CN116314659B - A mixed-phase structured layered oxide and its preparation method and application - Google Patents
A mixed-phase structured layered oxide and its preparation method and applicationInfo
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Abstract
本发明提供了一种混合相结构的层状氧化物及其制备方法和应用，属于钠离子电池正极材料技术领域。本发明通过在O3相材料表面包覆一层P2相材料，该包覆结构结合了高容量核心O3相和结构稳定的外壳P2相，提高了材料的可逆性和空气稳定性，降低了表面残碱并改善了倍率性能。而且，本发明不需要Li的掺杂来调控形成复合相，降低了生产成本。
The present invention provides a layered oxide with a mixed-phase structure, its preparation method, and its application, belonging to the technical field of sodium-ion battery positive electrode materials. This invention coats an O3 phase material with a layer of P2 phase material. This coating structure combines a high-capacity core O3 phase with a structurally stable outer P2 phase, improving the material's reversibility and air stability, reducing surface residual alkali, and improving rate performance. Furthermore, this invention eliminates the need for lithium doping to control the formation of the composite phase, reducing production costs.
Description
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a layered oxide with a mixed phase structure, a preparation method and application thereof.
Background
Sodium resources are abundant and widely distributed, so that the sodium ion battery has the advantage of low cost, and therefore, the sodium ion battery is widely focused and is considered to be effectively supplemented and replaced by the lithium ion battery, and particularly in the field of energy storage. In the positive electrode material of the sodium ion battery, the layered transition metal oxide is a main research focus due to the simple structure, easy synthesis, environmental friendliness and excellent electrochemical performance. Layered oxide cathode materials are divided into different phases such as P2, O2, P3 and O3 according to Na + coordination configuration and oxygen polyhedral stacking sequence. In general, the electrochemical properties of the P2 and O3 phases are better. The O3 phase has a higher sodium content and generally has a higher theoretical capacity, but since Na ions need to overcome a higher energy barrier through tetrahedral gaps, the electrochemical kinetics of most O3 phase materials are poor, the phase change process is complex, and the capacity decays rapidly. And most O3 phase materials have poor air stability and when exposed to humid air, residual alkali (NaOH and Na 2CO3) is formed, which damages the material properties. The P2 phase material has better multiplying power performance and better structural stability due to wider diffusion channel of prismatic space and easy diffusion of sodium ions, but has lower gram capacity due to lower sodium content. To combine the advantages of the two phases, researchers synthesized P2/O3 intergeneric Na 0.8Li0.2Ni0.5Mn0.5O2 (adv. EnergyMater.4 (2014) 1400458) by Li substitution, and patent CN113651368A discloses a P2 phase material and P2/O3 mixed phase material prepared by regulating the doping amount of Li. But the lithium resource is less, the price is high, and the economic value is low.
Disclosure of Invention
The invention aims to provide a layered oxide with a mixed phase structure, a preparation method and application thereof, which combines a high-capacity core O3 phase and a shell P2 phase with stable structure, improves the reversibility and air stability of the material, reduces residual alkali on the surface and improves the rate performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a layered oxide with a mixed phase structure, which comprises an O3 phase material and a P2 phase material coated on the surface of the O3 phase material;
the O3 phase material has a chemical composition shown in a formula 1:
na xNiaFebMncMdO2±β, the formula 1,
In the formula 1, ni is positive divalent, fe is positive trivalent, mn is positive trivalent and/or positive tetravalent, M is an ion for doping and substituting one or more of three transition metals of Ni, fe and Mn, M comprises one or more of Mg2+、Cu2+、Zn2+、Al3+、B3+、Co3+、Y3+、Ti4 +、Zr4+、Sn4+ and Nb 5+;
In the formula 1, x, a, b, c, d and 2+/-beta are the mol number occupied by the corresponding elements respectively, x is more than or equal to 0.67 and less than or equal to 1, a+b+c+d=1, and d is more than or equal to 0 and less than or equal to 1;
The P2 phase material has a chemical composition shown in a formula 2:
na yMneGfO2 is used as a catalyst for the preparation of the catalyst for the,
In the formula 2, y, e and f are the mol number occupied by the corresponding elements respectively, mn is positive trivalent and/or positive tetravalent, G comprises one or more of Mg 2 +、Cu2+、Zn2+、Ni2+ and Co 2+, y is more than 0 and less than or equal to 0.67, e+f=1, and e is more than 0 and less than or equal to 1.
Preferably, the mass ratio of the P2 phase material to the O3 phase material is 0.02-0.15:1.
