CN117431633B - Layered oxide material and preparation method thereof - Google Patents

Layered oxide material and preparation method thereof Download PDF

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CN117431633B
CN117431633B CN202311733512.4A CN202311733512A CN117431633B CN 117431633 B CN117431633 B CN 117431633B CN 202311733512 A CN202311733512 A CN 202311733512A CN 117431633 B CN117431633 B CN 117431633B
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manganese
oxide material
layered oxide
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sodium
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CN117431633A (en
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蔡伟华
赖正杰
赵建明
郭启涛
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Shenzhen Huaxin Material Co ltd
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Abstract

The invention relates to a layered oxide material and a preparation method thereof. The layered oxide material has a chemical general formula: na (Na) x Mn i M y O 2+β The method comprises the steps of carrying out a first treatment on the surface of the M is other metal elements except manganese, specifically at least 3 of Li, K, ca, zn, al, ni, fe, cu, ti, mg, co, ba, sr, B, cr, co, V, zr, nb; x is more than or equal to 0.67 and less than or equal to 1; i is more than or equal to 0.6<1, i is more than y, i+y=1, -0.02 is more than or equal to beta and less than or equal to 0.02; the body center of the particle core region of the layered oxide material coincides with the particle body center, and the manganese content is in a decreasing concentration gradient from the particle body center toward the particle surface. The invention can regulate and control the types and distribution of elements on the surface of particles, has a certain concentration gradient of manganese element, can effectively reduce the appearance of manganese dissolution on the surface, is beneficial to improving the structural stability and the consistency of products of the material, can effectively improve the multiplying power performance and the cycle performance of the material, and has low production cost.

Description

Layered oxide material and preparation method thereof
Technical Field
The invention relates to the field of sodium ion batteries, in particular to a layered oxide material and a preparation method thereof.
Background
With the development of sodium ion batteries, the first oxide materials specifically designed for sodium ion batteries mainly comprise NaCoO 2 And NaMnO 2 Etc. They exhibit certain electrochemical properties but have low capacity and short cycle life, limiting their use.
In order to improve the performance of sodium ion batteries, second generation sodium ion battery cathode materials have been further developed. Among them, layered oxide materials have been the focus of research, including P2 phases (e.g., na 0.67 Mn 0.675 Ni 0.125 Co 0.125 O 2 ) And O3 phase (e.g. NaNi 0.33 Mn 0.33 Cu 0.33 O 2 ) Etc. The materials can realize higher energy storage density and cycle stability, and are commonly used positive electrode materials in sodium ion batteries at present. However, the existing layered oxide cathode material has the problems of poor cycle performance, poor air stability and the like. For this reason, chinese patent publication No. CN104617288A discloses a copper-based sodium-rich layered oxide material, in which Cu is used to replace the P2 phase of expensive and toxic Ni and Co, thereby reducing the cost and improving the air-water stability. But the pure P2 phase material has lower sodium proportion, lower reversible deintercalation active sodium, low capacity, and in the charge and discharge process, the P2 phase material can generate volume expansion, possibly cause material structure damage, reduce cycle life and have poor conductivity. In addition, chinese patent publication No. CN116154116A also discloses a sodium-electricity anode material for preparing a core-shell structure, wherein the inner core is O3 phase anode material, and the outer shell is a mixture of metal oxide and carbon. The metal oxide modifies the surface interface of the positive electrode material, improves the structural stability of the material, improves the electronic conductivity of the material, and improves the cycle and rate capability of the material. The carbon source is decomposed to generate carbon, and the carbon layer plays a hydrophobic effect, so that the problem of Na+ dissolution in the material is effectively inhibited, and the air stability of the material is improved. However, the core layer and the shell layer of the shell-core structure have large phase difference, stress concentration is easy to generate at the junction, so that the structural stability and mechanical property of the material are poor, the material is easy to break in the process of preparing the positive electrode plate or charging and discharging, the processability and the cycle performance of the material are affected, and the carbon coating layer can possibly increase the charge transmission path between the electrode material and the electrolyte, so that the reaction time is prolonged, and the rate performance of the battery is further affected.
Thus for bagsThe sodium-electricity positive electrode material with high sodium proportion of O3 phase shows higher initial capacity but has high initial capacity for CO in air 2 And H 2 O is very sensitive, and NaOH and Na are generated on the surface of particles when contacted with air 2 CO 3 At the same time, the interior of the material has residual alkaline substance Na 2 CO 3 Resulting in a very high pH of the material. Therefore, how to prepare the sodium-electricity positive electrode material with strong air stability, excellent processability and cycle performance and low cost is a key for solving the large-scale application of the current sodium-electricity positive electrode material.
