pressure is 0.17MPa, the heating temperature is 1600 ℃, the heating time is 10 seconds, and cooling to obtain the lithium-rich manganese-based anode material with the surface coated by the nano lithium aluminate and the alumina in a composite mode.
Example 8
(1) Preparing aluminum nitrate and water into 0.2mol/L salt solution, and preparing matrix Li 1.1 Ni 0.05 Co 0.05 Mn 0.8 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of 1:0.01, adding an aluminum nitrate solution into the suspension, soaking for 20min, stirring for 30min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate into a heat treatment device by using air flow, burning and heating the intermediate by using isobutane gas, wherein the pressure is 0.19MPa, the heating temperature is 1300 ℃, the heating time is 25 seconds, and cooling to obtain the lithium-rich manganese-based anode material with the surface coated by the nano lithium aluminate and the alumina in a composite manner.
Example 9
(1) Preparing aluminum nitrate and water into a salt solution of 2mol/L, and adding a matrix Li 1.5 Mn 0.5 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.02, adding an aluminum nitrate solution into the suspension, soaking for 2min, stirring for 8min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate into a heat treatment device by using air flow, burning and heating the intermediate by using natural gas under the pressure of 0.16MPa, at the heating temperature of 1500 ℃ for 60 seconds, and cooling to obtain the lithium-rich manganese-based anode material with the surface being compositely coated by the nano lithium aluminate and the alumina.
Example 10
(1) Preparing 5mol/L salt solution of aluminum nitrate and water, and preparing matrix Li 1.2 Ni 0.4 Mn 0.4 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of 1:0.03, adding an aluminum nitrate solution into the suspension, soaking for 5min, stirring for 15min, filtering, and drying to obtain an intermediate;
(3) And then conveying the intermediate into a heat treatment device by using gas flow, burning and heating the intermediate by using ethane gas, wherein the pressure is 0.24MPa, the heating temperature is 1600 ℃, the heating time is 50 seconds, and cooling to obtain the lithium-rich manganese-based anode material with the surface coated by the nano lithium aluminate and the alumina in a composite mode.
Example 11
9g of the lithium aluminate and alumina-coated Li obtained in example 1 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 0.5g of acetylene black, 0.5g of polyvinylidene fluoride and 30g of N-methyl pyrrolidone are mixed at normal temperature and normal pressure to form slurry, and the slurry is uniformly coated on the surface of an aluminum foil to prepare the pole piece.
Drying the obtained pole piece at 80 ℃, compacting, and cutting into pieces with the area of 1.32cm 2 The round thin sheet of (2) was used as a positive electrode, a pure lithium sheet was used as a negative electrode, and 1mol/L LiPF was used 6 The solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte, wherein the volume ratio of EC to DMC is 1:1, and then assembling the lithium ion battery in a glove box filled with argon.
Comparative example 1
Matrix Li described in example 1 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 A lithium-rich manganese-based positive electrode material.
Comparative example 2
(1) Preparing 1mol/L salt solution of aluminum nitrate and water, and preparing matrix Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Adding into water to prepare suspension;
(2) According to the molar ratio of the matrix to the aluminum element of 1:0.02, adding an aluminum nitrate solution into the suspension, soaking for 5min, stirring for 10min, filtering, and drying to obtain an intermediate;
(3) And then putting the intermediate into a muffle furnace, heating at 800 ℃ for 6h, and naturally cooling to obtain the lithium ion battery anode material with the surface coated with the aluminum oxide.
Comparative example 3
9g of the uncoated Li obtained in comparative example 1 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 0.5g of acetylene black, 0.5g of polyvinylidene fluoride and 30g of N-methyl pyrrolidone are mixed at normal temperature and normal pressure to form slurry, and the slurry is uniformly coated on the surface of an aluminum foil to obtain the pole piece.