The invention provides a preparation method of the layered oxide, which comprises the following steps of dispersing O3 phase material into ethanol to obtain solution A;
dissolving polyvinylpyrrolidone into ethanol to obtain a solution B;
Adding the solution B into the solution A, and forming a PVP coating layer on the surface of the O3 phase material to obtain a complex solution;
According to the theoretical composition of Na, mn and G in the formula 2, dissolving sodium acetate, manganese acetate and acetate containing G element into ethanol to obtain a solution C;
And under the heating condition, adding the solution C into the complex solution, calcining the obtained solid after the ethanol is completely volatilized, and generating a P2 phase material on the surface of the O3 phase material to obtain the layered oxide with a mixed phase structure.
Preferably, the preparation method of the O3 phase material comprises the following steps of mixing water-soluble salts of divalent Ni, water-soluble salts of divalent Fe and water-soluble salts of divalent Mn with water according to theoretical compositions of Ni, fe and Mn in the formula 1 to obtain a mixed metal salt solution;
mixing the mixed metal salt solution, an alkali metal hydroxide solution and ammonia water, performing coprecipitation reaction under the condition that the pH value is 10-12, and aging to obtain a hydroxide precursor;
Mixing the hydroxide precursor with a sodium source to obtain a solid mixture;
or mixing the hydroxide precursor, a sodium source and an M source to obtain a solid mixture;
Sequentially performing first sintering, heating and second sintering on the solid mixture to obtain an O3 phase material, wherein the temperature of the first sintering is 400-500 ℃, and the temperature of the second sintering is 800-950 ℃;
The mass of Na in the sodium source is 2-5% excess relative to the theoretical mass of Na calculated according to formula 1, and the mass of M in the M source is the theoretical mass of M calculated according to formula 1.
Preferably, the total concentration of sodium acetate, manganese acetate and acetate containing G element in the solution C is (0.001-1) G/mL.
Preferably, the temperature of the heating condition is 60-80 ℃.
Preferably, the calcination temperature is 800-850 ℃, and the heat preservation time is 10-15 h.
Preferably, the calcination is performed under an air or oxygen atmosphere.
Preferably, the mass ratio of polyvinylpyrrolidone in the solution B to the O3 phase material in the solution A is 0.005-0.05:1.
The invention provides application of the layered oxide prepared by the scheme or the preparation method of the scheme as a positive electrode material in sodium ion batteries.
According to the invention, the surface of the O3 phase material is coated with a layer of P2 phase material, and the coating structure combines a high-capacity core O3 phase and a shell P2 phase with stable structure, so that the reversibility and air stability of the material are improved, the residual alkali on the surface is reduced, and the rate performance is improved. In addition, the invention does not need Li doping to regulate and control the formation of a composite phase, thereby reducing the production cost.
The invention provides a preparation method of the layered oxide with the mixed phase structure, and the additive polyvinylpyrrolidone (PVP) selected by the invention has a plurality of excellent properties such as low toxicity, film forming property, complexation property, surface activity, chemical stability and the like. PVP has a long chain structure, carbonyl oxygen on a molecular chain can provide a pair of electrons for metal cations, or complex chemical bonds are formed between nitrogen and metal ions in a five-membered nitrogen-containing hetero ring, and PVP can be paired with the metal ions on the surface of an original O3 phase material in an ethanol solvent to form a uniform PVP coating due to the wettability of PVP. Subsequently, metal acetate is added, and dissolved metal ions are also adsorbed by the PVP coating to form a thin metal acetate layer. PVP as high molecular compound has high thermal decomposition temperature, and the structure is not destroyed in the solvent evaporation process, so that the complex metal acetate thin layer can be well maintained. Finally, the P2 phase is generated by the reaction of the high-temperature calcination and partial residual alkali on the surface of the O3 phase material, so that the residual alkali on the surface of the original O3 phase material can be greatly reduced.
The P2 phase material is generated on the surface of the O3 phase material through liquid phase coating and high-temperature sintering, the P2 phase material with controllable thickness and adjustable components is coated on the surface of the O3 phase material (the thickness of the coating layer can be controlled by controlling the addition amount of PVP), and the method has the advantages of simple process route and easy operation, and expensive raw materials are not used.