Disclosure of Invention
Aiming at the problems and the defects, the invention provides the layered oxide material which can regulate and control the types and the distribution of surface elements, has a certain manganese element concentration gradient, can effectively reduce the appearance of manganese dissolution on the surface, is beneficial to improving the structural stability and the product consistency of the material, and effectively improves the multiplying power performance and the cycle performance of the material, and has low production cost, and the preparation method.
The technical scheme of the invention is as follows:
the layered oxide material of the invention is characterized in that: the chemical general formula of the layered oxide material is as follows: na (Na) x Mn i M y O 2+β ；
Wherein M is other metal elements except manganese, and is specifically at least 3 of Li, K, ca, zn, al, ni, fe, cu, ti, mg, co, ba, sr, B, cr, co, V, zr, nb;
0.67≤x≤1； 0.6≤i<1，i＞y ，i+y=1，-0.02≤β≤0.02；
and the body center of the particle inner core region of the layered oxide material coincides with the particle body center of the layered oxide material, and the manganese content is in a concentration gradient decreasing from the particle body center toward the particle surface.
The method further comprises the following steps: the manganese valence state of the inner core region of the particle is lower than that of the surface of the particle. Preferably, the manganese valence state of the particle surface is stable 4 valence, and manganese dioxide is used as the manganese source. The valence state of manganese in the core area of the particle is lower than 4, and at least a manganese source with the valence less than 4 is added in the manganese source.
Wherein the volume of the inner core region of the particle is 15% -60% of the total volume of the particle. Preferably 20% -50%.
The mass k of manganese on the surface of the layered oxide material particles, the mass j, i=j+k, k: y= (0.8-1.2) 1 of manganese in the layered oxide material particles. Controlling this ratio range firstly ensures that the metal M on the surface of the material is substantially equivalent to the Mn content, and secondly, beyond this ratio range, it is difficult to form a manganese concentration gradient from the inner core to the outer surface. Further preferred are: i=0.7, k y=1:1.
Further, the method comprises the following steps: the ratio of manganese content (i) of the layered oxide material particles to manganese content (n (Mn)) of the material surface ranges from: 1.1.ltoreq.i.n (Mn).ltoreq.1.8, n (Mn) being the molar ratio of Mn element on the surface of the layered oxide particles to all metal elements except sodium.
Preferably, it is: the particles of the layered oxide material are single crystals having an average particle size of 1.0-9.0 microns. Internal Na of layered oxide material 2 CO 3 <1000ppm, material surface H 2 O<300ppm，NaOH /（NaOH+H 2 O）<0.9。
The invention also relates to a preparation method of the layered oxide material, which comprises the following steps:
step (1): ball milling a first manganese source serving as a particle core to obtain first manganese source powder, and mixing a sodium source and the first manganese source powder according to the following steps of Na:Mn=x: and mixing the j molar ratio in a solvent to obtain a suspension, and performing spray drying on the suspension to obtain a manganese source powder coated sodium-manganese mixture.
Step (2): according to Mn: m=k: the second manganese source used as surface manganese is mixed with the M metal source in the y molar ratio, and then presintered for 2-8 hours at 600-800 ℃ to obtain the oxide precursor.
Step (3): and mixing the sodium-manganese mixture with an oxide precursor, and sintering at 800-1200 ℃ for 5-12h to obtain the layered oxide material.
The invention is designed to form an inner core (not sintered) firstly, then, an outer layer of a plurality of elements is mixed on the basis of the inner core, and after the material is sintered, micro diffusion can occur due to high manganese content of the inner core, so that a manganese gradient from the inner core to the surface is formed. Because of the limited diffusion capacity, there is essentially no diffusion of surface and core manganese, so a manganese content gradient is formed.
The first manganese source in the invention is at least one of manganese sesquioxide, manganese tetraoxide and manganese dioxide. Preferably one of manganese sesquioxide, manganous oxide or a mixture of manganese sesquioxide and manganous oxide; or a mixture of manganese sesquioxide and manganese dioxide. The second manganese source is preferably manganese dioxide for better surface stability.
The sodium source is sodium carbonate or sodium hydroxide or a combination thereof, and the solvent is one or more of pure water, ethanol or other organic solvents.