Drying the obtained pole piece at 80 ℃, compacting, and cutting into pieces with the area of 1.32cm 2 The round thin sheet of (1) was used as a positive electrode, a pure lithium sheet was used as a negative electrode, and LiPF was added at a concentration of 1mol/L 6 The solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) is used as electrolyte, wherein the volume ratio of EC to DMC is 1:1, and then assembled into a lithium ion battery in a glove box filled with argon.
Comparative example 4
9g of the alumina-coated Li obtained in comparative example 2 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 0.5g of acetylene black, 0.5g of polyvinylidene fluoride and 30g of N-methyl pyrrolidone are mixed at normal temperature and normal pressure to form slurry, and the slurry is uniformly coated on the surface of an aluminum foil to prepare the pole piece.
Drying the obtained pole piece at 80 ℃, then pressing the pole piece tightly, and cutting the pole piece into pieces with the area of 1.32cm 2 The round thin sheet of (1) was used as a positive electrode, a pure lithium sheet was used as a negative electrode, and LiPF was added at a concentration of 1mol/L 6 The Ethylene Carbonate (EC) and dimethyl carbonate (DMC) solution is used as electrolyte, wherein the volume ratio of EC to DMC is 1:1, and then assembled into a lithium ion battery in a glove box filled with argon.
Matrix Li as described in comparative example 1 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Lithium-rich manganese-based positive electrode material and nano-alumina and nano-lithium aluminate composite coated Li obtained in example 1 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 Scanning electron microscope tests are carried out, and the results are respectively shown in fig. 1 and fig. 2; wherein FIG. 1 shows a matrix Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 The SEM image of the lithium-rich manganese-based cathode material shows that the material is in a secondary spherical shape with the particle size of primary particles, the surface is smooth, and no coating layer exists; FIG. 2 shows the Li clad with nano-sized alumina and nano-sized lithium aluminate obtained in example 1 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 The SEM image shows that the material has a secondary spherical shape formed by primary particles, has a rough surface and obvious nano-coating particles.
The lithium ion batteries obtained in example 11, comparative example 3, and comparative example 4 were subjected to an alternating current impedance test using an electrochemical workstation, and the results are shown in fig. 3; the ac impedance test was performed on the lithium ion batteries of example 11, comparative example 3, and comparative example 4 after cycling for 3 weeks, and the results are shown in fig. 4. As can be seen from fig. 3, the lithium-rich manganese-based positive electrode material obtained in comparative example 1 has no coating layer on the surface, and therefore the charge transfer resistance of the surface of the positive electrode material of the lithium ion battery obtained in comparative example 3 is the lowest; the diffusion resistance of lithium ions in the surface layer of the lithium-rich manganese-based positive electrode material obtained in example 1 is lower than that of the lithium-rich manganese-based positive electrode material obtained in comparative example 2. As can be seen from fig. 4, the lithium-rich manganese-based positive electrode material obtained in comparative example 1 generates a side reaction with the electrolyte to generate a substance that is not favorable for charge transfer, and therefore the diffusion resistance of lithium ions in the surface layer of the positive electrode material is the greatest after 3 cycles; the diffusion resistance of lithium ions in the surface layer of the lithium-rich manganese-based positive electrode material obtained in example 1 after 3 cycles was lower than that of the lithium-rich manganese-based positive electrode material obtained in comparative example 2. The test results shown in FIGS. 3 and 4 show that the nano-alumina and nano-lithium aluminate obtained in example 1 compositely coated with Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 The surface of the material has the best charge transport capacity at the conductive combination position and has the best compatibility with electrolyte.