Drawings
FIG. 1 is a scanning electron microscope test chart of a material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope test chart of the material prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope test chart of the material prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope test chart of the material prepared in comparative example 1 of the present invention;
FIG. 5 is an X-ray powder diffraction test chart of the materials prepared in example 1, example 2, example 3 and comparative example 1 of the present invention;
fig. 6 is a charge-discharge curve of the sodium ion battery provided in example 1 of the present invention;
fig. 7 is a charge-discharge curve of a sodium ion battery according to example 2 of the present invention;
fig. 8 is a charge-discharge curve of a sodium ion battery according to example 3 of the present invention;
fig. 9 is a charge-discharge graph of a sodium ion battery provided in comparative example 1 of the present invention;
fig. 10 is a graph showing the cycle performance test of the sodium ion batteries according to the present invention at different rates as provided in example 1, example 2, example 3 and comparative example 1.
Detailed Description
The invention provides a layered oxide with a mixed phase structure, which comprises an O3 phase material and a P2 phase material coated on the surface of the O3 phase material;
the O3 phase material has a chemical composition shown in a formula 1:
na xNiaFebMncMdO2±β, the formula 1,
In the formula 1, ni is positive divalent, fe is positive trivalent, mn is positive trivalent and/or positive tetravalent, M is an ion for doping and substituting one or more of three transition metals of Ni, fe and Mn, M comprises one or more of Mg2+、Cu2+、Zn2+、Al3+、B3+、Co3+、Y3+、Ti4 +、Zr4+、Sn4+ and Nb 5+;
In the formula 1, x, a, b, c, d and 2+/-beta are the mol number occupied by the corresponding elements respectively, x is more than or equal to 0.67 and less than or equal to 1, a+b+c+d=1, and d is more than or equal to 0 and less than or equal to 1;
The P2 phase material has a chemical composition shown in a formula 2:
na yMneGfO2 is used as a catalyst for the preparation of the catalyst for the,
In the formula 2, y, e and f are the mol number occupied by the corresponding elements respectively, mn is positive trivalent and/or positive tetravalent, G comprises one or more of Mg 2 +、Cu2+、Zn2+、Ni2+ and Co 2+, y is more than 0 and less than or equal to 0.67, e+f=1, and e is more than 0 and less than or equal to 1.
The O3 phase material will be described first.
In the invention, the O3 phase material has a chemical composition shown in a formula 1, namely Na xNiaFebMncMdO2±β formula 1. In formula 1, x may be 0.75, 0.8, 0.9 or 1, d may be 0, 0.05 or 0.1, and β may be 0, 0.05 or 0.1. In the invention, the O3 phase material satisfies valence conservation and is electrically neutral.
In an embodiment of the present invention, the chemical composition of the O3 phase material is NaNi 1/3Fe1/3Mn1/3O2.
The specific position of the substitution of M is not particularly limited in the present invention.
In the present invention, the particle size of the O3 phase material is preferably 4 to 10. Mu.m.
The P2 phase material is described below.
In the invention, the P2 phase material has a chemical composition shown in a formula 2, namely Na yMneGfO2 formula 2.
In formula 2, y may be specifically 0.67, and e may be specifically 0.7 or 1;f may be specifically 0.3. In an embodiment of the present invention, the P2 phase material is specifically Na 2/3MnO2 or Na 2/3Mn0.7Mg0.3O2
In the invention, the mass ratio of the P2 phase material to the O3 phase material is preferably 0.02-0.15:1, more preferably 0.05-0.1:1.
According to the invention, the surface of the O3 phase material is coated with a layer of P2 phase material, and the coating structure combines a high-capacity core O3 phase and a shell P2 phase with stable structure, so that the reversibility and air stability of the material are improved, the residual alkali on the surface is reduced, and the rate performance is improved. In addition, the invention does not need Li doping to regulate and control the formation of a composite phase, thereby reducing the production cost.
The invention provides a preparation method of the layered oxide, which comprises the following steps:
Dispersing the O3 phase material into ethanol to obtain a solution A;
dissolving polyvinylpyrrolidone into ethanol to obtain a solution B;
Adding the solution B into the solution A, and forming a PVP coating layer on the surface of the O3 phase material to obtain a complex solution;
According to the theoretical composition of Na, mn and G in the formula 2, dissolving sodium acetate, manganese acetate and acetate containing G element into ethanol to obtain a solution C;
And under the heating condition, adding the solution C into the complex solution, calcining the obtained solid after the ethanol is completely volatilized, and generating a P2 phase material on the surface of the O3 phase material to obtain the layered oxide with a mixed phase structure.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The O3 phase material is prepared by a method well known in the art without special requirements on the source of the O3 phase material.
