CN107180961B - Modification method for aluminum oxide coated lithium-rich manganese-based layered positive electrode material - Google Patents
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention discloses a modification method of an aluminum oxide coated lithium-rich manganese-based layered anode material. The invention takes dry ice as a precipitator, and has the advantages of environmental protection, abundant sources, low price and the like. By slowly changing the pH value of the precipitation reaction, the surface of the spherical lithium-rich manganese-based positive electrode material is uniformly coated with the alumina layer, so that the first coulombic efficiency of the material is effectively improved, and the excellent charge-discharge cycle stability is shown.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, relates to a lithium-rich manganese-based layered positive electrode material, and particularly relates to a modification method for an aluminum oxide-coated lithium-rich manganese-based layered positive electrode material.
Background
The lithium-rich layered cathode material has high reversible specific capacity (more than 250mAh g)-1) However, it is charged to 4.5V or more and electrochemically activated. This electrochemical activation process is irreversible and is accompanied by a series of serious problems such as large first irreversible capacity, reduced cycling stability, severe voltage decay and voltage hysteresis during cycling, and the like. In a lithium ion battery taking carbon as a negative electrode, if the first coulombic efficiency of a positive electrode material is low, a part of lithium ions can not be inserted into the positive electrode material in a discharging process. These lithium ions retained in the negative electrode may form lithium dendrites on the surface of the negative electrode with charge and discharge cycles, easily penetrate the separator, and cause short-circuiting of the battery, thereby causing a safety problem. Therefore, in order to improve the safety of the batteryThe completeness and the service life of the anode material are improved, and the first coulombic efficiency of the anode material is required to be improved. At present, one effective method for improving the first coulombic efficiency of the positive electrode material is to use a lithium-rich layered positive electrode material in combination with lithium ion "hosts" capable of intercalating lithium, wherein the lithium ion hosts comprise V2O5、VO2、LiV3O8、Li4Mn5O12And the like. These lithium-intercalatable compounds are capable of accepting lithium ions during discharge that cannot be re-intercalated into the lithium-rich layered material, thereby increasing the coulombic efficiency of the overall composite positive electrode material. However, this method cannot fundamentally improve and enhance the stability of the surface structure of the lithium-rich layered material during charge and discharge. Therefore, the cycle stability of the composite positive electrode material is still seriously degraded.
It was found that the surface coating is extremely effective for improving the electrochemical performance of the lithium-rich layered positive electrode material. The surface coating layer can avoid direct contact of the active electrode material and electrolyte, and relieve corrosion of the electrolyte to the surface of the electrode material and dissolution of active transition metal. A commonly used cladding material is Al2O3、AlF3、CeO2、ZrO2、ZnO、AlPO4And the like, which are not electrochemically active. In fact, the surface coating modification can not only reduce the irreversible capacity loss of the electrode material, but also obviously improve the cycling stability and rate capability of the electrode material. At present, the surface coating method mainly comprises a solid phase method and a wet chemical method. The solid phase method has simple operation and low cost, is suitable for large-scale use, but has the defects of non-uniform coating and difficult complete coating. But a uniform and complete surface coating is very important. Although the wet chemical method can achieve very uniform and complete coating, the process is complex, the cost is high, and the method is not favorable for large-scale use.
Disclosure of Invention
In order to solve the defects of the prior art, one of the purposes of the invention is to provide a modification method of an aluminum oxide coated lithium-rich manganese-based layered cathode material, which has the advantages of environmental protection, low price and the like, can effectively improve the first coulombic efficiency of the material, and can show excellent charge-discharge cycle stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the modification method of the aluminum oxide coated lithium-rich manganese-based layered cathode material comprises the steps of taking dry ice as a precipitator and metaaluminate as an aluminum source, reacting under the heating and sealing conditions to enable aluminum ions in water to be precipitated on the surface of the lithium-rich manganese-based layered cathode material, and finally calcining to enable the aluminum oxide to coat the surface of the lithium-rich manganese-based layered cathode material.
