CN116314640A - Sodium ion battery layered oxide positive electrode material and preparation method thereof - Google Patents

Sodium ion battery layered oxide positive electrode material and preparation method thereof Download PDF

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CN116314640A
CN116314640A CN202211499940.0A CN202211499940A CN116314640A CN 116314640 A CN116314640 A CN 116314640A CN 202211499940 A CN202211499940 A CN 202211499940A CN 116314640 A CN116314640 A CN 116314640A
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sintering
source
equal
sodium
layered oxide
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李宇
寇亮
张�诚
张超
王继峰
屈涛
李彦
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Jinghe Xincheng Shaanxi Coal Technology Research Institute New Energy Materials Co ltd
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract

The invention discloses a sodium ion battery anode material and a preparation method thereof, and the chemical formula is Na x Ni a Fe b Mn c Me d O 2 X, a, b, c, d satisfy 0.6.ltoreq.x.ltoreq.1.5, 0 simultaneously<a≤0.6，0≤b≤0.5，0<c is less than or equal to 0.5, d is less than or equal to 0 and less than or equal to 0.4, and a+b+c+d=1. Me is one of Ti, al, cu, mg, zr or Zn. Mixing nickel source, sodium source, manganese source, iron source, me source and additive, and sintering to obtain primary sintered productThe method comprises the steps of carrying out a first treatment on the surface of the Mixing the primary combustion product with a surface modifier and sintering to obtain a secondary combustion product; and mixing the two-firing product with a coating agent, and sintering to obtain the layered oxide cathode material. The invention solves the problems of high difficulty, high sintering temperature, serious agglomeration, high total alkali, poor processing performance, and poor capacity and cycle performance of the prepared single crystal material for preparing the layered oxide single crystal anode material in the prior art.