The layered oxide material is applied to sodium ion batteries.
The invention has the beneficial effects that:
1. the inner core manganese content of the layered oxide material is larger than the surface manganese content, and a certain concentration gradient exists, so that the appearance of surface manganese dissolution can be effectively reduced, and the structural stability of the material is improved.
2. The total content difference between the Mn element and the M element on the surface is small, and the types of the metal elements on the surface are at least 4, so that the material stress can be obviously reduced, the electronic conductivity of the positive electrode material can be effectively improved, and the rate capability of the material can be improved; and Mn on the surface is mainly stable 4-valence, so that the material structure can be stabilized, and the material cannot generate larger distortion in the charging and discharging processes and the valence changing processes of various metal elements, thereby improving the cycle performance of the material.
3. According to the preparation method, the sodium source and the first manganese source of the inner core are mixed and then dried, so that the problems that the sodium source absorbs water in the subsequent sintering process and the dispersibility of raw materials is reduced, the elements in the sodium-electricity anode material cannot be uniformly mixed, the element content of each particle is greatly different, the product consistency is poor and the like can be effectively avoided. And after the manganese source is coated on the surface of the sodium source, the humidity requirement on the reaction condition or the storage condition is lower than that of the traditional preparation method or the storage requirement in the subsequent sintering or transportation process, thereby being beneficial to reducing the production cost.
4. According to the preparation method, the manganese source with the valence less than 4 is added into the first manganese source, and the manganese dioxide is used for the second manganese source, so that the valence state of the manganese source in the material core is lower than that of the manganese source on the surface, and the material capacity is improved while the stability of the material structure is maintained.
The invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic view of the structure of a material particle according to the present invention;
FIG. 2 is an SEM image of example 1;
fig. 3 is an SEM image of comparative example 1;
fig. 4 is a graph of the first-turn charge-discharge performance of example 1 and comparative example 1.
Detailed Description
The layered oxide material has a chemical general formula: na (Na) x Mn i M y O 2+β ；
Wherein M is other metal elements except manganese, and is specifically at least 3 of Li, K, ca, zn, al, ni, fe, cu, ti, mg, co, ba, sr, B, cr, co, V, zr, nb; x is more than or equal to 0.67 and less than or equal to 1; i is more than or equal to 0.6 and less than or equal to 1, i is more than or equal to y, i+y=1, -0.02 and less than or equal to 0.02;
and the body center of the particle inner core region of the layered oxide material coincides with the particle body center of the layered oxide material, and the manganese content is in a concentration gradient decreasing from the particle body center toward the particle surface.
The method further comprises the following steps: the manganese valence state of the inner core region of the particle is lower than that of the surface of the particle. The manganese source of the manganese element on the surface of the particle can be manganese dioxide, and the manganese source of the manganese element in the inner core area of the particle is manganese sesquioxide, manganese tetraoxide or a mixture thereof or a mixture of manganese sesquioxide and manganese dioxide, so that the valence state of the manganese in the inner core area of the particle is lower than that of the manganese on the surface.
The volume of the inner core region of the particles of the present invention is 15% -60% of the total volume of the particles, as shown in fig. 1. Preferably 20% -50%.
The mass k of manganese on the surface of the layered oxide material particles, the mass j, i=j+k, k: y= (0.8-1.2) 1 of manganese in the layered oxide material particles. This ratio ensures firstly that the metal M content on the surface of the material is substantially equivalent to the Mn content, and secondly that it is difficult to develop a manganese concentration gradient from the inner core to the outer surface beyond this ratio range.
Further, the method comprises the following steps: the ratio of the manganese content (i) of the layered oxide material particles to the manganese content n (Mn) of the material surface ranges from: 1.1.ltoreq.i.n (Mn).ltoreq.1.8, n (Mn) being the molar ratio of Mn element on the surface of the layered oxide particles to all metal elements except sodium.
Preferably, it is: the particles of the layered oxide material are single crystals having an average particle size of 1.0-9.0 microns. Internal Na of layered oxide material 2 CO 3 <1000ppm, material surface H 2 O<300ppm，NaOH /（NaOH+H 2 O）<0.9。
The invention also relates to a preparation method of the layered oxide material, which comprises the following steps:
step (1): ball milling a first manganese source serving as a particle core to obtain first manganese source powder, and mixing a sodium source and the first manganese source powder according to the following steps of Na:Mn=x: and mixing the mixture in a solvent uniformly in a molar ratio j to obtain a suspension, and carrying out spray drying on the suspension to obtain a manganese source powder coated sodium-manganese mixture, wherein j is the mass of manganese in the layered oxide material particles.