In the present invention, the preparation method of the O3 phase material preferably includes the steps of:
according to the theoretical composition of Ni, fe and Mn in the formula 1, mixing water-soluble salts of divalent Ni, water-soluble salts of divalent Fe and water-soluble salts of divalent Mn with water to obtain a mixed metal salt solution;
mixing the mixed metal salt solution, an alkali metal hydroxide solution and ammonia water, performing coprecipitation reaction under the condition that the pH value is 10-12, and aging to obtain a hydroxide precursor;
Mixing the hydroxide precursor with a sodium source to obtain a solid mixture;
or mixing the hydroxide precursor, a sodium source and an M source to obtain a solid mixture;
Sequentially performing first sintering, heating and second sintering on the solid mixture to obtain an O3 phase material, wherein the temperature of the first sintering is 400-500 ℃, and the temperature of the second sintering is 800-950 ℃;
The mass of Na in the sodium source is 2-5% excess relative to the theoretical mass of Na calculated according to formula 1, and the mass of M in the M source is the theoretical mass of M calculated according to formula 1.
According to the theoretical composition of Ni, fe and Mn in the formula 1, the water-soluble salt of bivalent Ni, the water-soluble salt of bivalent Fe and the water-soluble salt of bivalent Mn are mixed with water to obtain a mixed metal salt solution.
In the embodiment of the invention, the water-soluble salt of divalent Ni, the water-soluble salt of divalent Fe and the water-soluble salt of divalent Mn are independently preferably one or more of chloride, nitrate, sulfate, acetate and citrate, and in the embodiment of the invention, the water-soluble salt of divalent Ni is nickel sulfate, the water-soluble salt of divalent Fe is ferrous sulfate and the water-soluble salt of divalent Mn is manganese sulfate.
The invention has no special requirement on the mixing process, and can completely dissolve the water-soluble salt of divalent Ni, the water-soluble salt of divalent Fe and the water-soluble salt of divalent Mn.
In the invention, the total concentration of metal ions in the mixed metal salt solution is preferably 1-3 mol/L, more preferably 1.5-2.5 mol/L.
After the mixed metal salt solution is obtained, the mixed metal salt solution, the alkali metal hydroxide solution and ammonia water are mixed, coprecipitation reaction is carried out under the condition that the pH value is 10-12, and the hydroxide precursor is obtained after aging.
In the invention, the alkali metal hydroxide solution is preferably obtained by dissolving alkali metal hydroxide in water, the alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide, and the concentration of the alkali metal hydroxide solution is preferably 2-5 mol/L, more preferably 3-4 mol/L. In the present invention, the alkali metal hydroxide solution serves as a precipitant.
In the present invention, the concentration of the aqueous ammonia is preferably 4 to 6mol/L, more preferably 5mol/L. In the present invention, the aqueous ammonia is used as a complexing agent.
In the invention, the mixed metal salt solution, the alkali metal hydroxide solution and the ammonia water are preferably added into a reaction kettle simultaneously and concurrently, and the pH value of the system is maintained to be 10-12 for coprecipitation reaction.
The method has no special requirement on the dosage of the alkali metal hydroxide solution and the ammonia water, and the pH value of the reaction system is stabilized to 10-12.
In the present invention, the temperature of the precipitation reaction is preferably 50 to 60 ℃, more preferably 52 to 56 ℃. In the precipitation reaction process, metal ions firstly form a complex with ammonia water, and then react with alkali metal oxides to form spherical metal hydroxide.
The method has no special requirement on the time of the precipitation reaction, and the average particle size of the hydroxide precursor is 4-10 mu m.
In the present invention, the aging time is preferably 10 to 30 hours, more preferably 15 to 25 hours. In the invention, the dissolution and crystallization in the aging process realize dynamic balance, the reaction is carried out in a direction with low energy, and the residual metal ions in the system continue to react on the surface of the metal hydroxide, so that the small particles further grow up, the rearrangement in the crystal is promoted, and the crystallization of the metal hydroxide precipitation is improved.
After the aging is finished, the invention preferably filters the aging product system, washes the aging product system with deionized water for 4 times, and dries the aging product system at 110 ℃ for 10 hours to obtain precursor powder.
After obtaining a spherical hydroxide precursor, the invention mixes the hydroxide precursor with a sodium source to obtain a solid mixture, or mixes the hydroxide precursor, the sodium source and an M source to obtain a solid mixture.
In the invention, the mass of Na in the sodium source is 2-5% excess relative to the theoretical mass of Na calculated according to formula 1, and the invention compensates the burning loss of Na by controlling the mass excess of Na. In the present invention, the mass of M in the M source is a theoretical mass of M calculated according to formula 1.