Description

Sodium ion battery layered oxide positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a sodium ion battery layered oxide positive electrode material and a preparation method of the sodium ion battery layered oxide positive electrode material.
Background
In recent years, with the gradual exposure of problems such as lithium resource scarcity, uneven distribution, difficult development and utilization, etc., sodium ion batteries with wide resource distribution are attracting attention again, and the search for low-cost alternatives is becoming a focus of attention. Meanwhile, the development of the energy storage market with lower energy density requirement lays confidence in the industrialization of sodium ion batteries. Sodium ion batteries are gradually mature in research in recent years, and the battery cost can be reduced by 30% -40% compared with that of lithium batteries due to the fact that sodium is rich in reserve and low in price, and the sodium batteries are more excellent in safety, high-low temperature and quick-charging performance, so that the sodium ion batteries have wide application prospects in markets of energy storage, two-wheelers and the like. In recent years, research on sodium ion batteries has been growing in a blowout manner, and global sodium ion battery companies are established, which marks the arrival of the sodium ion battery industrialization age.
Currently, sodium-electricity cathode materials that are widely focused by researchers mainly include layered oxides, prussian blue-based compounds, and polyanion-based compounds. Wherein the layered oxide material has high specific capacity and comprehensive performance. Layered transition metal oxide (Na x MO 2 ) The structure is similar to that of a lithium ion ternary material, and transition metal layers and alkali metal layers are alternately arranged. Stacks based on coordination environment of sodium ions and oxygenThe integration modes are different, and can be divided into O3 phase (octahedral type) and P2 phase (triangular prism type), and the O3 type structure has low capacity retention rate, but Na + High content and high energy density. The P2 structure is complementary with the structure, the cycle performance is better, and the specific capacity is limited.
The layered metal oxide is used as the most mature route for development, has the highest specific capacity and obvious advantages of compact density, and has the potential of preparing sodium ion batteries with higher energy density. And the preparation process is simple, easy to amplify and easy to conduct from the technical end to the industrial end. The existing industrialized preparation process of the layered metal oxide of the sodium ion battery mainly comprises a liquid phase method and a solid phase method, wherein the liquid phase method is highly consistent with the preparation process of the ternary positive electrode material of the lithium ion battery except for raw materials and specific process parameters, corresponding precursors are prepared through coprecipitation, and the corresponding precursors are further sintered with a sodium source to obtain the positive electrode material. Compared with the liquid phase method, the solid phase method does not need a precursor preparation step, has short process flow, small environmental pollution and the like. However, the precursor sintering obtained by the existing liquid phase method is difficult to obtain single crystal materials, and the flow is long. The solid phase method needs to mix various raw materials, and is difficult to ensure uniform mixing of the various raw materials during preparation, so that the performance of the anode material is easy to be poor. The solid phase technology is high in sintering temperature, long in reaction time, irregular in material morphology, low in compaction, high in material residual alkali, and poor in electrochemical performance, and the processing performances such as battery pulping and coating are seriously affected.
Disclosure of Invention
The invention aims to provide a layered oxide cathode material of a sodium ion battery, which solves the problems of high difficulty in preparing a layered oxide single crystal cathode material, high sintering temperature, poor processability, poor capacity and poor cycle performance caused by irregular morphology, serious agglomeration and high total alkali of the prepared single crystal material in the prior art.
The invention further aims to provide a preparation method of the layered oxide cathode material of the sodium ion battery.
The first technical scheme adopted by the invention is that the sodium ion battery layered oxide positive electrode material has the chemical formula: na (Na) x Ni a Fe b Mn c Me d O 2 Wherein x, a, b, c and d are mole percentages of the corresponding elements respectively.
The first aspect of the present invention is also characterized in that,
x, a, b, c, d satisfy the following conditions simultaneously: x is more than or equal to 0.6 and less than or equal to 1.5, b is more than or equal to 0< a and less than or equal to 0.6,0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.4, and a+b+c+d=1.
Me is one of Ti, al, cu, mg, zr or Zn.
The second technical scheme adopted by the invention is that the preparation method of the sodium ion battery layered oxide cathode material is implemented according to the following steps:
step 1, uniformly mixing a nickel source, a sodium source, a manganese source, an iron source, a Me source, an auxiliary agent and a doping agent according to a proportion to obtain a mixture, carrying out primary sintering on the mixture in an air or oxygen atmosphere, heating up the mixture for a period of time, heating up again, continuously carrying out sintering, cooling to a tapping temperature after sintering is finished, and finally tapping, crushing and screening to obtain a sintered product;
step 2, mixing the primary combustion product obtained in the step 1 with a surface modifier, heating to a reaction temperature in an air or oxygen atmosphere after uniformly mixing, performing secondary sintering, cooling to a tapping temperature after the secondary sintering is finished, discharging from a furnace, crushing, and screening to obtain a secondary combustion product;
and step 3, uniformly mixing the product obtained in the step 2 with a coating agent, performing third sintering under air or oxygen atmosphere, and screening the third sintering product to obtain the O3 or P2 layered oxide anode material.
The second aspect of the present invention is also characterized in that,