The dry ice is used as a precipitator, and has the advantages of environmental protection, rich sources, low price and the like compared with the common precipitator ammonia water, sodium hydroxide and the like; and secondly, the dry ice is used as a precipitator, the pH value of the precipitation reaction can be slowly changed, so that the surface of the spherical lithium-rich manganese-based positive electrode material is uniformly coated with an aluminum oxide layer, the first coulombic efficiency of the material can be effectively improved, and the excellent charge-discharge cycle stability is shown. Thirdly, as the dry ice is weakly acidic after being dissolved in water and has poor water solubility, the meta-aluminate can provide aluminum element and can adjust the solution to be alkaline, so that the solubility of the gasified carbon dioxide in the water is increased, and the reaction rate is accelerated.
The invention also aims to provide a modified lithium-rich manganese-based layered cathode material prepared by the modification method.
The invention also aims to provide an application of the modified lithium-rich manganese-based layered cathode material in a lithium ion battery.
The invention has the beneficial effects that:
the invention adopts dry ice as a precipitator, and compared with the common precipitator ammonia water, sodium hydroxide and the like, the dry ice has the advantages of environmental protection, rich sources, low price and the like. By slowly changing the pH value of the precipitation reaction, the surface of the spherical lithium-rich manganese-based positive electrode material is uniformly coated with the alumina layer, so that the first coulombic efficiency of the material is effectively improved, and the excellent charge-discharge cycle stability is shown.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 shows a Li-rich manganese-based layered material prepared in example 11.2Mn0.58Ni0.18Co0.04O2SEM magnified photograph of (a);
FIG. 2 shows the Li-rich manganese-based layered material coated with alumina in example 11.2Mn0.58Ni0.18Co0.04O2SEM magnified photograph of (a);
FIG. 3 shows the Li-rich manganese-based layered material coated with alumina in example 11.2Mn0.58Ni0.18Co0.04O2The EDS energy spectrum of the scanning electron microscope;
FIG. 4 shows a Li-rich manganese-based layered material Li in example 11.2Mn0.58Ni0.18Co0.04O2First charge-discharge curves before and after coating alumina;
FIG. 5 shows a Li-rich manganese-based layered material Li1.2Mn0.58Ni0.18Co0.04O2The charge-discharge cycle performance curve before and after coating with alumina.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The lithium-rich manganese-based layered cathode material is a cathode material of a lithium ion battery and has a chemical formula of xLi2MnO3·(1-x)LiMO2(0<x<1, M is one or any combination of Mn, Ni and Co).
As introduced in the background art, the defects of complex modification process and high cost of a wet chemical method exist in the prior art, and in order to solve the technical problems, the application provides a modification method for an aluminum oxide coated lithium-rich manganese-based layered positive electrode material.
In a typical embodiment of the application, dry ice is used as a precipitator, metaaluminate is used as an aluminum source, the reaction is performed under a heating and sealing condition, aluminum ions in water are precipitated on the surface of the lithium-rich manganese-based layered cathode material, and finally, the aluminum oxide is calcined to coat the surface of the lithium-rich manganese-based layered cathode material.
The dry ice is used as a precipitator, and has the advantages of environmental protection, rich sources, low price and the like compared with the common precipitator ammonia water, sodium hydroxide and the like; and secondly, the dry ice is used as a precipitator, the pH value of the precipitation reaction can be slowly changed, so that the surface of the spherical lithium-rich manganese-based positive electrode material is uniformly coated with an aluminum oxide layer, the first coulombic efficiency of the material can be effectively improved, and the excellent charge-discharge cycle stability is shown. Thirdly, as the dry ice is weakly acidic after being dissolved in water and has poor water solubility, the meta-aluminate can provide aluminum element and can adjust the solution to be alkaline, so that the solubility of the gasified carbon dioxide in the water is increased, and the reaction rate is accelerated.
In order to prevent potential safety hazards caused by overhigh temperature and over-high dry ice gasification rate, the dry ice gasification furnace is preferably heated to 50-55 ℃.
In order to ensure that the aluminum oxide can be uniformly coated on the surface of the lithium-rich manganese-based layered cathode material, the method is preferred in the application, and the stirring reaction is carried out for 1-2 hours.
Since the meta-aluminate contains other metal cations which cannot be gasified, in order to reduce the influence of the metal cations on the battery performance of the material, the product obtained after the reaction is preferably washed. So as to remove impurity ions such as sodium, potassium and the like attached in the material.
