CN111233042A - Lithium manganate positive electrode material precursor, lithium manganate positive electrode material and preparation method thereof - Google Patents

Lithium manganate positive electrode material precursor, lithium manganate positive electrode material and preparation method thereof Download PDF

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CN111233042A
CN111233042A CN202010046044.3A CN202010046044A CN111233042A CN 111233042 A CN111233042 A CN 111233042A CN 202010046044 A CN202010046044 A CN 202010046044A CN 111233042 A CN111233042 A CN 111233042A
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lithium
lithium manganate
positive electrode
aluminum
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CN111233042B (en
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夏娟
张朋
王旗
李敏
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Fuyang Normal University
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Abstract

The invention provides a lithium manganate anode material precursor, a lithium manganate anode material and a preparation method thereof. The lithium manganate provided by the invention has a median particle diameter D50 of 15-30 μm, has high compacted density and gram capacity, and can improve the energy density of a lithium ion battery. The preparation method has the advantages of simple process, environmental protection, energy conservation, lower production cost and easy large-scale production.

Description

Lithium manganate positive electrode material precursor, lithium manganate positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium manganate positive electrode material precursor, a lithium manganate positive electrode material and a preparation method thereof.
Background
With the development of technology, people can not keep lithium ion batteries in production and life, and the requirements on the energy density of the lithium ion batteries are higher and higher. Lithium manganate, as one of the lithium ion battery positive electrode materials which have been successfully commercialized, has the advantages of abundant resource reserves, good safety performance, low price and the like, but the application of lithium manganate in the field of lithium ion batteries is restricted by lower energy density.
The energy density of the lithium ion battery can be effectively improved by improving the compaction density of the anode material, namely more anode materials are filled in the limited battery space. Research proves that the particle size distribution of the positive electrode material is in a direct proportion relation with the compacted density, and the large-particle spherical positive electrode material generally has larger compacted density.
For example, chinese patent publication No. CN102267726B discloses a method for preparing spherical lithium manganate, which comprises mixing an aqueous solution of lithium salt and an aqueous solution of manganese salt to form a true solution or a metastable colloidal solution, then spray-drying to obtain a spherical particle precursor, and then subjecting the spherical particle precursor to a dynamic baking heat treatment to obtain the spherical lithium manganate, so that the lithium ion battery has high power performance and high capacity retention rate. However, the spherical particles prepared by the spray drying method have larger gaps among primary particles, and are easy to break when the positive pole piece of the battery is rolled, so that the compaction density is low, and the energy density of the lithium ion battery is difficult to improve. In addition, in the production process of the spray drying method, a large amount of water and heat energy are consumed to form spherical particles from the salt in the solution, and the requirements of energy conservation and environmental protection in China are not met.
For example, chinese patent publication No. CN109244450A discloses a method for preparing a high-compaction and high-capacity lithium manganate composite cathode material for blending ternary materials, which comprises preparing a lithium manganate cathode material with small particles and narrow particle size distribution, then preparing a lithium manganate cathode material with large particles and wide particle size distribution, and then mixing the lithium manganate cathode materials with two particle size distributions to obtain the composite cathode material. The defects of insufficient compaction of a single material are overcome and the appearance defects caused by conventional secondary grading are avoided by mixing according to a certain proportion. For example, chinese patent publication No. CN106532033A discloses a method for preparing a mixed lithium manganate material, (1) preparing a large-particle lithium manganate material; (2) preparing a small-particle lithium manganate material; (3) and mixing the large particles and the small particles to obtain the mixed lithium manganate material. The lithium manganate material with high compaction and high multiplying power is prepared by a large and small particle mixing technology. Although the particles with different particle size distributions can obtain a better filling effect in a limited space, the small-particle cathode material has a larger specific surface area, so that the degree of side reactions of the lithium ion battery is much stronger than that of the large-particle cathode material, the polarization of the cathode material in the battery is accelerated, and the cycle performance of the battery is poor.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a lithium manganate positive electrode material precursor, a lithium manganate positive electrode material and a preparation method thereof. The preparation method is simple and easy for large-scale production.
