CN114335488A - 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 Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 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 through nano-alumina and nano-lithium aluminate to obtain a composite material with stable chemical propertiesThe coating layer is combined, 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, so that the cycle performance and the rate capability of the lithium-rich manganese-based positive electrode material are improved.
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 with publication number CN103441252A discloses a preparation method of a lithium-rich manganese-based anode material of a nano-oxide coated lithium ion battery, which comprises the steps of uniformly mixing a nano-metal oxide and the lithium-rich manganese-based anode material, drying, and keeping the temperature at 400-1000 ℃ for 2-20 hours to obtain the lithium-rich manganese-based anode material coated by the 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 with publication number CN105932251A discloses a preparation method and application of a metal oxide coated lithium ion positive electrode material, wherein nano-scale metal powder and the positive electrode material are mixed by ball milling, water is added into the obtained mixture to react to obtain the positive electrode material with the surface coated with metal hydroxide colloid, and then the positive electrode material is calcined at the high temperature of 200-900 ℃ for 5-20 hours to obtain the positive electrode material of the metal oxide coated lithium ion battery with a layer of compact, uniform and good stability formed on the surface. 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 a preparation process of an oxide positive electrode material precursor, then, in a high-temperature heat treatment process, the coating material is oxidized and decomposed on the surface of an oxide positive electrode material matrix and is precipitated in situ, and the coating material 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, wherein the lithium ion battery positive electrode material, 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 after roasting for 2-48 hours at 200-1000 ℃ all the coated anode material for the lithium ion battery. Taking alumina as an example of the coating, alpha-Al2O3The 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, the suspension, the aluminum-containing hydroxide and the aluminum oxide are roasted at the temperature of 200-1000 ℃ to synthesize the alpha-Al2O3、γ-Al2O3、δ-Al2O3、η-Al2O3、θ-Al2O3When 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 forms2O3Therefore, the above invention has not fully realized the α -Al2O3And (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 cathode material, the evaporation of lithium oxide and oxygen can occur, so that the crystal structure on the surface of the lithium-rich manganese-based cathode material is converted from a layered 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 Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 1.
Preferably, the lithium aluminate is a nanocrystal, the size of the crystal is 2 nm-10 nm, and the lithium aluminate continuously coats 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 matrix1+aNixCoyMnzO2Adding 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 30 min.
Preferably, said combustible gas in step c) is selected from those having a heating value of 20MJ/Nm3～180MJ/Nm3The combustible gas of (1).
Preferably, the pressure of the combustible gas in step c) is 0.15 to 2 MPa.
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 Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 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.
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 an 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 with reference to the following embodiments of the present invention, and it should be understood 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 provides a coating modified lithium-rich manganese-based positive electrode material with a molecular formula of Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 1.
In the invention, the coating modified lithium-rich manganese-based cathode material has the molecular formula of Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 1. In a preferred embodiment of the invention, the matrix is Li1.2Ni0.13Co0.13Mn0.54O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.3Ni0.1Co0.1Mn0.5O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.4Ni0.1Co0.1Mn0.4O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.2Ni0.1Co0.1Mn0.6O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.1Ni0.3Co0.3Mn0.3O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.25Ni0.15Co0.05Mn0.55O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.1Ni0.05Co0.05Mn0.8O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.5Mn0.5O2(ii) a In another preferred embodiment of the present invention, the matrix is Li1.2Ni0.4Mn0.4O2。
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 aluminum oxide 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 of an aluminum source and water, and adding Li to the matrix1+aNixCoyMnzO2Adding 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 matrix1+ aNixCoyMnzO2Adding into water to obtain suspension. In the present invention, the aluminum source is preferably aluminum nitrate; the present invention is not particularly limited in its origin, 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 2 mol/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. By regulating the concentration of the aluminum nitrate solution, the molar ratio of the matrix to the aluminum element and the dipping time, a technician can regulate the thickness of the aluminum hydroxide nano coating layer; 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 30 min.
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 intermediate is rapidly heated by using combustible gas, so that the surface temperature of the intermediate can instantly reach 1200-2500 ℃, and aluminum hydroxide coated on the surface reacts with lithium salt remained on the surface of the intermediate to obtain an inner nano lithium aluminate coating; 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 constructs an electrolyte coating layer on the surface of the lithium-rich manganese-based anode material, so that the lithium ion mobility of the surface interface of the material can be improved, and the rate capability 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 those having a heating value of 20MJ/Nm3～180MJ/Nm3Including 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/Nm3～150MJ/Nm3Including but not limited to combustible gases ofIn one or more of ethane, isobutane, butylene, acetylene, propyne, butyne, natural gas and liquefied petroleum gas, and more preferably has a heat value of 50MJ/Nm3～140MJ/Nm3Including 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 0.5 MPa.
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 aluminum oxide 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 Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 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.
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.
To further illustrate the present invention, the following examples are provided for illustration.