In the present invention, the sodium source is preferably one or more of sodium nitrate, sodium peroxide, sodium superoxide, sodium carbonate, sodium hydroxide and sodium oxalate, more preferably sodium carbonate or sodium hydroxide.
In the present invention, the M source is preferably one or a combination of several of an oxide, boride, hydroxide, oxyhydroxide, carbonic acid compound, nitric acid compound and acetic acid compound containing M element, more preferably an oxide, hydroxide or oxyhydroxide.
The invention has no special requirement on the mixing mode of the obtained solid mixture, and can uniformly mix all the substances.
After the solid mixture is obtained, the solid mixture is subjected to first sintering, heating and second sintering in sequence to obtain the O3 phase material.
In the invention, the temperature of the first sintering is 400-500 ℃, preferably 420-480 ℃, the heat preservation time is preferably 3-6 hours, more preferably 4-5 hours, and the temperature rising rate from the room temperature to the temperature of the first sintering is preferably 2-6 ℃ per minute -1, more preferably 3-5 ℃ per minute -1. In the first sintering process, the metal hydroxide precursor is subjected to thermal decomposition reaction to generate water and metal oxide, and impurities of solid mixed substances are removed, so that slow permeation in the crystal after the subsequent sodium source decomposition is facilitated, the reaction is more uniform, the formation of a subsequent layered structure is facilitated, and the crystallinity is improved.
In the present invention, the rate of increasing the temperature from the temperature of the first sintering to the temperature of the second sintering is preferably 2 to 6 ℃ min -1, preferably 2 to 5 ℃ min -1.
In the invention, the temperature of the second sintering is 800-950 ℃, preferably 850-900 ℃, and the heat preservation time is preferably 10-20 hours, more preferably 12-18 hours, and even more preferably 14-16 hours. In the present invention, the first sintering and the second sintering are preferably performed under an air atmosphere.
In the second sintering process, the sodium source is melted to participate in crystallization reaction, and M doping replaces part of sites of transition metal.
After the second sintering is completed, the invention preferably cools to room temperature, and the resulting material is ground through a 250 mesh screen to obtain the O3 phase material.
After the O3 phase material is obtained, the O3 phase material is dispersed into ethanol to obtain a solution A.
In the present invention, the ethanol is preferably absolute ethanol. In the invention, the solid-to-liquid ratio of the O3 phase material to ethanol is preferably 1 g:1.5-2.5 mL. In the present invention, the dispersion is preferably performed under ultrasonic conditions, and the time of the ultrasonic treatment is preferably 10 minutes.
According to the invention, polyvinylpyrrolidone is dissolved in ethanol to obtain a solution B. In the invention, the concentration of PVP in the solution B is preferably 8-16 g/L.
After the solution A and the solution B are obtained, the solution B is added into the solution A under the stirring condition, and a PVP coating layer is formed on the surface of the O3 phase material to obtain a complex solution.
In the invention, the mass ratio of polyvinylpyrrolidone in the solution B to the O3 phase material in the solution A is preferably 0.005-0.05:1, more preferably 0.01-0.04:1, and even more preferably 0.02-0.03:1.
In the invention, the adding mode of the solution B is preferably dropwise adding, and the invention has no special requirement on the dropping speed, and the solution B can be dropwise added. In the invention, PVP has a long chain structure, carbonyl oxygen on a molecular chain can provide a pair of electrons for metal cations, or complex chemical bonds are formed between nitrogen and metal ions in a five-membered nitrogen-containing hetero ring, and PVP can be paired with metal ions on the surface of an original O3 phase material in an ethanol solvent to form a uniform PVP coating layer due to the wettability of PVP. By adjusting the amount of PVP, one skilled in the art can adjust the thickness of the coating.
According to the theoretical composition of Na, mn and G in the formula 2, sodium acetate, manganese acetate and acetate containing G element are dissolved in ethanol to obtain a solution C.
In the invention, the sodium acetate is preferably sodium acetate trihydrate, the manganese acetate is preferably manganese acetate tetrahydrate, and the ethanol is preferably absolute ethanol. In the present invention, the total concentration of sodium acetate, manganese acetate and acetate containing G element in the solution C is preferably (0.001 to 1) G/mL, more preferably (0.01 to 0.9) G/mL, still more preferably (0.1 to 0.8) G/mL, and most preferably (0.2 to 0.7) G/mL.
