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CN118841560B - Double-coated modified sodium ion battery positive electrode material and preparation method thereof, sodium ion battery - Google Patents

Double-coated modified sodium ion battery positive electrode material and preparation method thereof, sodium ion battery Download PDF

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CN118841560B
CN118841560B CN202411311514.9A CN202411311514A CN118841560B CN 118841560 B CN118841560 B CN 118841560B CN 202411311514 A CN202411311514 A CN 202411311514A CN 118841560 B CN118841560 B CN 118841560B
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ion battery
metal oxide
transition metal
sodium ion
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CN118841560A (en
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李光胤
李冬
王桥
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Ganzhou Norway Technology Co ltd
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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Abstract

本发明提供双包覆改性钠离子电池正极材料，包括O3型钠过渡金属氧化物基体和覆盖基体至少部分表面的包覆层，所述包覆层由内而外依次包括P2/P3型钠过渡金属氧化物和无定形InRu材料，所述P2/P3型钠过渡金属氧化物的化学式为NatNix2Mny2Mg1‑x2‑y2O2。本发明依次利用P2/P3型钠过渡金属氧化物与无定形InRu材料对O3相钠过渡金属氧化物基体改性，能有效提高O3相基体材料首次充放电的容量和循环性能，提高正极材料的电化学稳定性。本发明还提供双包覆改性钠离子电池正极材料的制备方法及包括所述双包覆改性钠离子电池正极材料的钠离子电池。

The present invention provides a double-coated modified sodium ion battery positive electrode material, comprising an O3 type sodium transition metal oxide matrix and a coating layer covering at least a portion of the surface of the matrix, wherein the coating layer comprises a P2/P3 type sodium transition metal oxide and an amorphous InRu material in sequence from the inside to the outside, and the chemical formula of the P2/P3 type sodium transition metal oxide is Na t Ni x2 Mn y2 Mg 1‑x2‑y2 O 2 . The present invention sequentially utilizes the P2/P3 type sodium transition metal oxide and the amorphous InRu material to modify the O3 phase sodium transition metal oxide matrix, which can effectively improve the capacity and cycle performance of the O3 phase matrix material during the first charge and discharge, and improve the electrochemical stability of the positive electrode material. The present invention also provides a preparation method for the double-coated modified sodium ion battery positive electrode material and a sodium ion battery comprising the double-coated modified sodium ion battery positive electrode material.

Description

Double-coated modified sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to modification of a sodium ion battery anode material.
Background
The sodium ion battery layered oxide positive electrode material is the first choice material for energy storage application because of simple preparation method, low cost, good wide temperature range performance and high safety. However, CO 2 and H 2 O in the air are embedded into the layered structure and the Na +/H+ exchanges generated NaOH, na 2CO3 and other surface residual alkali, so that the active sodium of the material is lost, the layered structure is destroyed, the O3 type material is invalid, and the production and storage cost of the O3 type material is increased. Meanwhile, the slow Na + diffusion rate of the O3 type material makes the high-rate discharge capacity low, which limits the practical development. Therefore, research and development of layered oxides with high capacity and high air stability are important breakthroughs for the industrial application of sodium ion batteries.
The coating strategy can effectively block the reaction of active sodium and substances in the air, and enhance the interface stability of the material. However, most of the currently used coating agents are coated by inert substances, which greatly reduces the volume energy density of the material. Meanwhile, the coating material blocks a sodium ion transmission channel, increases interface impedance and increases energy loss. Therefore, new coating materials having excellent ionic conductivity and electronic conductivity are urgently required to improve the overall performance of the positive electrode material.
Disclosure of Invention
Aiming at the technical problems, the application provides a modified sodium ion battery anode material, a preparation method thereof and a sodium ion battery.
In order to achieve the above purpose, the present application proposes the following technical scheme:
In a first aspect, a double-coated modified sodium ion battery anode material is provided, and comprises an O3 type sodium transition metal oxide substrate and a coating layer covering at least part of the surface of the substrate, wherein the coating layer sequentially comprises a P2/P3 type sodium transition metal oxide and an amorphous InRu material from inside to outside, the chemical formula of the P2/P3 type sodium transition metal oxide is Na tNix2Mny2Mg1-x2-y2O2, and t is more than or equal to 0.6 and less than or equal to 0.8,0.16 and less than or equal to x2 and less than or equal to 0.36,0.3 and y2 and less than or equal to 0.7,0.04 and less than or equal to 1-x2-y2 and less than or equal to 0.1.