Because the product after the reaction contains partial free water, if the product with the free water is directly calcined, the calcining temperature is higher, so that the vaporization speed of the free water in the material is too high, and the coating structure is damaged, therefore, the method is further preferable in the application, and the washed product is dried. The drying temperature is lower than the calcining temperature, generally not more than 100 ℃, free water can be removed, and because the temperature does not exceed the boiling point of water, the removal of the free water is mainly volatile, and the damage of a coating structure caused by the excessively high vaporization speed of the free water can be prevented. The drying temperature is 75-85 ℃. At this temperature, the drying speed is fast.
In order to remove the bound water in the product after the reaction, the calcination temperature is preferably 300-350 ℃. The temperature can ensure that the bound water of the product is removed, and simultaneously, the energy consumption can be effectively reduced.
As the dry ice is solid carbon dioxide, the boiling point is low, the reaction is in a closed condition, and in order to prevent the pressure in the reaction system from being too high due to excessive addition of the dry ice, so that potential safety hazards are generated, the application is preferred that the pressure in the closed reaction system is not more than 1MPa due to the addition of the dry ice.
The preparation method of the lithium-rich manganese-based layered positive electrode material comprises the steps of preparing a mixed solution from manganese salt, nickel salt and cobalt salt, adding carbonate into the mixed solution, adjusting the pH to 8.2-8.5, carrying out a heating reaction, drying after the reaction, uniformly mixing the dried product with lithium carbonate, and then calcining to obtain the lithium-rich manganese-based layered positive electrode material, wherein the calcining process comprises the steps of firstly heating to 500 +/-10 ℃ for calcining for a period of time, and then continuously heating to 900 +/-10 ℃ for calcining for a period of time.
The application also provides a modified lithium-rich manganese-based layered positive electrode material prepared by the modification method.
The application also provides an application of the modified lithium-rich manganese-based layered cathode material in a lithium ion battery.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific examples and comparative examples.
Examples
Manganese sulfate, nickel sulfate and cobalt sulfate are prepared into a mixed solution with the total concentration of 2M according to the proportion (29:9:2), and 200mL of 0.1mol L of the mixed solution is added into a 2L self-made reaction kettle-1Adding acetic acid into the sodium carbonate solution, adjusting the temperature to be about 8.3 ℃, and heating to 60 ℃. Stirring the sulfate of nickel, cobalt and manganese and 2.1mol L of-1The sodium carbonate precipitator is added into the reaction kettle in parallel for reaction, the stirring speed in the precipitation process is controlled to be 100-1000rpm, the pH value is controlled to be 8.2-8.5, and the feeding speed is controlled to be 250mL h-1The total reaction time was 12 hours. And (3) after the reaction is finished, washing the precipitation product to be nearly neutral by using hot water, and then drying at 110 ℃ for 12 hours to obtain the nickel-cobalt-manganese precipitation precursor. Calcining the obtained precursor material at 500 ℃ for 8 hours to convert the precursor material into an oxide composite, uniformly mixing lithium carbonate and the oxide composite (according to the molar ratio of 1.5:2) according to the ratio of lithium ions to transition metals (Li/M ═ 1+ x)/(1-x) in a target product, pre-calcining the mixture in a muffle furnace at 500 ℃ for 2 hours, then calcining the mixture at 900 ℃ for 1 hour, and raising the temperature at 2 ℃ for min-1Cooling to obtain the target product material Li1.2Mn0.58Ni0.18Co0.04O2The tap density of the electrode material is 2.4g/cm-3The obtained material is shown in FIG. 1, Li is prepared1.2Mn0.58Ni0.18Co0.04O2The electrode material is spherical, and the spherical shape is a secondary particle and is formed by stacking primary nano particles.
0.2g of spherical lithium-rich manganese-based layered cathode material is dispersed into 50ml of 3mmol/L sodium metaaluminate aqueous solution and transferred into a 100 ml reaction kettle. Then, 1 g of dry ice was added, the reaction vessel was sealed, and the reaction was stirred at 50 ℃ for 1 hour. Washing the product obtained by the reaction with deionized water, and drying at 80 ℃. Finally sintering at 300 ℃ in a muffle furnace4 hours later, the lithium-rich manganese-based layered positive electrode material with the surface coated with the aluminum oxide is obtained and is marked as 3 wt% Al2O3500, whose morphology is shown in fig. 2, further demonstrating the coating of alumina on the surface of the material according to the spectral information shown in fig. 3.