Step (2): according to Mn: m=k: and (3) uniformly mixing a second manganese source serving as surface manganese with an M metal source in a y molar ratio, and presintering at 600-800 ℃ for 2-8h to obtain an oxide precursor, wherein k is the mass of manganese on the surface of the layered oxide material particles.
Step (3): and uniformly mixing the sodium-manganese mixture and the oxide precursor, and sintering at 800-1200 ℃ for 5-12h to obtain the layered oxide material.
The first manganese source in the invention is at least one of manganese sesquioxide, manganese tetraoxide and manganese dioxide. Preferably one of manganese sesquioxide, manganous oxide or a mixture thereof, or a mixture of manganese sesquioxide and manganese dioxide. The second manganese source is preferably manganese dioxide for better surface stability.
The sodium source is sodium carbonate or sodium hydroxide or a combination thereof, and the solvent is one or more of pure water, ethanol or other organic solvents.
Example 1:
a layered oxide material, the method of preparation comprising the steps of:
step (1): ball milling manganese trioxide to obtain manganese trioxide powder, and mixing sodium carbonate and manganese trioxide powder according to the following ratio of Na:Mn=1: mixing and stirring uniformly in pure water at a molar ratio of 0.56 to obtain a suspension, and spray-drying the suspension to obtain a manganese oxide powder coated sodium-manganese mixture.
Step (2): according to the molar ratio Na: mn: ni: cu: al=1:0.24:0.1:0.05:0.05 manganese dioxide, nickel oxide, copper oxide and aluminum oxide are respectively mixed and stirred uniformly, and presintered for 4 hours at 650 ℃ to obtain an oxide precursor. Wherein Na in the step is Na in the step (1), and other transition metal elements are added according to the proportion of Na in the step (1).
Step (3): uniformly mixing the sodium-manganese mixture and the oxide precursor, and sintering for 10 hours at 950 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Example 2:
a layered oxide material, the method of preparation comprising the steps of:
step (1): ball milling manganese trioxide to obtain manganese trioxide powder, and mixing sodium carbonate and manganese trioxide powder according to the following ratio of Na:Mn=1: uniformly mixing the mixture in pure water at a molar ratio of 0.6 to obtain a suspension, and performing spray drying on the suspension to obtain a manganese oxide powder coated sodium-manganese mixture.
Step (2): according to the molar ratio Na: mn: ni: cu: al=1:0.2:0.1:0.05:0.05 manganese dioxide, nickel oxide, copper oxide and aluminum oxide are uniformly mixed respectively, and pre-sintered for 4 hours at 650 ℃ to obtain an oxide precursor. Na in this step is Na in step (1).
Step (3): uniformly mixing the sodium-manganese mixture and the oxide precursor, and sintering for 10 hours at 950 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Example 3:
a layered oxide material, the method of preparation comprising the steps of:
step (1): ball milling manganese trioxide to obtain manganese trioxide powder, and mixing sodium carbonate and manganese trioxide powder according to the following ratio of Na:Mn=1: mixing the above materials in pure water at a molar ratio of 0.64 to obtain a suspension, and spray-drying the suspension to obtain a manganese-sodium mixture coated with manganese trioxide powder.
Step (2): according to the molar ratio Na: mn: ni: cu: al=1:0.16:0.1:0.05:0.05 manganese dioxide, nickel oxide, copper oxide, aluminum oxide were mixed, and pre-sintered at 650 ℃ for 4 hours, respectively, to obtain an oxide precursor. Na in this step is Na in step (1).
Step (3): mixing the sodium-manganese mixture with the oxide precursor, and sintering for 10 hours at 950 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Example 4:
a layered oxide material, the method of preparation comprising the steps of:
step (1): manganese oxide and manganese dioxide were mixed according to 8: ball milling to obtain first manganese source mixed powder, and mixing sodium carbonate and the first manganese source mixed powder according to Na:Mn=1: mixing the mixture in pure water at a molar ratio of 0.56 to obtain a suspension, and spray-drying the suspension to obtain a sodium-manganese mixture coated by the first manganese source mixed powder.
Step (2): according to the molar ratio Na: mn: ni: cu: al=1:0.24:0.1:0.05:0.05 manganese dioxide, nickel oxide, copper oxide, aluminum oxide were mixed, and pre-sintered at 650 ℃ for 4 hours, respectively, to obtain an oxide precursor. Na in this step is Na in step (1).