Further, the chemical formula of the O3 type sodium transition metal oxide matrix is NaNi x1Fey1Mn1-x1-y1O2, wherein x1 is more than or equal to 0.2 and less than or equal to 0.4, y1 is more than or equal to 0.1 and less than or equal to 0.4,0.3 and is more than or equal to 1-x1-y1 is more than or equal to 0.7.
Further, the mass ratio of the P2/P3 type sodium transition metal oxide to the O3 type sodium transition metal oxide matrix is 2-10wt% to 1.
Further, the mass ratio of the amorphous InRu material to the O3 type sodium transition metal oxide matrix is 0.2-2wt%: 1.
In a second aspect, a method for preparing a double-coated modified sodium ion battery positive electrode material is provided, comprising:
S1, mixing a sodium source, a nickel source, a manganese source and a magnesium source to obtain a P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor, wherein t is more than or equal to 0.6 and less than or equal to 0.8,0.16, x2 is more than or equal to 0.36,0.3, y2 is more than or equal to 0.7,0.04 and less than or equal to 1-x2-y2 is more than or equal to 0.1;
S2, mixing the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor, the O3 type sodium transition metal oxide matrix and a nonaqueous solvent to obtain a dispersion liquid, heating and stirring the dispersion liquid until the solvent volatilizes to obtain a mixture;
S3, sintering the mixture to obtain a material A of the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material coated modified O3 type sodium transition metal oxide;
and S4, mixing the amorphous InRu powder with the material A, and performing low-temperature sintering in an air atmosphere to obtain the double-coated modified sodium ion battery anode material.
Further, in the step S3, the sintering temperature is 700-800 ℃, the sintering time is 12-18 h, and the sintering atmosphere is at least one of air atmosphere and oxygen atmosphere.
Further, in the step S4, the low-temperature sintering temperature is 280-350 ℃, and the low-temperature sintering time is 2-3 hours.
Further, the preparation method of the amorphous InRu powder comprises the steps of dissolving In (acac) 3、Ru(acac)3 and potassium nitrate In a solvent, uniformly stirring, drying to obtain mixed powder, heating the mixed powder to 280-290 ℃ In a tubular furnace, preserving heat for 80-120 min, cooling, washing and drying to obtain amorphous InRu powder.
Further, in step S4, the mass ratio of In (acac) 3、Ru(acac)3 to potassium nitrate is 25:1:50.
Further, in step S4, the solvent is a mixed solution of absolute ethanol and deionized water.
Further, the chemical formula of the O3 type sodium transition metal oxide matrix is NaNi x1Fey1Mn1-x1-y1O2, wherein x1 is more than or equal to 0.2 and less than or equal to 0.4, y1 is more than or equal to 0.1 and less than or equal to 0.4,0.3 and is more than or equal to 1-x1-y1 is more than or equal to 0.7.
Further, the mass ratio of the Na tNix2Mny2Mg1-x2-y2O2 material which can be prepared in theory by the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor to the O3 type sodium transition metal oxide matrix is 2-10wt%.
Further, the mass ratio of the amorphous InRu powder to the material A is 0.2-2wt% to 1.
Further, the O3 type sodium transition metal oxide matrix is prepared by a solid phase sintering method, a sol-gel method, a spray drying method, an oxalic acid precursor method and a coprecipitation method.
In step S2, the non-aqueous solvent is one or more of absolute ethanol, acetone and methanol, the heating and stirring are performed in an environment with humidity lower than 10%, and the temperature of the heating and stirring is 60-80 ℃.
In a third aspect, a sodium ion battery is provided, comprising the double-coated modified sodium ion battery positive electrode material or the double-coated modified sodium ion battery positive electrode material prepared by the preparation method.
Compared with the prior art, one or more of the technical schemes can achieve at least one of the following beneficial effects:
according to the double-coating modified sodium ion battery anode material provided by the application, the P2/P3 phase Na tNix2Mny2Mg1-x2-y2O2 and the amorphous InRu material are sequentially used for coating and modifying the O3 phase sodium transition metal oxide matrix, so that the capacity and the cycle performance of the O3 phase matrix material for the first charge and discharge can be effectively improved, and the electrochemical stability of the anode material is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an XRD pattern of the matrix material prepared in example 1.
Fig. 2 is a TEM image of the amorphous InRu material prepared in example 1.
Fig. 3 is an XRD pattern of the positive electrode material prepared in example 1.
Fig. 4 is an SEM image of the positive electrode material prepared in example 1.
Fig. 5 is a TEM image of the positive electrode material prepared in example 1.