The invention provides a lithium manganate anode material precursor, which is prepared from Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler with a chemical formula of xMnCO3·yAl(OH)3，0.8≤x≤0.995、0.005≤y≤0.2、x+y＝1。
The invention also provides a preparation method of the lithium manganate anode material precursor, which is characterized by comprising the following steps:
A) mixing an aluminum-containing salt solution and ammonia water according to a certain proportion, uniformly stirring, and adjusting the pH value to 6-8 to obtain Al (OH)3A suspension of the gel;
B) adding the solution containing manganese salt and the solution of sodium carbonate or sodium bicarbonate into Al (OH) according to certain comparison3Stirring the gel suspension uniformly;
C) precipitating for 2-12 hours, washing and drying to obtain Al (OH)3Gel network skeleton and MnCO3The filler constitutes a spherical precursor.
Preferably, the solution containing aluminum salt is selected from one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, sodium aluminate or tetrahydroxy sodium aluminate solution; more preferably, the solution containing aluminum salt is selected from one or more of aluminum nitrate, aluminum acetate and sodium aluminate solution.
Preferably, the molar ratio of the aluminum ions to the ammonium ions in the mixed solution of the aluminum-containing salt solution and the ammonia water is 1: (3-5); more preferably, the molar ratio of the aluminum ions to the ammonium ions in the mixed solution of the aluminum-containing salt solution and the ammonia water is 1: (3.1-3.5).
Preferably, the manganese-containing salt solution is selected from one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate solution; more preferably, the manganese-containing salt solution is selected from one or more of manganese sulfate or manganese acetate solution.
Preferably, the molar ratio of the aluminum ions to the manganese ions in the reaction solution is x: y, wherein x is more than or equal to 0.8 and less than or equal to 0.995, y is more than or equal to 0.005 and less than or equal to 0.2, and x + y is equal to 1; more preferably, the molar ratio of aluminum ions to manganese ions in the reaction solution is x: y, x is more than or equal to 0.95 and less than or equal to 0.99, y is more than or equal to 0.01 and less than or equal to 0.05, and x + y is equal to 1.
The invention also provides a lithium manganate positive electrode material, which is characterized by being prepared by using the lithium manganate positive electrode material precursor and lithium salt in the claim 1. Preferably, the median particle diameter of the positive electrode material is 15 ≦ D50Less than or equal to 30 mu m; more preferably, the median particle diameter of the positive electrode material is 18. ltoreq. D50≤25μm。
The invention also provides a preparation method of the lithium manganate positive electrode material, which is characterized by comprising the following steps:
A) uniformly mixing the lithium manganate positive electrode material precursor prepared in the claim 2 with lithium salt according to a certain proportion to obtain a mixture;
B) adding the obtained mixture into a rotary kiln for sintering, and spraying a surface fluxing agent in a high-temperature sintering area;
C) and cooling and sieving to obtain the lithium manganate cathode material.
Preferably, the surface fluxing agent is one or more of lithium hydroxide, lithium aluminate, lithium borate and boric acid; more preferably, the surface fluxing agent is one or more of lithium hydroxide and lithium aluminate.
Preferably, the surface fluxing agent accounts for 0.1 to 5 percent of the mixture by mass; more preferably, the surface fluxing agent accounts for 0.1 to 5 percent of the mixture by mass.
Preferably, the high-temperature sintering temperature is 600-850 ℃, and the sintering time is 6-24 hours; more preferably, the high-temperature sintering temperature is 700-800 ℃, and the sintering time is 12-18 hours.
Compared with the prior art, the invention provides a preparation method of a lithium manganate positive electrode material precursor, which utilizes Al (OH)3Gel pair MnCO3The precipitate has strong adsorption effect, and can quickly form a spherical precursor by stirring. The precursor is made of Al (OH)3Gel network skeleton and MnCO3The filler is formed, has larger particle size distribution and very compact structure, and can improve the compaction density of the lithium manganate cathode material.
Compared with the prior art, the preparation method of the lithium manganate anode material provided by the invention has the advantages that the surface fluxing agent is sprayed in the high-temperature sintering area, so that on one hand, the lithium manganate in sintering can be cooled, shrunk and regrown through heat absorption of the solution, and the compactness of the lithium manganate anode material is improved, on the other hand, a lithium aluminate or lithium borate coating layer can be formed on the surface of the lithium manganate anode material, the lithium content in the lithium manganate anode material is improved, and the lithium manganate has higher gram capacity.