After the solution C is obtained, the solution C is added into the complex solution under the heating condition, and after ethanol is completely volatilized, the obtained solid is calcined, and a P2 phase material is generated on the surface of the O3 phase material, so that the layered oxide with a mixed phase structure is obtained.
In the present invention, the temperature of the heating condition is preferably 60 to 80 ℃. In the present invention, the addition mode of the solution C is preferably dropwise addition. In the present invention, after the addition of the metal acetate, the dissolved metal ions are also adsorbed by the PVP coating to form a thin metal acetate layer. PVP as high molecular compound has high thermal decomposition temperature, and the structure is not destroyed in the solvent evaporation process, so that the complex metal acetate thin layer can be well reserved.
The present invention preferably pulverizes the solids prior to the calcination.
In the invention, the calcination temperature is preferably 800-850 ℃, more preferably 810-830 ℃, and the heat preservation time is preferably 10-15 h, more preferably 12-13 h. In the present invention, the calcination is preferably performed under an air or oxygen atmosphere. In the calcining process, the metal acetate thin layer reacts with part of residual alkali on the surface of the O3 phase material to generate the P2 phase, so that the residual alkali on the surface of the original O3 phase material can be greatly reduced.
The invention provides application of the layered oxide prepared by the scheme or the preparation method of the scheme as a positive electrode material in sodium ion batteries.
The layered oxide of the mixed phase structure, the preparation method and application thereof, which are provided by the present invention, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The O3 phase material in each of the following examples and comparative examples is NaNi 1/3Fe1/3Mn1/3O2, and the preparation method is as follows:
weighing ferrous sulfate, manganese sulfate and nickel sulfate according to the molar ratio of nickel to iron to manganese of 1/3:1/3:1/3, dissolving in deionized water to prepare a metal salt solution with the concentration of 1mol/L, preparing a precipitant sodium hydroxide into a sodium hydroxide solution with the concentration of 5mol/L, and preparing a complexing agent ammonia water into a solution with the concentration of 5 mol/L.
And (3) simultaneously and concurrently adding the mixed metal salt solution, the sodium hydroxide solution and the ammonia water into a reaction kettle, maintaining the pH at 10-12, performing coprecipitation reaction, aging and standing for 12 hours after the particle size reaches 4-10 mu m, filtering, washing with deionized water for 4 times, and drying at 110 ℃ for 10 hours to obtain precursor powder.
Uniformly mixing the Ni 1/3Fe1/3Mn1/3(OH)2 precursor with 105wt% of sodium carbonate with required stoichiometry, transferring into a corundum crucible, calcining in a muffle furnace under the air atmosphere, keeping the temperature for 5 hours at the temperature rising speed of 5 ℃ and min -1 under the air atmosphere in the first stage, keeping the temperature for 12 hours at the temperature rising speed of 3 ℃ and min -1 and 880 ℃ in the second stage, cooling to room temperature, and grinding the calcined material to pass through a 250-mesh screen to obtain the O3 phase material.
Example 1
Preparation of layered oxide cathode material coated with 0.5wt% of P2-Na 2/3MnO2 (NM-0.5, i.e. P2 phase material is 0.5wt% of O3 phase material, the meaning of the rest of examples is the same, and no further description is given):
Adding 50mL of ethanol into 20g NaNi 1/3Fe1/3Mn1/3O2 mL of the solution, performing ultrasonic dispersion for 5min, and continuously stirring to form solution A. 0.2g PVP was dissolved completely in 20mL ethanol to form solution B, which was then added dropwise to the continuously stirred solution A with a dropper to obtain a complex solution.
0.2396g Mn(CH3COO)2·4H2O、0.0888g C2H3O2Na·3H2O, Was dissolved in 20mL of ethanol as solution C. Dropwise adding the solution C into the complex solution by using a dropper, and stirring at a constant temperature of 80 ℃ until the absolute ethyl alcohol is completely evaporated. After the obtained precipitate was pulverized, it was calcined at 810℃for 11 hours under an air atmosphere.
Example 2
Preparation of layered oxide cathode material (NM-1) coated with 1wt% P2-Na 2/3MnO2:
0.4792g of Mn (CH 3COO)2·4H2O、0.1766g CH3COONa·3H2 O) was dissolved in 30mL of ethanol as a C solution, and the rest was the same as in example 1.
Example 3
Preparation of layered oxide cathode Material coated with 1wt% P2-Na 2/3Mn0.7Mg0.3O2 (NMM-1) 0.3687g Mn(CH3COO)2·4H2O、0.1382g C4H14MgO8·4H2O、0.1949gCH3COONa·3H2O, was dissolved in 30mL of ethanol as a C solution, and the rest of the procedure was as in example 1.