Detailed Description
The invention provides a double-coating modified sodium ion battery anode material which comprises an O3 type sodium transition metal oxide substrate and a coating layer covering at least part of the surface of the substrate, wherein the coating layer sequentially comprises a P2/P3 type sodium transition metal oxide and an amorphous InRu material from inside to outside, the chemical formula of the P2/P3 type sodium transition metal oxide is Na tNix2Mny2Mg1-x2- y2O2, and t is more than or equal to 0.6 and less than or equal to 0.8,0.16, x2 is more than or equal to 0.36,0.3, y2 is more than or equal to 0.7,0.04 and less than or equal to 1-x2-y2 is more than or equal to 0.1.
In some preferred embodiments, the O3 sodium transition metal oxide matrix has a chemical formula NaNi x1Fey1Mn1-x1-y1O2, wherein 0.2.ltoreq.x1.ltoreq.0.4, 0.1.ltoreq.y1.ltoreq. 0.4,0.3.ltoreq.1-x 1-y1.ltoreq.0.7.
In a part of preferred embodiments, the mass ratio of the P2/P3 type sodium transition metal oxide to the O3 type sodium transition metal oxide matrix is 2-10wt%.
In a part of preferred embodiments, the mass ratio of the amorphous InRu material to the O3 type sodium transition metal oxide matrix is 0.2-2wt%.
The invention also provides a preparation method of the double-coated modified sodium ion battery anode material, which comprises the following steps:
S1, mixing a sodium source, a nickel source, a manganese source and a magnesium source to obtain a P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor, wherein t is more than or equal to 0.6 and less than or equal to 0.8,0.16, x2 is more than or equal to 0.36,0.3, y2 is more than or equal to 0.7,0.04 and less than or equal to 1-x2-y2 is more than or equal to 0.1;
S2, mixing the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor, the O3 type sodium transition metal oxide matrix and a nonaqueous solvent to obtain a dispersion liquid, heating and stirring the dispersion liquid until the solvent volatilizes to obtain a mixture;
S3, sintering the mixture to obtain a material A of the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material coated modified O3 type sodium transition metal oxide;
and S4, mixing the amorphous InRu powder with the material A, and performing low-temperature sintering in an air atmosphere to obtain the double-coated modified sodium ion battery anode material.
In a part of preferred embodiments, in the step S3, the sintering temperature is 700-800 ℃, the sintering time is 12-18 hours, and the sintering atmosphere is at least one of an air atmosphere and an oxygen atmosphere.
In a part of preferred embodiments, in the step S4, the temperature of the low-temperature sintering is 280-350 ℃, and the time of the low-temperature sintering is 2-3 hours.
In step S1, the sodium source, the nickel source, the manganese source and the magnesium source may be raw materials conventional in the art, for example, the sodium source is one or more of sodium oxide, sodium hydroxide and thermally decomposable sodium salt, and the nickel source, the manganese source and the magnesium source are one or more of nickel oxide, hydroxide and thermally decomposable salt.
In step S1, the raw materials may be mixed by conventional mechanical mixing, for example, ball milling.
According to some embodiments, the amorphous InRu powder is prepared by the existing method, and the preparation method comprises the steps of dissolving In (acac) 3、Ru(acac)3 and potassium nitrate In a solvent, uniformly stirring, drying to obtain mixed powder, heating the mixed powder to 280-290 ℃ In a tubular furnace, preserving heat for 80-120 min, cooling, washing and drying to obtain amorphous InRu powder.
In a partially preferred embodiment, the mass ratio of In (acac) 3 (indium acetylacetonate), ru (acac) 3 (ruthenium acetylacetonate), and potassium nitrate is 25:1:50.
In some preferred embodiments, the solvent is a mixed solution of absolute ethyl alcohol and deionized water, and preferably, the absolute ethyl alcohol and the deionized water are mixed according to a volume ratio of 5-8:1.
In some preferred embodiments, the O3 sodium transition metal oxide matrix has a chemical formula NaNi x1Fey1Mn1-x1-y1O2, wherein 0.2.ltoreq.x1.ltoreq.0.4, 0.1.ltoreq.y1.ltoreq. 0.4,0.3.ltoreq.1-x 1-y1.ltoreq.0.7.
In some preferred embodiments, the mass ratio of the Na tNix2Mny2Mg1-x2-y2O2 material which can be prepared in theory by the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor to the O3 type sodium transition metal oxide matrix is 2-10wt%.
In a part of preferred embodiments, the mass ratio of the amorphous InRu powder to the material A is 0.2-2wt% to 1.