The preparation method provided by the invention has the advantages of simple process, environmental protection, energy conservation, lower production cost and easiness in large-scale production.
Drawings
FIG. 1 is an SEM image of a precursor of the lithium manganate positive electrode material of example 1;
FIG. 2 is an SEM photograph of the lithium manganate positive electrode material of example 1;
FIG. 3 is an SEM photograph of the lithium manganate positive electrode material of comparative example 1;
fig. 4 is a graph showing charge and discharge curves of the lithium manganate positive electrode material of example 1 and the lithium manganate positive electrode material of comparative example 1.
Detailed Description
In order to further understand the present invention, the lithium manganate positive electrode material precursor, the lithium manganate positive electrode material and the preparation method thereof of the present invention are described below with reference to the examples and the drawings, but not limited thereto, and all modifications or equivalent substitutions made to the technical solutions of the present invention should be protected by the present invention.
Example 1
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.1, mixing the aluminum sulfate solution with ammonia water, stirring uniformly, and adjusting the pH value to 7.8 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.01: 0.99: 1.05, adding manganese sulfate solution and sodium carbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 6 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of 0.99MnCO3·0.01Al(OH)3。
According to the mol ratio of 1: 1 mixing 0.99MnCO3·0.01Al(OH)3Mixing with lithium hydroxide uniformly to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium aluminate in a high-temperature sintering area at 750 ℃, wherein the lithium aluminate accounts for 0.1 percent of the mass of the mixture, and sintering for 16 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 19.5 mu m, the gram volume is 132.5mAh/g, and the compacted density is 3.26g/cm3。
Example 2
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.4, mixing the aluminum nitrate solution and ammonia water, stirring uniformly, and adjusting the pH value to 8.0 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.02: 0.98: 1.1 manganese sulfate solution and sodium bicarbonate solution were added to Al (OH)3Stirring the gel suspension uniformly; precipitating for 8 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler with a chemical formula of 0.98MnCO3·0.02Al(OH)3。
According to the mol ratio of 1: 0.51 part of 0.98MnCO3·0.02Al(OH)3Uniformly mixing the lithium carbonate and lithium carbonate to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium hydroxide in a high-temperature sintering area at 810 ℃, wherein the mass percent of the lithium hydroxide in the mixture is 0.2%, and sintering for 12 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 19.2 mu m, the gram volume is 127mAh/g, and the compaction density is 3.25g/cm3。。
Example 3
According to the molar ratio of aluminum ions to ammonium ions of 1: 3, mixing the aluminum sulfate solution with ammonia water, stirring uniformly, and adjusting the pH value to 7.2 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.03: 0.97: 1.06, respectively adding a manganese sulfate solution and a sodium carbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 6 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of 0.97MnCO3·0.03Al(OH)3。
According to the mol ratio of 1: 0.5 part of 0.97MnCO3·0.02Al(OH)3Uniformly mixing the lithium carbonate and the lithium carbonate to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium hydroxide in a high-temperature sintering area at 850 ℃, wherein the lithium hydroxide accounts for 0.3 percent of the mass of the mixture, and sintering for 18 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 20.1 mu m, the gram volume is 128.1mAh/g, and the compacted density is 3.31g/cm3。
Example 4
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.2, mixing the aluminum chloride solution and ammonia water, stirring uniformly, and adjusting the pH value to 7.9 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.01: 0.99: 1.05, respectively adding the manganese chloride solution and the sodium bicarbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 4 hours, washing and drying to obtain the product Al (OH)3GelNetwork-like skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of 0.99MnCO3·0.01Al(OH)3。
According to the mol ratio of 1: 1.02 mixing 0.99MnCO3·0.01Al(OH)3Mixing with lithium hydroxide uniformly to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium borate in a high-temperature sintering area at 720 ℃, wherein the lithium borate accounts for 0.1 percent of the mass of the mixture, and sintering for 15 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 16.5 mu m, the gram volume is 126.6mAh/g, and the compacted density is 3.18g/cm3。