Comparative example 1
Is O3 phase lamellar cathode material NaNi 1/3Fe1/3Mn1/3O2.
Structure and performance characterization:
The morphology of the prepared layered positive electrode material was analyzed by using a field emission Scanning Electron Microscope (SEM) (Hitachi Regulus 8100), and scanning electron microscope diagrams of the layered oxide positive electrode materials prepared in examples 1 to 3 and comparative example 1 are shown in fig. 1, fig. 2, fig. 3 and fig. 4, respectively. The surface of NaNi 1/3Fe1/3Mn1/3O2 primary particles in comparative example 1 is relatively smooth and the outline is clear, the layered oxide positive electrode material (NM-0.5) coated with 0.5wt% of P2-Na 2/3MnO2 prepared in example 1 has a clearer appearance due to a smaller coating amount of primary particles, only the edges of the primary particles are obviously coated, the layered oxide positive electrode material (NM-1) coated with 1wt% of P2-Na 2/ 3MnO2 prepared in example 2 and the layered oxide positive electrode material (NMM-1) coated with 1wt% of P2-Na 2/3Mn0.7Mg0.3O2 prepared in example 3 have a more coating amount, the appearance of primary particles is blurred, and the primary particles are obviously filled with the coating.
The materials of examples 1 to 3 and comparative example 1 were subjected to phase analysis by using an XRD diffractometer (the Netherlands PANALYTICAL X' PERT PROMPD), and XRD patterns of the layered oxide cathode materials prepared in examples 1 to 3 and comparative example 1 are shown in FIG. 5, and are each typical O3 type phase structures (JCPDS card No. 54-0887). The XRD patterns of example 1, example 2 and example 3 do not show diffraction peaks of other phases due to the smaller coating amount, except that the intensity and sharpness of the diffraction peaks are slightly reduced relative to comparative example 1. Sharp diffraction peaks indicate that they are highly crystalline.
Further, the residual alkali content of the surface of the material is detected by a potentiometric titration method. The test results are shown in Table 1.
TABLE 1 residual alkali content on the surface of layered oxide materials prepared in examples 1 to 3 and comparative example 1
| Sequence number | Na 2CO3 content/% | NaOH content/% |
| Example 1 | 0.612 | 0.191 |
| Example 2 | 0.520 | 0.162 |
| Example 3 | 0.498 | 0.153 |
| Comparative example 1 | 0.985 | 0.263 |
As can be seen from table 1, the coating treatment helps to reduce residual alkali on the surface of the material, thereby improving cycle performance.
First charge and discharge test:
Mixing the prepared positive electrode material, a binder and conductive carbon black in NMP (N-methyl pyrrolidone) according to a mass ratio of 90:5:5 in a drying room with a dew point lower than-40 ℃, homogenizing, controlling the solid content to be 45%, coating the mixture on an aluminum foil current collector, baking the mixture in vacuum at 100-110 ℃ for 5-8 hours, pressing and forming the mixture, and preparing the sodium positive electrode sheet through punching. The button half cell was assembled in an argon filled glove box with a metallic sodium plate as the counter electrode, PE as the separator and 1mol/L NaPF 6 EC/DMC (Vol 1: 1) as the electrolyte. And performing charge and discharge test on the button cell. The test equipment of the button cell is a commercial LAND cell test system of blue electric electronic Co., ltd. The first reversible capacity and efficiency of the sodium positive electrode materials in examples and comparative examples were measured.
And (3) performing charge and discharge tests on the battery under the conditions of 2.0-4.0V and 0.1C multiplying power. Fig. 6,7, 8 and 9 are graphs of the first charge and discharge tests of example 1, example 2, example 3 and comparative example 1, the specific test results are shown in table 2, and the capacity of the layered oxide cathode materials prepared in example 1, example 2 and example 3 after coating is slightly reduced.
Table 2 charge and discharge properties of examples and comparative examples
And (3) testing the cycle performance:
the cells were tested in a 25 ℃ constant temperature environment on a commercial LAND cell test system from martial arts, blue electronics, inc, with 5 cycles of 0.1C, 0.2C, 0.5C, and 10 cycles of 1.0C in sequence.