The O3 type sodium transition metal oxide matrix material may be prepared by a preparation method conventional in the art, for example, a solid phase sintering method, a sol-gel method (sol-gel method for preparing gel, then sintering gel), a spray drying method (spray drying method for preparing mixed powder, then sintering mixed powder), an oxalic acid precursor method (oxalic acid precursor method for preparing a precursor, then sintering a precursor), a coprecipitation method (coprecipitation method for preparing a precursor, then sodium mixing sintering), and the like. The preparation raw material of the O3 type sodium transition metal oxide matrix material may be realized by using raw materials conventional in the art.
In a part of preferred embodiments, in step S2, the non-aqueous solvent is one or more of absolute ethanol, acetone and methanol, and the non-aqueous solvent is used as a solvent, so that adverse effects caused by side reactions between water and the O3 type positive electrode material can be avoided, and further, absolute ethanol is preferred, which is a solvent with low cost, most common and non-toxicity. It should be noted that the amount of nonaqueous solvent used in the preparation of the dispersion may be conventionally determined according to the need for dispersion and the subsequent order to obtain a relatively uniform mixture.
In some preferred embodiments, the heating and stirring are performed in an environment with a humidity lower than 10%, so that adverse effects caused by side reactions between water and the O3 type positive electrode material can be avoided in an environment with a lower humidity.
In some embodiments, the temperature of the heating and stirring is 60-80 ℃, and it is required to be noted that the heating temperature corresponding to the heating and stirring is only higher than the volatilization temperature of the nonaqueous solvent, when the heating and stirring temperature is increased, the volatilization time of the solvent is reduced, and similarly, the mixing and stirring time period of the mixed materials is reduced, the moderate increase of the mixing and stirring time period is favorable for improving the mixing uniformity of the materials, and when the volatilization time period is too long, the preparation efficiency of the materials is seriously reduced, so that the heating and stirring temperature can be adjusted conventionally according to the solvent consumption and the mixing uniformity requirement.
In some preferred embodiments, the preparation of the dispersion is performed under ultrasonic conditions, which is favorable for improving the dispersion uniformity of the materials in the nonaqueous solvent, and it is noted that the power and time of the ultrasonic waves can be adjusted conventionally according to the requirement of the dispersion effect.
In some preferred embodiments, the preparation of the dispersion is performed in a closed environment, which can reduce the moisture entering the dispersion from air, thereby reducing the side reaction with the O3 type positive electrode material in the dispersion, and in each example, the O3 type matrix material and the P2 type precursor are added into a container filled with absolute ethyl alcohol, sealed by a preservative film, and placed in an ultrasonic machine for oscillation.
The invention also provides a sodium ion battery, which comprises the double-coated modified sodium ion battery anode material or the double-coated modified sodium ion battery anode material prepared by the preparation method.
The invention will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the invention, but the scope of the invention is not limited to the following specific embodiments.
Example 1
(1) Na 2CO3、Ni(CH3COO)2·4H2O、Fe2O3、MnO2 and Na 3834 are weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then are filled into a mixing tank, are mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), are placed in a muffle furnace at 900 ℃ for heat preservation for 12 hours, are cooled to room temperature along with the furnace to obtain a matrix material, the XRD pattern is shown as figure 1, the prepared matrix material is a pure-phase O3 phase, and the chemical formula of the matrix material can be determined to be NaNi 0.3Fe0.3Mn0.4O2 according to the raw materials.
(2) Na2CO3、Ni(CH3COO)2·4H2O、MnO2、Mg(CH3COO)2·4H2O Is weighed according to the mole ratio of Na to Ni, mn and Mg of 0.67:0.2:0.7:0.1, poured into a mixing tank and mixed for 1h, and the rotating speed of the mixing tank is 900rpm, and the mixing tank is marked as powder 1.
(3) Taking 80ml of absolute ethyl alcohol, pouring 5g of O3 type matrix material and 0.5g of powder 1 into a beaker filled with the absolute ethyl alcohol, sealing with a preservative film, placing the beaker in an ultrasonic machine for shaking for 20min, then placing the two beakers in an oil bath pot, tearing the preservative film, adding a stirrer until all solvents volatilize, transferring the powder into a muffle furnace at 800 ℃ for heat preservation for 12h, and cooling to room temperature along with the furnace to obtain a powder material 2.
(4) Amorphous InRu powder was prepared by the prior art by dissolving 100mg In (acac) 3,4mg Ru(acac)3 and 200mg KNO 3 In 70ml of a mixed solution (volume ratio of absolute ethyl alcohol to deionized water is 6:1) and stirring, drying the mixed solution to obtain a mixed powder, heating the mixed powder to 280 ℃ In a tube furnace with air, preserving heat for 90min, then cooling to room temperature, washing the obtained product with deionized water for several times, and obtaining amorphous InRu material powder, TEM is shown In fig. 2.