Example 5
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.3, mixing the aluminum acetate solution with ammonia water, stirring uniformly, and adjusting the pH value to 7.3 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.03: 0.97: 1.02, adding a manganese sulfate solution and a sodium carbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 5 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of 0.97MnCO3·0.03Al(OH)3。
According to the mol ratio of 1: 1 mixing 0.97MnCO3·0.03Al(OH)3Mixing with lithium hydroxide uniformly to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying boric acid in a high-temperature sintering area at 750 ℃, wherein the boric acid accounts for 0.1 percent of the mass of the mixture, and sintering for 18 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 19.4 mu m, the gram volume is 127.1mAh/g, and the compacted density is 3.27g/cm3。
Example 6
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.35, mixing the tetrahydroxy sodium aluminate solution and ammonia water, stirring uniformly, and adjusting the pH value to 7.4 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.01: 0.99: 1.01, mixing manganese nitrate solution withAdding Al (OH) into the sodium carbonate solution respectively3Stirring the gel suspension uniformly; precipitating for 8 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of 0.99MnCO3·0.01Al(OH)3。
According to the mol ratio of 1: 0.5 part of 0.99MnCO3·0.01Al(OH)3Uniformly mixing the lithium carbonate and the lithium carbonate to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium hydroxide in a high-temperature sintering area at 840 ℃, wherein the mass percent of the lithium hydroxide in the mixture is 0.2.5%, and sintering for 13 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 21.2 mu m, the gram volume is 125mAh/g, and the compaction density is 3.23g/cm3。
Example 7
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.9, mixing the sodium aluminate solution and ammonia water, stirring uniformly, and adjusting the pH value to 7.9 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.006: 0.994: 1, adding a manganese sulfate solution and a sodium carbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 9 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler with a chemical formula of 0.994MnCO3·0.006Al(OH)3。
According to the mol ratio of 1: 1 mixing 0.994MnCO3·0.006Al(OH)3Mixing with lithium hydroxide uniformly to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium borate in a high-temperature sintering area at 790 ℃, wherein the lithium borate accounts for 0.5 percent of the mass of the mixture, and sintering for 24 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 17.4 mu m, the gram volume is 130.2mAh/g, and the compacted density is 3.12g/cm3。
Example 8
According to the molar ratio of aluminum ions to ammonium ions of 1: 5, mixing the aluminum nitrate solution and ammonia water, uniformly stirring, and adjusting the pH value to 80, Al (OH) is obtained3A suspension of the gel; according to the mole ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.04: 0.96: 1.04, respectively adding the manganese nitrate solution and the sodium bicarbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 2 hours, washing and drying to obtain a precipitate consisting of Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of 0.96MnCO3·0.04Al(OH)3。
According to the mol ratio of 1: 1.02 mixing 0.96MnCO3·0.04Al(OH)3Mixing with lithium hydroxide uniformly to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium hydroxide in a high-temperature sintering area at 850 ℃, wherein the lithium hydroxide accounts for 0.15 percent of the mass of the mixture, and sintering for 16 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 25.1 mu m, the gram volume is 125.8mAh/g, and the compacted density is 3.23g/cm3。
Example 9
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.1, mixing the aluminum sulfate solution with ammonia water, stirring uniformly, and adjusting the pH value to 7.8 to obtain Al (OH)3A suspension of the gel; according to the certain mole ratio of aluminum ions, manganese ions and carbonate ions of 0.008: 0.992: 1.05, add manganese sulfate solution and sodium bicarbonate solution to Al (OH)3Stirring the gel suspension uniformly; precipitating for 6 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler with a chemical formula of 0.992MnCO3·0.008Al(OH)3。
According to the mol ratio of 1: 1 mixing 0.992MnCO3·0.008Al(OH)3Mixing with lithium hydroxide uniformly to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium aluminate in a high-temperature sintering area at 750 ℃, wherein the lithium aluminate accounts for 0.1 percent of the mass of the mixture, and sintering for 16 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 18.5 mu m, the gram volume is 134.0mAh/g, and the compacted density is 3.20g/cm3。
Example 10