Step (3): mixing the sodium-manganese mixture with the oxide precursor, and sintering for 10 hours at 950 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Example 5:
a layered oxide material, the method of preparation comprising the steps of:
step (1): ball milling manganese trioxide to obtain manganese trioxide powder, and mixing sodium carbonate and manganese trioxide powder according to the following ratio of Na:Mn=1: mixing the above materials in pure water at a molar ratio of 0.4 to obtain a suspension, and spray-drying the suspension to obtain a manganese-sodium mixture coated with manganese trioxide powder.
Step (2): according to the molar ratio Na: mn: ni: cu: al=1:0.3:0.1:0.1:0.1 manganese dioxide, nickel oxide, copper oxide, aluminum oxide were mixed, and pre-sintered at 650 ℃ for 4 hours, respectively, to obtain an oxide precursor. Na in this step is Na in step (1).
Step (3): mixing the sodium-manganese mixture with the oxide precursor, and sintering for 10 hours at 950 ℃ to obtain the layered oxide material NaMn 0.7 Ni 0.1 Cu 0.1 Al 0.1 O 2 。
Example 6:
a layered oxide material, the method of preparation comprising the steps of:
step (1): ball milling manganese dioxide to obtain manganese dioxide powder, and mixing sodium carbonate and manganese dioxide powder according to Na:Mn=1: mixing the mixture in pure water at a molar ratio of 0.56 to obtain a suspension, and spray-drying the suspension to obtain a manganese dioxide powder-coated sodium-manganese mixture.
Step (2): according to the molar ratio Na: mn: ni: cu: al=1:0.24:0.1:0.05:0.05 manganese dioxide, nickel oxide, copper oxide, aluminum oxide were mixed, and pre-sintered at 650 ℃ for 4 hours, respectively, to obtain an oxide precursor. Na in this step is Na in step (1).
Step 3: mixing the sodium-manganese mixture with the oxide precursor, and sintering for 10 hours at 950 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Comparative example 1:
step 1: sodium carbonate and manganese dioxide, copper oxide, aluminum oxide according to the stoichiometric ratio of Na, mn, ni, cu, al, 1:0.8:0.1:0.05:0.05, mixing to obtain a precursor;
step 2: uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
step 3: placing the precursor powder into a muffle furnace, and performing heat treatment for 12 hours in an air atmosphere at 900 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Comparative example 2:
step 1: sodium carbonate and manganese oxide, copper oxide, aluminum oxide, in stoichiometric ratio 1:0.8:0.1:0.05:0.05, mixing to obtain a precursor;
step 2: uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
step 3: placing the precursor powder into a muffle furnace, and performing heat treatment for 12 hours in an air atmosphere at 900 ℃ to obtain the layered oxide material NaMn 0.8 Ni 0.1 Cu 0.05 Al 0.05 O 2 。
Table 1 below shows the physicochemical property test results of examples 1 to 6 and comparative examples 1 to 2:
table 1:
the layered oxide materials prepared in examples 1 to 6 and comparative examples 1 to 2 were used to prepare sodium ion button cells at room temperature for electrochemical performance testing. The test results are shown in Table 2 below:
table 2:
from tables 1 and 2, it can be derived that: under the condition of ensuring that the layered oxide material forms a manganese concentration gradient (examples 1-3), the proportion of the manganese substance k and the metal y in the outer layer of the surface of the material is adjusted to form different concentration gradients of manganese, and the closer the proportion of k and y is, the better the air stability of the material is, namely, the sodium carbonate inside the material and the water content and the sodium hydroxide content of the surface are the lowest (example 2); the more tetravalent manganese is selected as the first manganese source (i.e., manganese dioxide is selected or partially selected as the first manganese source) (examples 4 and 6), the higher the surface moisture, sodium hydroxide and internal sodium carbonate are, i.e., the worse the air stability of the material is, and the worse the air stability is than the case that tetravalent manganese is not selected as the first manganese source; when the manganese content of the material component is regulated to be 0.7, the concentration gradient of manganese on the inner core and the surface of the material is better, the proportion of manganese on the surface and the proportion of manganese on the M metal are equal, the air stability of the material is best, and the internal sodium carbonate is the lowest (example 5). The above examples are all superior to the comparative examples because of the higher structural stability of the material surface due to the introduction of various M metal elements.