(5) Taking 0.05g of amorphous InRu material, uniformly mixing the powder material 2 prepared in the step 3 in a ball milling tank at the rotating speed of 300rpm for 40 minutes. And transferring the prepared powder into a muffle furnace at 300 ℃ for heat preservation for 2 hours to obtain the amorphous outermost layer, the P2/P3 outer layer and the positive electrode material of the O3 matrix.
As can be seen from fig. 3, the XRD pattern of the obtained positive electrode material includes an O3 phase and a P2/P3 phase, and since the matrix material is an O3 phase, the binding material can be known as Na tNi02Mn0.7Mg0.1O2 of P2/P3, and thus the chemical formula of the obtained positive electrode material can be determined as NaNi 0.3Fe0.3Mn0.4O2 @p2/P3 phase Na tNi0.2Mn0.7Mg0.1O2 positive electrode material. The SEM image of the obtained positive electrode material is shown in fig. 4, the TEM image is shown in fig. 5, and the positive electrode material can be determined to be an amorphous outer coating material + a layered structure matrix material by combining fig. 5.
Comparative example 1
(1) Na 2CO3、Ni(CH3COO)2·4H2O、Fe2O3、MnO2 is weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then is filled into a mixing tank, is mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), is placed in a muffle furnace at 900 ℃ for heat preservation for 12 hours, is cooled to room temperature along with the furnace to obtain a matrix material, and the prepared matrix material is pure phase O3 phase NaNi 0.3Fe0.3Mn0.4O2.
Comparative example 2
(1) Na 2CO3、Ni(CH3COO)2、Fe2O3、MnO2 and Na 3834 are weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then are filled into a mixing tank, are mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), are placed in a muffle furnace at 900 ℃ for heat preservation for 12 hours, and are cooled to room temperature along with the furnace to obtain a matrix material pure phase O3 phase NaNi 0.3Fe0.3Mn0.4O2.
(2) Na2CO3、Ni(CH3COO)2·4H2O、MnO2、Mg(CH3COO)2·4H2O Is weighed according to the mole ratio of Na to Ni, mn and Mg of 0.67:0.2:0.7:0.1, poured into a mixing tank and mixed for 1h, and the rotating speed of the mixing tank is 900rpm, and the mixing tank is marked as powder 1.
(3) Taking 80ml of absolute ethyl alcohol, pouring 5g of O3 type matrix material and 0.5g of powder 1 into a beaker filled with the absolute ethyl alcohol, sealing with a preservative film, placing the beaker in an ultrasonic machine for vibrating for 20min, then placing the two beakers in an oil bath pot, tearing the preservative film, adding a stirrer until all solvents volatilize, transferring the powder into a muffle furnace at 800 ℃ for heat preservation for 12h, and cooling to room temperature along with the furnace to obtain the coated modified cathode material.
Comparative example 3
Na 2CO3、Ni(CH3COO)2·4H2O、Fe2O3、MnO2 and Na 3834 are weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then are filled into a mixing tank, are mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), are placed in a muffle furnace at 900 ℃ for heat preservation for 12 hours, and are cooled to room temperature along with the furnace to obtain a matrix material pure phase O3 phase NaNi 0.3Fe0.3Mn0.4O2.
5G of pure O3 phase NaNi 0.3Fe0.3Mn0.4O2 and 0.05g of amorphous InRu material were mixed in a ball mill at 300rpm for 40 minutes. And transferring the prepared powder into a muffle furnace at 300 ℃ for heat preservation for 2 hours to obtain the amorphous InRu material coated O3 phase matrix positive electrode material.
Example 2
(1) Na 2CO3、Ni(CH3COO)2·4H2O、Fe2O3、MnO2 and Na 3834 are weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then are put into a mixing tank, are mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), are placed into a muffle furnace at 900 ℃ for heat preservation for 12 hours, and are cooled to room temperature along with the furnace to obtain a matrix material, wherein the matrix material is pure-phase O3 phase NaNi 0.3Fe0.3Mn0.4O2.
(2) Na2CO3、Ni(CH3COO)2·4H2O、MnO2、Mg(CH3COO)2·4H2O Is weighed according to the mole ratio of Na to Ni, mn and Mg of 0.67:0.2:0.7:0.1, poured into a mixing tank and mixed for 1h, and the rotating speed of the mixing tank is 900rpm, and the mixing tank is marked as powder 1.