According to the molar ratio of aluminum ions to ammonium ions of 1: 3.08, mixing the aluminum acetate solution with ammonia water, stirring uniformly, and adjusting the pH value to 7.2 to obtain Al (OH)3A suspension of the gel; according to the mol ratio of aluminum ions, manganese ions and carbonate ions, the ratio of aluminum ions to manganese ions to carbonate ions is 0.02: 0.98: 1.02, adding the manganese acetate solution and the sodium carbonate solution into Al (OH)3Stirring the gel suspension uniformly; precipitating for 10 hours, washing and drying to obtain the product Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler with a chemical formula of 0.98MnCO3·0.02Al(OH)3。
According to the mol ratio of 1: 0.52 to 0.98MnCO3·0.02Al(OH)3Uniformly mixing the lithium carbonate and the lithium carbonate to obtain a mixture; adding the obtained mixture into a rotary kiln, spraying lithium aluminate in a high-temperature sintering area at 780 ℃, wherein the lithium aluminate accounts for 0.1 percent of the mass of the mixture, and sintering for 16 hours; cooling and sieving to obtain the lithium manganate cathode material, wherein the median particle size D50 is 17.7 mu m, the gram volume is 126.3mAh/g, and the compacted density is 3.18g/cm3。
Comparative example 1
According to the element mole ratio Li: mn: al 1.10: 1.97: 0.03 weighing electrolytic manganese dioxide with D50 of 20 mu m, lithium carbonate and nano aluminum oxide, uniformly mixing, and sintering at 750 ℃ for 16 hours to obtain large particles with D50 of 20 mu m; according to the element mole ratio Li: mn: al 1.10: 1.97: 0.03 weighing electrolytic manganese dioxide with D50 of 4 mu m, lithium carbonate and nano aluminum oxide, uniformly mixing, and sintering at 750 ℃ for 16 hours to obtain small particles with D50 of 4 mu m; and (3) mixing the prepared lithium manganate particles in a mass ratio of 3: 1 was mixed to give the lithium manganate of comparative example 1 having a median particle size D50 of 16.2. mu.m, a gram-volume of 124.3mAh/g and a compacted density of 3.01g/cm3。

Claims (7)

1. The precursor of the lithium manganate positive electrode material is characterized in that the precursor of the positive electrode material is prepared from Al (OH)3Gel network skeleton and MnCO3A spherical precursor composed of filler and having a chemical formula of xMnCO3·yAl(OH)3，0.8≤x≤0.995、0.005≤y≤0.2、x+y＝1。
2. The method for preparing the lithium manganate positive electrode material precursor of claim 1, characterized by comprising the following steps:
A) mixing an aluminum-containing salt solution and ammonia water according to a certain proportion, uniformly stirring, and adjusting the pH value to 6-8 to obtain Al (OH)3A suspension of the gel;
B) adding the solution containing manganese salt and the solution of sodium carbonate or sodium bicarbonate into Al (OH) according to certain comparison3Stirring the gel suspension uniformly;
C) precipitating for 2-12 hours, washing and drying to obtain Al (OH)3Gel network skeleton and MnCO3The filler constitutes a spherical precursor.
3. The method of claim 2, wherein the aluminum-containing salt solution is selected from one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, sodium aluminate, and tetrahydroxysodium aluminate solutions;
the molar ratio of aluminum ions to ammonium ions in the mixed solution of the aluminum-containing salt solution and the ammonia water is 1: (3-5);
the manganese-containing salt solution is selected from one or more of manganese sulfate, manganese nitrate, manganese chloride or manganese acetate solution;
the molar ratio of aluminum ions to manganese ions in the reaction solution is x: y is more than or equal to 0.8 and less than or equal to 0.995, y is more than or equal to 0.005 and less than or equal to 0.2, and x + y is equal to 1.
4. A lithium manganate positive electrode material characterized by being produced by using the lithium manganate positive electrode material precursor of claim 1 and a lithium salt, said positive electrode material having a median particle diameter of 15. ltoreq. D50≤30μm。
5. The preparation method of the lithium manganate positive electrode material as set forth in claim 4, characterized by comprising the steps of:
A) uniformly mixing the lithium manganate positive electrode material precursor prepared in the claim 2 with lithium salt according to a certain proportion to obtain a mixture;
B) adding the obtained mixture into a rotary kiln for sintering, and spraying a surface fluxing agent in a high-temperature sintering area;
C) and cooling and sieving to obtain the lithium manganate cathode material.
6. The preparation method according to claim 5, wherein the surface fluxing agent is one or more of lithium hydroxide, lithium aluminate, lithium borate and boric acid, and the mass percent of the surface fluxing agent in the mixture is 0.1-5%.
7. The method according to claim 5, wherein the high-temperature sintering temperature is 600 to 850 ℃ and the sintering time is 6 to 24 hours.
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