Example 2
This example is the same as example 1, except that 0.2g of spherical lithium-rich manganese-based layered positive electrode material was dispersed in 50ml of 2mmol/L aqueous sodium metaaluminate solution to obtain a lithium-rich manganese-based layered positive electrode material coated with alumina, which was recorded as 2 wt% Al2O3-500。
Example 3
This example is the same as example 1, except that 0.2g of the spherical lithium-rich manganese-based layered positive electrode material was dispersed in 50ml of a 1mmol/L aqueous solution of sodium metaaluminate to obtain a surface-alumina-coated lithium-rich manganese-based layered positive electrode material, which was recorded as 1 wt% Al2O3-500。
The charge and discharge performance characteristics of examples 1 to 3 were as follows:
to Li before and after coating alumina1.2Mn0.58Ni0.18Co0.04O2The electrode material is characterized by a first charge-discharge test, and the result is shown in figure 4, wherein the voltage interval of charge-discharge is 4.5-2.0V, and the current density is 20mA g-1. FIG. 4 shows that the specific discharge capacity of the electrode material coated with aluminum oxide is slightly improved (10 mAh g)-1) But the first coulombic efficiency is obviously improved: the original 67 percent is improved to 85 percent (3 percent by weight of Al)2O3)。
To Li before and after coating alumina1.2Mn0.58Ni0.18Co0.04O2The electrode material was subjected to charge-discharge cycle performance test, and the results are shown in FIG. 5, in which the electrode material was circulated between 4.8-2.0V and the current density was 20mA g-1。
Comparative example
The preparation method of this comparative example is the same as that of example 1 except that 0.2g of the spherical lithium-rich manganese-based layered positive electrode material was dispersed in 50ml of a 3mmol/L aqueous aluminum chloride solution and transferred to a reaction vessel. Then, 10 ml of 0.045mol/L ammonia water was added, the reaction vessel was sealed, and the reaction was stirred at 50 ℃ for 1 hour. Washing the product obtained by the reaction with deionized water, and drying at 80 ℃. And finally, sintering the mixture for 4 hours in a muffle furnace at 300 ℃ to obtain the lithium-rich manganese-based layered positive electrode material with the surface coated with the aluminum oxide.
The material is characterized by a first charge-discharge test, and the result shows that the method can only improve the first coulombic efficiency to 75%.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (3)
1. A modification method for coating a lithium-rich manganese-based layered cathode material with aluminum oxide is characterized in that dry ice is used as a precipitator, metaaluminate is used as an aluminum source, the reaction is carried out under the heating and sealing conditions, aluminum ions in water are precipitated on the surface of the lithium-rich manganese-based layered cathode material, and finally the aluminum oxide is calcined to coat the surface of the lithium-rich manganese-based layered cathode material, wherein:
the heating temperature is 50-55 ℃;
stirring and reacting for 1-2 h;
washing and drying a product obtained after the reaction; the drying temperature is 75-85 ℃;
the calcination temperature is 300-350 ℃;
adding dry ice in an amount such that the pressure in the closed reaction system does not exceed 1 MPa;
the preparation method of the lithium-rich manganese-based layered cathode material comprises the following steps: preparing a mixed solution from manganese salt, nickel salt and cobalt salt, adding carbonate into the mixed solution, adjusting the pH value to 8.2-8.5, heating for reaction, drying after the reaction, uniformly mixing the dried product with lithium carbonate, and calcining to obtain a lithium-rich manganese-based layered positive electrode material; the calcining process comprises the following steps: firstly heating to 500 +/-10 ℃ for calcining for a period of time, and then continuously heating to 900 +/-10 ℃ for calcining for a period of time.
2. The modified lithium-rich manganese-based layered cathode material prepared by the modification method of claim 1.
3. The application of the modified lithium-rich manganese-based layered cathode material of claim 2 in a lithium ion battery.
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