(3) Taking 80ml of absolute ethyl alcohol, pouring 5g of O3 type matrix material and 0.25g of powder 1 into a beaker filled with the absolute ethyl alcohol, sealing with a preservative film, placing the beaker into an ultrasonic machine for vibrating for 20min, then placing the two beakers into an oil bath pot, tearing the preservative film, adding a stirrer until all solvents volatilize, transferring the powder into a muffle furnace at 700 ℃ for heat preservation for 12h, and cooling to room temperature along with the furnace to obtain a powder material 2.
(4) Preparing amorphous InRu powder by adopting the prior art, namely dissolving 200mg of In (acac) 3,8mg Ru(acac)3 and 400mg of KNO 3 In 140ml of mixed solution (the volume ratio of absolute ethyl alcohol to deionized water is 6:1) and stirring, drying the mixed solution to obtain mixed powder, heating the mixed powder to 280 ℃ In a tubular furnace which is filled with air, preserving heat for 90min, cooling to room temperature, and washing the obtained product with deionized water for a plurality of times to obtain amorphous InRu material powder;
(5) Taking 0.1g of amorphous InRu material, uniformly mixing the powder material 2 prepared in the step 3 in a ball milling tank at the rotating speed of 300rpm for 40 minutes. And transferring the prepared powder into a muffle furnace at 300 ℃ for heat preservation for 2 hours to obtain the amorphous outermost layer, the P2/P3 outer layer and the positive electrode material of the O3 matrix.
Example 3
(1) Na 2CO3、Ni(CH3COO)2·4H2O、Fe2O3、MnO2 and Na 3834 are weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then are filled into a mixing tank, are mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), are placed in a muffle furnace at 900 ℃ for heat preservation for 12 hours, and are cooled to room temperature along with the furnace to obtain a matrix material pure phase O3 phase NaNi 0.3Fe0.3Mn0.4O2.
(2) Na2CO3、Ni(CH3COO)2·4H2O、MnO2、Mg(CH3COO)2·4H2O Is weighed according to the mole ratio of Na to Ni, mn and Mg of 0.67:0.2:0.7:0.1, poured into a mixing tank and mixed for 1h, and the rotating speed of the mixing tank is 900rpm, and the mixing tank is marked as powder 1.
(3) Taking 80ml of absolute ethyl alcohol, pouring 5g of O3 type matrix material and 0.4g of powder 1 into a beaker filled with the absolute ethyl alcohol, sealing with a preservative film, placing the beaker into an ultrasonic machine for vibrating for 20min, then placing the two beakers into an oil bath pot, tearing the preservative film, adding a stirrer until all solvents volatilize, transferring the powder into a muffle furnace at 750 ℃ for heat preservation for 12h, and cooling to room temperature along with the furnace to obtain a powder material 2.
(4) Preparing amorphous InRu powder by adopting the prior art, namely dissolving 200mg of In (acac) 3,8mg Ru(acac)3 and 400mg of KNO 3 In 140ml of mixed solution (the volume ratio of absolute ethyl alcohol to deionized water is 6:1) and stirring, drying the mixed solution to obtain mixed powder, heating the mixed powder to 280 ℃ In a tubular furnace which is filled with air, preserving heat for 90min, cooling to room temperature, and washing the obtained product with deionized water for a plurality of times to obtain amorphous InRu material powder;
(5) Taking 0.075g of amorphous InRu material, uniformly mixing the powder material 2 prepared in the step 3 in a ball milling tank at the rotating speed of 300rpm for 40 minutes. And transferring the prepared powder into a muffle furnace at 300 ℃ for heat preservation for 2 hours to obtain the amorphous outermost layer, the P2/P3 outer layer and the positive electrode material of the O3 matrix.
Example 4
(1) Na 2CO3、Ni(CH3COO)2·4H2O、Fe2O3、MnO2 and Na 3834 are weighed according to the mole ratio of Na, ni, fe, mn atoms of 1.03:0.3:0.3:0.4, then are filled into a mixing tank, are mixed in the mixing tank for 1 hour (the rotating speed is 900 rpm), are placed in a muffle furnace at 900 ℃ for heat preservation for 12 hours, and are cooled to room temperature along with the furnace to obtain a matrix material pure phase O3 phase NaNi 0.3Fe0.3Mn0.4O2.
(2) Na2CO3、Ni(CH3COO)2·4H2O、MnO2、Mg(CH3COO)2·4H2O Is weighed according to the mole ratio of Na to Ni, mn and Mg of 0.67:0.2:0.7:0.1, poured into a mixing tank and mixed for 1h, and the rotating speed of the mixing tank is 900rpm, and the mixing tank is marked as powder 1.