Fig. 10 is a graph showing the cycle performance of the sodium ion batteries provided in examples 1 to 3 and comparative example 1 at different rates, and it can be seen from fig. 10 that the sodium ion batteries provided in example 1, example 2 and example 3 have a significantly better cycle performance at 1.0C rate than comparative example 1, and in particular, the sodium ion battery provided in example 3 has a higher capacity at 1.0C rate than comparative example 1, although the initial capacity is slightly lower than comparative example 1. The surface is coated with a shell P2 phase with stable structure, so that the reversibility and structural stability of the material under the circulating condition are improved, and the rate capability is improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The layered oxide with the mixed phase structure is characterized by comprising an O3 phase material and a P2 phase material coated on the surface of the O3 phase material;
the chemical composition of the O3 phase material is NaNi 1/3Fe1/3Mn1/3O2;
The chemical composition of the P2 phase material is Na 2/3Mn0.7Mg0.3O2;
The P2 phase material is 1wt% of the O3 phase material;
the preparation method of the layered oxide comprises dispersing O3 phase material into ethanol to obtain solution A;
dissolving polyvinylpyrrolidone into ethanol to obtain a solution B;
Adding the solution B into the solution A, and forming a PVP coating layer on the surface of the O3 phase material to obtain a complex solution;
According to the theoretical composition of Na, mn and Mg in the formula Na 2/3Mn0.7Mg0.3O2, dissolving sodium acetate, manganese acetate and acetate containing Mg element in ethanol to obtain a solution C;
And under the heating condition, adding the solution C into the complex solution, calcining the obtained solid after the ethanol is completely volatilized, and generating a P2 phase material on the surface of the O3 phase material to obtain the layered oxide with a mixed phase structure.
2. The method for preparing the layered oxide according to claim 1, comprising the steps of dispersing an O3 phase material into ethanol to obtain a solution A;
dissolving polyvinylpyrrolidone into ethanol to obtain a solution B;
Adding the solution B into the solution A, and forming a PVP coating layer on the surface of the O3 phase material to obtain a complex solution;
According to the theoretical composition of Na, mn and Mg in the formula Na 2/3Mn0.7Mg0.3O2, dissolving sodium acetate, manganese acetate and acetate containing Mg element in ethanol to obtain a solution C;
And under the heating condition, adding the solution C into the complex solution, calcining the obtained solid after the ethanol is completely volatilized, and generating a P2 phase material on the surface of the O3 phase material to obtain the layered oxide with a mixed phase structure.
3. The method according to claim 2, wherein the O3 phase material is prepared by mixing a water-soluble salt of divalent Ni, a water-soluble salt of divalent Fe and a water-soluble salt of divalent Mn with water according to the theoretical composition of Ni, fe and Mn in formula NaNi 1/3Fe1/3Mn1/3O2 to obtain a mixed metal salt solution;
mixing the mixed metal salt solution, an alkali metal hydroxide solution and ammonia water, performing coprecipitation reaction under the condition that the pH value is 10-12, and aging to obtain a hydroxide precursor;
Mixing the hydroxide precursor with a sodium source to obtain a solid mixture;
Or mixing the hydroxide precursor and a sodium source to obtain a solid mixture;
Sequentially performing first sintering, heating and second sintering on the solid mixture to obtain an O3 phase material, wherein the temperature of the first sintering is 400-500 ℃, and the temperature of the second sintering is 800-950 ℃;
The mass of Na in the sodium source is 2-5% excess relative to the theoretical mass of Na calculated according to formula NaNi 1/3Fe1/3Mn1/3O2.
4. The preparation method according to claim 2, wherein the total concentration of sodium acetate, manganese acetate and acetate containing Mg element in the C solution is (0.001-1) g/mL.
5. The preparation method according to claim 2, wherein the heating condition is at a temperature of 60-80 ℃.
6. The preparation method according to claim 2, wherein the calcination temperature is 800-850 ℃ and the heat preservation time is 10-15 h.
7. The method of claim 2 or 5, wherein the calcination is performed in an air or oxygen atmosphere.
8. The preparation method of claim 2, wherein the mass ratio of polyvinylpyrrolidone in solution B to O3 phase material in solution a is 0.005-0.05:1.
9. The layered oxide of claim 1 or the layered oxide prepared by the preparation method of any one of claims 2 to 8 is used as a positive electrode material in a sodium ion battery.
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Application publication date: 20230623 Assignee: Ganzhou Anxun New Materials Co.,Ltd. Assignor: Ganzhou Litan New Energy Technology Co.,Ltd. Contract record no.: X2025980037789 Denomination of invention: A layered oxide with a mixed phase structure its preparation method and application Granted publication date: 20250808 License type: Common License Record date: 20251124 |