Electrochemical performance tests were performed on the lithium ion batteries obtained in example 11, comparative example 3, and comparative example 4 using an electrochemical performance tester, and the cut-off voltage for charging was 4.6V and the cut-off voltage for discharging was 2.0V, and the electrochemical performance curves obtained were as shown in fig. 5. As can be seen from fig. 5, the battery manufactured in example 11 has a 0.1C specific discharge capacity of 223.7mAh/g, a 0.2C specific discharge capacity of 194.8mAh/g, a 0.2C/0.1C ratio of 87.1%, and a discharge capacity retention rate of 94.3% after 20 weeks; the battery prepared in the comparative example 3 has the specific discharge capacity of 0.1C of 231.2mAh/g, the specific discharge capacity of 0.2C of 156.3mAh/g, the ratio of 0.2C to 0.1C of 67.6 percent and the discharge capacity retention rate of 93.6 percent after 20 weeks; the battery prepared in comparative example 4 had a 0.1C specific discharge capacity of 245.2mAh/g, a 0.2C specific discharge capacity of 190.8mAh/g, a 0.2C/0.1C ratio of 77.8%, and a discharge capacity retention rate of 63.8% at 20 weeks. Therefore, the 0.2C specific discharge capacity of the battery fabricated in example 11 was higher than that of comparative examples 3 and 4, the rate performance and cycle performance of the battery fabricated in example 11 were better than those of comparative examples 3 and 4, and the compatibility of the battery fabricated in example 11 with the electrolyte was better than those of comparative examples 3 and 4.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. The coating modified lithium-rich manganese-based positive electrode material is characterized by having the molecular formula of Li 1+a Ni x Co y Mn z O 2 The compound of (1) is a composite coating structure with a matrix, lithium aluminate as a secondary outer layer and alumina as an outer layer; wherein a is more than or equal to 0.1 and less than or equal to 0.5, x is more than or equal to 0 and less than or equal to 0.3, y is more than or equal to 0 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.9, a + x + y + z =1; the lithium aluminate is a nanocrystal, the size of the crystal is 2nm-10nm, and the lithium aluminate is continuously coated on the surface of the matrix; the aluminum oxide is a nanocrystal, the size of the crystal is 50nm to 300nm, and the crystal is discontinuously coated on the surface of the secondary outer layer;
the preparation method of the coating modified lithium-rich manganese-based positive electrode material comprises the following steps:
a) Preparing an aluminum source solution with the concentration of 0.1 mol/L-10 mol/L from an aluminum source and water, and adding Li to a matrix 1+a Ni x Co y Mn z O 2 Adding the mixture into water to prepare suspension; the aluminum source is aluminum nitrate;
b) According to the molar ratio of 1: (0.0005 to 0.2), adding an aluminum source solution into the suspension, soaking for 1min to 30min, stirring for 1min to 30min, filtering, and drying to obtain an intermediate;
c) And conveying the intermediate into a heat treatment device by using an air flow, burning and heating the intermediate by using combustible gas, wherein the pressure of the combustible gas is 0.15MPa to 2MPa, the heating temperature is 1200 ℃ to 2500 ℃, the heating time is 1s to 300s, and cooling to obtain the coated and modified lithium-rich manganese-based positive electrode material.
2. The coating modified lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the concentration of the aluminum source solution in step a) is 0.2-5 mol/L.
3. The coating-modified lithium-rich manganese-based positive electrode material according to claim 1, wherein the molar ratio of the matrix to the aluminum element in step b) is 1: (0.01 to 0.08).
4. The coating-modified lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the impregnation time in step b) is from 1min to 20min, and the stirring time is from 5min to 30min.
5. The coating-modified lithium-rich manganese-based positive electrode material according to claim 1, characterized in that the combustible gas in step c) is selected from the group consisting of heating values of 20MJ/Nm 3 ~180MJ/Nm 3 The combustible gas of (1).
6. The coating-modified lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the heating temperature in step c) is 1300 ℃ to 2200 ℃ and the heating time is 5s to 100s.
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| CN114843501A (en) * | 2022-05-11 | 2022-08-02 | 宁波容百新能源科技股份有限公司 | Lithium nickel manganese oxide positive electrode material and preparation method and application thereof |
| CN115198342B (en) * | 2022-08-10 | 2024-06-14 | 中南大学 | Lithium-rich cobalt-free monocrystal material of rapid ion conductor coated metal doping modified material and preparation method thereof |
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| CN116544406A (en) * | 2023-07-07 | 2023-08-04 | 宜宾锂宝新材料有限公司 | Positive electrode material, preparation method thereof, positive electrode and lithium ion battery |
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