(3) Taking 80ml of absolute ethyl alcohol, pouring 5g of O3 type matrix material and 0.1g of powder 1 into a beaker filled with the absolute ethyl alcohol, sealing with a preservative film, placing the beaker into an ultrasonic machine for vibrating for 20min, then placing the two beakers into an oil bath pot, tearing the preservative film, adding a stirrer until all solvents volatilize, transferring the powder into a 775 ℃ muffle furnace for heat preservation for 12h, and cooling to room temperature along with the furnace to obtain a powder material 2.
(4) Preparing amorphous InRu powder by adopting the prior art, namely dissolving 200mg of In (acac) 3,8mg Ru(acac)3 and 400mg of KNO 3 into 140mL of mixed solution (the volume ratio of absolute ethyl alcohol to deionized water is 6:1) and stirring, drying the mixed solution to obtain mixed powder, heating the mixed powder to 280 ℃ In a tubular furnace which is filled with air, preserving heat for 90min, cooling to room temperature, and washing the obtained product with deionized water for a plurality of times to obtain amorphous InRu material powder;
(5) Taking 0.025g of amorphous InRu material, uniformly mixing the powder material 2 prepared in the step 3 in a ball milling tank at the rotating speed of 300rpm for 40 minutes. And transferring the prepared powder into a muffle furnace at 300 ℃ for heat preservation for 2 hours to obtain the amorphous outermost layer, the P2/P3 outer layer and the positive electrode material of the O3 matrix.
Preparation of button cell:
In a clean room with humidity lower than 10%, weighing the anode materials prepared in each example and comparative example, acetylene black (C) and a binder (PVDF) according to a mass ratio of 8:1:1, pouring the weighed materials into a mortar, grinding uniformly, adding a proper amount of N-methylpyrrolidone (NMP) into the mortar to enable the powder materials to be completely dissolved to obtain anode material slurry, then coating the slurry on aluminum foil with a thickness of 12 mu m by using a 200 mu m scraper, drying in a 90 ℃ oven for 12 hours to obtain an anode plate, and cutting the anode plate into round plates with a thickness of 12 mu m for standby.
The prepared positive electrode round pole piece is taken as a positive electrode, a hard carbon round pole piece with the diameter of 14 mu m is taken as a negative electrode, NC-019 model NaClO 4 and porous glass fiber (Whatman, GF/D) are taken as a diaphragm for electrolyte, and the button cell is assembled in a glove box filled with argon.
The button cells assembled by the positive electrode materials prepared in each example and comparative example are subjected to charge and discharge test, the charge and discharge voltage range is 2-4V, and the temperature is 25 ℃.
TABLE 1
As can be seen from table 1, the initial discharge specific capacity of the battery assembled from the positive electrode materials of each example was high, and the 1C cycle performance was good. According to analysis, the initial capacity and the cycle performance of the battery assembled by the positive electrode material in the embodiment 1 are superior to those of the battery assembled by the non-double-coated modified positive electrode material in the embodiment 1, and the analysis shows that the Na + in the secondary outer coating material and the Na + in the O3 type matrix material jointly transfer charges between the positive electrode and the negative electrode due to the fact that the P2/P3 phase Na xNi0.2Mn0.7Mg0.1O2 material has an active sodium supplementing effect, so that the specific discharge capacity of the material is improved, the loss of active Na + of the O3 phase matrix material in the first charge and discharge process can be compensated, na +/space existing in the structure can provide more occupying sites and diffusion sites for Na + in the matrix material, a proper amount of Na +/space is generated in the O3 type matrix material after the first charge and discharge, the shielding effect between Na +—Na+ in the matrix material is weakened, the Na layer distance is increased, the diffusion energy barrier of + is reduced, the ion diffusion kinetics is enhanced, the lattice distortion of the material is reduced, the loss of the active Na + in the O3 type matrix material in the first charge and the open channel can be relieved, the stability of the diffusion energy is reduced, the stability is improved, and the stability of the diffusion can be improved, and the stability is improved. Meanwhile, the introduction of the amorphous InRu material relieves the irreversible phase change of the material, increases the eutectic region of O3-P3, improves the specific discharge capacity of the material and stabilizes the electrochemical interface. The composite material has excellent specific capacity and stability through the synergistic effect of the secondary outer layer and the outermost layer.
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 (10)

1. The double-coated modified sodium ion battery anode material is characterized by comprising an O3 type sodium transition metal oxide substrate and a coating layer covering at least part of the surface of the substrate, wherein the coating layer sequentially comprises a P2/P3 type sodium transition metal oxide and an amorphous InRu material from inside to outside, the chemical formula of the P2/P3 type sodium transition metal oxide is Na tNix2Mny2Mg1-x2- y2O2, and t is more than or equal to 0.6 and less than or equal to 0.8,0.16, x2 is more than or equal to 0.36,0.3, y2 is more than or equal to 0.7,0.04 and less than or equal to 1-x2-y2 is more than or equal to 0.1.