Example 1
(1) Preparing 1mol/L salt solution of aluminum nitrate and water, and preparing matrix Li1.2Ni0.13Co0.13Mn0.54O2Adding 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 Li1.2Ni0.13Co0.13Mn0.54O2Adding into water to prepare suspension;
(2) according to the molar ratio of the matrix to the aluminum element 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 Li1.3Ni0.1Co0.1Mn0.5O2Adding 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 Li1.4Ni0.1Co0.1Mn0.4O2Adding 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 preparing matrix Li1.2Ni0.1Co0.1Mn0.6O2Adding 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 at 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 coated by the nano lithium aluminate and the alumina in a composite mode.
Example 6
(1) Preparing aluminum nitrate and water into a salt solution of 4mol/L, and adding a matrix Li1.1Ni0.3Co0.3Mn0.3O2Adding 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 coated by the nano lithium aluminate and the alumina in a composite mode.
Example 7
(1) Preparing aluminum nitrate and water into 0.5mol/L salt solution, and preparing matrix Li1.25Ni0.15Co0.05Mn0.55O2Adding into water to prepare suspension;
(2) according to the molar ratio of the matrix to the aluminum element 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 Li1.1Ni0.05Co0.05Mn0.8O2Adding into water to prepare suspension;
(2) according to the molar ratio of the matrix to the aluminum element 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 Li1.5Mn0.5O2Adding 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 coated by the nano lithium aluminate and the alumina in a composite manner.
Example 10
(1) Preparing 5mol/L salt solution of aluminum nitrate and water, and preparing matrix Li1.2Ni0.4Mn0.4O2Adding 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 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 11.2Ni0.13Co0.13Mn0.54O20.5g 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 1.32cm2The 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/L6The 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 assembling the lithium ion battery in a glove box filled with argon.
Comparative example 1
Matrix Li described in example 11.2Ni0.13Co0.13Mn0.54O2A lithium-rich manganese-based positive electrode material.
Comparative example 2
(1) Preparing 1mol/L salt solution of aluminum nitrate and water, and preparing matrix Li1.2Ni0.13Co0.13Mn0.54O2Adding into water to make into suspensionLiquid;
(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 11.2Ni0.13Co0.13Mn0.54O20.5g 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 1.32cm2The 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/L6The 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 assembling the lithium ion battery in a glove box filled with argon.
Comparative example 4
9g of the alumina-coated Li obtained in comparative example 21.2Ni0.13Co0.13Mn0.54O20.5g 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 1.32cm2The 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/L6The 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 assembling the lithium ion battery in a glove box filled with argon.
Matrix Li as described in comparative example 11.2Ni0.13Co0.13Mn0.54O2Lithium-rich manganese-based positive electrode material and nano-alumina and nano-lithium aluminate composite obtained in example 1Alloy coated Li1.2Ni0.13Co0.13Mn0.54O2Performing scanning electron microscope test, and the results are respectively shown in fig. 1 and fig. 2; wherein FIG. 1 shows a matrix Li1.2Ni0.13Co0.13Mn0.54O2The 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 11.2Ni0.13Co0.13Mn0.54O2The 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 ac 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 lithium ion battery positive electrode material obtained in comparative example 3 has the lowest surface charge transfer resistance; 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 results of the tests shown in FIGS. 3 and 4 show that the nano-alumina and nano-lithium aluminate obtained in example 1 are coated with Li in a composite manner1.2Ni0.13Co0.13Mn0.54O2The 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 at a charge cut-off voltage of 4.6V and a discharge cut-off voltage of 2.0V, and the electrochemical performance curves thereof were obtained 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 manufactured in the comparative example 4 has a specific 0.1C discharge capacity of 245.2mAh/g, a specific 0.2C 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 (10)
1. The coating modified lithium-rich manganese-based positive electrode material is characterized by having the molecular formula of Li1+aNixCoyMnzO2The 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, and a + x + y + z is equal to 1.
2. The coated and modified lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the lithium aluminate is a nanocrystal with a crystal size of 2nm to 10nm, and is continuously coated on the surface of the substrate.
3. The coating modified lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein the aluminum oxide is a nanocrystal with a crystal size of 50 nm-300 nm, and is discontinuously coated on the surface of the secondary outer layer.
4. The preparation method of the coating modified lithium-rich manganese-based cathode material of claim 1, comprising 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 matrix1+aNixCoyMnzO2Adding 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.
5. The method of claim 4, wherein the aluminum source in step a) is aluminum nitrate; the concentration of the aluminum source solution is 0.2-5 mol/L.
6. The method according to claim 4, wherein the molar ratio of the matrix to the aluminum element in step b) is 1: (0.01-0.08).
7. The method according to claim 4, wherein the dipping time in the step b) is 1 to 20min, and the stirring time is 5 to 30 min.
8. The method for preparing as claimed in claim 4, wherein the combustible gas in step c) is selected from the group consisting of those having a calorific value of 20MJ/Nm3～180MJ/Nm3The combustible gas of (1).
9. The method according to claim 8, wherein the pressure of the combustible gas in step c) is 0.15 to 2 MPa.
10. The method according to claim 4, wherein the heating temperature in step c) is 1300 ℃ to 2200 ℃ and the heating time is 5s to 100 s.
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