Under the condition of ensuring that the manganese concentration gradient is formed by the material (examples 1-3), the proportion of the manganese substance k and the metal y in the outer layer of the surface of the material is adjusted to form different concentration gradients of manganese, and the proportion of k and y is found to be closer to the initial capacity and better cycle performance of the material (example 2); the more tetravalent manganese is selected as the first manganese source (i.e., manganese dioxide is selected or partially selected as the first manganese source) (examples 4 and 6), the lower the initial capacity of the material and the poorer the cycle performance, and the worse the first manganese source is than the tetravalent manganese is not selected (examples 1 to 3); when the manganese content of the material component is regulated to be 0.7, the concentration gradient of manganese on the inner core and the surface of the material is better, the proportion of manganese on the surface and manganese on the M metal are equal, the initial capacity of the material is the highest, and the circulation is the best (example 5). The above examples are all superior to the comparative examples because the surface structure stability of the material is stronger when various M metal elements are introduced into the surface of the material.
As can be seen from fig. 2 and 3, the adoption of the surface multielement composition can effectively improve the structural stability of the material, and the design of the manganese concentration gradient enables the material to react with sodium carbonate more fully, so that the surface of the material is smoother and free of foreign matters (as shown in fig. 2), and the surface of the material without the design is poorer in smoothness (as shown in fig. 3). As can be seen from fig. 4, the structural stability of the material can be effectively improved by adopting the surface multielement composition, and the design of the manganese concentration gradient enables the material to react with sodium carbonate more fully, so that the charge-discharge capacity of the material is higher (example 1), and the capacity of the material without the design is lower than that of 1.
Although the invention has been described with reference to specific embodiments, this description is not meant to limit the invention. Other variations to the disclosed embodiments can be envisioned by those skilled in the art with reference to the description of the invention, and such variations are intended to fall within the scope of the appended claims.

Claims (7)

1. A layered oxide material characterized by: the chemical general formula of the layered oxide material is as follows: na (Na) x Mn i M y O 2+β ；
Wherein M is other metal elements except manganese, and is specifically 3 of Al, ni and Cu;
0.67≤x≤1； 0.6≤i<1，i＞y ，i+y=1，-0.02≤β≤0.02；
the body centers of the particle inner core areas of the layered oxide material are coincident with the particle body centers of the layered oxide material, the manganese content is in a reduced concentration gradient from the particle body centers to the particle surfaces, the manganese valence state of the particle inner core areas of the layered oxide material is lower than that of the particle surfaces, and the manganese valence state of the particle surfaces is stable and 4 valence; the mass k of manganese on the surface of the layered oxide material particles, the mass j, i=j+k, k: y= (0.8-1.2) 1 of manganese in the layered oxide material particles.
2. The layered oxide material of claim 1, wherein: the volume of the inner core region of the particle is 15% -60% of the total volume of the particle.
3. The layered oxide material of claim 1, wherein: the particles of the layered oxide material are single crystals having an average particle size of 1.0-9.0 microns.
4. The layered oxide material of claim 1, wherein: internal Na of layered oxide material 2 CO 3 <1000ppm, surface H 2 O<300ppm，NaOH /（NaOH+H 2 O）<0.9。
5. A method for producing the layered oxide material according to any one of claims 1 to 4, characterized by comprising the steps of:
step (1): ball milling a first manganese source serving as a particle core to obtain first manganese source powder, and mixing a sodium source and the first manganese source powder according to the following steps of Na:Mn=x: mixing the j molar ratio in a solvent to obtain a suspension, and carrying out spray drying on the suspension to obtain a manganese source powder coated sodium-manganese mixture, wherein j is the mass of manganese in the layered oxide material particles;
step (2): according to Mn: m=k: mixing a second manganese source serving as surface manganese with an M metal source in a y molar ratio, and presintering at 600-800 ℃ for 2-8 hours to obtain an oxide precursor, wherein k is the mass of manganese on the surface of the layered oxide material particles;
step (3): and mixing the sodium-manganese mixture with an oxide precursor, and sintering at 800-1200 ℃ for 5-12h to obtain the layered oxide material.
6. The method for producing a layered oxide material according to claim 5, characterized in that: the first manganese source is at least one of manganous oxide and manganic oxide, and the second manganese source is manganese dioxide.
7. The method for producing a layered oxide material according to claim 5, characterized in that: the sodium source is sodium carbonate or sodium hydroxide or a combination thereof, and the solvent is pure water or ethanol.
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