2. The double coated modified sodium ion battery positive electrode material of claim 1, wherein the O3 type sodium transition metal oxide matrix has a chemical formula NaNi x1Fey1Mn1-x1-y1O2, wherein 0.2.ltoreq.x1.ltoreq.0.4, 0.1.ltoreq.y1.ltoreq. 0.4,0.3.ltoreq.1-x 1-y1.ltoreq.0.7.
3. The double-coated modified sodium ion battery positive electrode material according to claim 1 or 2, wherein the mass ratio of the P2/P3 type sodium transition metal oxide to the O3 type sodium transition metal oxide matrix is 2% -10%: 1, and the mass ratio of the amorphous InRu material to the O3 type sodium transition metal oxide matrix is 0.2% -2%: 1.
4. The method for preparing the double-coated modified sodium ion battery anode material according to any one of claims 1 to 3, which is characterized by comprising the following steps:
S1, mixing a sodium source, a nickel source, a manganese source and a magnesium source to obtain a P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor, wherein t is more than or equal to 0.6 and less than or equal to 0.8,0.16, x2 is more than or equal to 0.36,0.3, y2 is more than or equal to 0.7,0.04 and less than or equal to 1-x2-y2 is more than or equal to 0.1;
S2, mixing the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor, the O3 type sodium transition metal oxide matrix and a nonaqueous solvent to obtain a dispersion liquid, heating and stirring the dispersion liquid until the nonaqueous solvent volatilizes to obtain a mixture;
S3, sintering the mixture to obtain a material A of the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material coated modified O3 type sodium transition metal oxide;
and S4, mixing the amorphous InRu powder with the material A, and performing low-temperature sintering in an air atmosphere to obtain the double-coated modified sodium ion battery anode material.
5. The preparation method of the double-coated modified sodium ion battery positive electrode material according to claim 4, wherein in the step S3, the sintering temperature is 700-800 ℃, the sintering time is 12-18 h, and the sintering atmosphere is at least one of air atmosphere and oxygen atmosphere;
in the step S4, the low-temperature sintering temperature is 280-350 ℃, and the low-temperature sintering time is 2-3 hours.
6. The method for preparing the double-coated modified sodium ion battery positive electrode material according to claim 4, wherein the preparation method of the amorphous InRu powder comprises the steps of dissolving In (acac) 3、Ru(acac)3 and potassium nitrate In a solvent, uniformly stirring, drying to obtain mixed powder, heating the mixed powder to 280-290 ℃ In a tubular furnace, preserving heat for 80-120 min, cooling, washing and drying to obtain amorphous InRu powder.
7. The method for preparing a double-coated modified sodium ion battery positive electrode material according to claim 6, wherein the mass ratio of In (acac) 3、Ru(acac)3 to potassium nitrate is 25:1:50;
The solvent is a mixed solution of absolute ethyl alcohol and deionized water.
8. The method for preparing a double-coated modified sodium ion battery positive electrode material according to claim 4, wherein the O3 type sodium transition metal oxide matrix material has a chemical formula of NaNi x1Fey1Mn1-x1-y1O2, wherein x1 is more than or equal to 0.2 and less than or equal to 0.4, y1 is more than or equal to 0.1 and less than or equal to 0.4,0.3 and less than or equal to 1-x1-y1 is more than or equal to 0.7;
The mass ratio of the Na tNix2Mny2Mg1-x2-y2O2 material which can be prepared in theory by the P2/P3 type Na tNix2Mny2Mg1-x2-y2O2 material precursor to the O3 type sodium transition metal oxide matrix is 2% -10%:1;
the mass ratio of the amorphous InRu powder to the O3 type sodium transition metal oxide matrix material is 0.2-2:1;
the O3 type sodium transition metal oxide matrix is prepared by adopting a solid phase sintering method, a sol-gel method, a spray drying method, an oxalic acid precursor method and a coprecipitation method.
9. The preparation method of the double-coated modified sodium ion battery positive electrode material according to claim 4, wherein in the step S2, the nonaqueous solvent is one or more of absolute ethyl alcohol, acetone and methanol, the heating and stirring are performed in an environment with humidity lower than 10%, and the temperature of the heating and stirring is 60-80 ℃.
10. A sodium ion battery, characterized by comprising the double-coated modified sodium ion battery positive electrode material according to any one of claims 1 to 3 or the double-coated modified sodium ion battery positive electrode material prepared by the preparation method according to any one of claims 4 to 9.
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