in the step 1, the nickel source is nickel hydroxide or nickel oxide after further presintering, the morphology is loose and porous, the nickel source is a secondary sphere or spheroid formed by stacking primary particles, wherein the primary particles are in a flake shape or a plate shape, the particle size of the secondary particles is 1-10 mu m, and the specific surface is 5-150m 2 /g; the sodium source is one or more of anhydrous sodium carbonate, sodium sulfate, sodium hydroxide, sodium nitrate or sodium acetate; the manganese source is dioxideOne or more of manganese, manganese oxide or manganese oxide; the iron source is one or more of ferric oxide or ferroferric oxide; the Me source is TiO 2 、Al 2 O 3 、CuO、ZrO 2 、MgO、ZnO 2 One of the following; the auxiliary agent is NaNO 3 The molar ratio m of the auxiliary agent to the sum of sodium sources is more than or equal to 0 and less than or equal to 1, the metal element in the doping agent is one or more of Mg, zr, W, ti, Y, cu, al, sr, mo, V, and the metal element in the doping agent accounts for 10-10000 ppm of the total mass of the anode material.
In the step 1, the mixing ratio of the nickel source, the sodium source, the manganese source, the iron source, the Me source, the auxiliary agent and the doping agent meets the following conditions: na (Na) x Ni a Fe b Mn c Me d O 2 Wherein x, a, b, c and d are the mole percentages of the corresponding elements respectively, and the following conditions are satisfied at the same time: x is more than or equal to 0.6 and less than or equal to 1.5,0<a≤0.6，0≤b≤0.5，0<c is less than or equal to 0.5, d is less than or equal to 0.4, and a+b+c+d=1.
The temperature of the first sintering in the step 1 is 200-500 ℃, the sintering time is 1-10 h, the temperature of the continuous sintering after the temperature is raised again is 800-1100 ℃, and the sintering time is 4-24 h; the temperature rising rate of the two times of temperature rising is 0.5-10 ℃/min, and the temperature reducing rate is 0.5-10 ℃/min.
In step 2, the surface modifier is (NH) 4 ) 2 HPO 4 、NH4H2PO4、H 3 PO 4 、HPO 3 、H 3 BO 3 、NH 4 HB 4 O 7 ·3H 2 One or more of O, the temperature of the second sintering is 100-700 ℃, the second sintering time is 2-20 h, the cooling rate is 0.5-10 ℃/min, and the surface modifier accounts for 100-10000 ppm of the total mass of the anode material.
In the step 3, the third sintering temperature is 100-700 ℃ and the sintering time is 2-20 h.
The coating agent in the step 3 is Al 2 O 3 、TiO 2 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 The metal element in the coating agent accounts for 10 to 10000ppm of the total mass of the anode material.
The invention has the beneficial effects that the morphology and the particle size of the product can be well controlled by adopting spherical nickel hydroxide with a large proportion or nickel oxide after further presintering as a nickel source and taking the nickel hydroxide as a reaction site and a template; in addition, the addition of the auxiliary agent in the primary sintering process can obtain the single-crystalline sodium-electricity layered oxide anode material in one step at a lower temperature and a lower reaction time, thereby effectively reducing energy consumption. As can be seen from electron microscope and granularity results, the morphology of the material obtained by the invention presents regular single crystal, the dispersibility is good, the tap density is high, and the particle size distribution is narrow; the monocrystal is favorable for improving the cycling stability of the material under high voltage, so that the monocrystal layered oxide positive electrode material has excellent capacity and electrochemical performance. The invention utilizes the surface modifier to carry out secondary sintering, effectively reduces the total base number of the material, improves the surface property of the material, can effectively improve the processing performance of the material in the subsequent battery pulping coating and other processes, and simultaneously the reduction of the total base number is beneficial to the gas production control of the battery. According to the invention, the material is further coated by the coating agent, so that the structural stability and the cyclic stability of the material are effectively improved. The invention has simple process and is suitable for large-scale industrialized production.
Drawings
FIG. 1 is an SEM image of a layered oxide cathode material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of a layered oxide cathode material prepared in example 1 of the present invention;
FIG. 3 is a buckling first charge-discharge curve of the layered oxide cathode material prepared in example 1 of the present invention;
FIG. 4 is an SEM image of a layered oxide cathode material prepared according to example 2 of the present invention;
fig. 5 is an SEM image of the layered oxide cathode material prepared in comparative example 1 of the present invention;
fig. 6 is an SEM image of the layered oxide cathode material prepared in comparative example 2 of the present invention;
fig. 7 is an SEM image of the layered oxide cathode material prepared in comparative example 3 of the present invention;
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a layered oxide positive electrode material of a sodium ion battery, which has the chemical formula: na (Na) x Ni a Fe b Mn c Me d O 2 Wherein x, a, b, c and d are mole percentages of the corresponding elements respectively. The positive electrode material of the sodium ion battery has an O3 phase or P2 phase crystal structure. x, a, b, c, d satisfy the following conditions simultaneously: x is more than or equal to 0.6 and less than or equal to 1.5,0<a≤0.6，0≤b≤0.5，0<c is less than or equal to 0.5, d is less than or equal to 0.4, and a+b+c+d=1. Me is one of Ti, al, cu, mg, zr or Zn. The invention takes regular spherical or quasi-spherical nickel hydroxide or nickel oxide with high specific surface as a nickel source, has higher reactivity, takes the nickel hydroxide or nickel oxide as a reaction site and a template, promotes sodium source, iron source, manganese source and the like to carry out high-temperature solid-phase reaction on the surface of the nickel source to generate a product, further carries out solid-phase diffusion to the inside of the nickel source to completely generate a target product, and finally obtains the monocrystalline material after the product is crushed. The nickel source can effectively promote solid-phase reaction, and the particle size of a single-crystal target product can be adjusted by adjusting the particle size of the nickel source within a certain range, so that the method has strong applicability.
The preparation method of the sodium ion battery layered oxide cathode material comprises the following specific steps:
step 1, uniformly mixing a nickel source, a sodium source, a manganese source, an iron source, a Me source, an auxiliary agent and a doping agent according to a proportion to obtain a mixture, performing primary sintering on the mixture in air or oxygen atmosphere, then heating up for reaction for a period of time, heating up again, continuously performing sintering, cooling to a tapping temperature after sintering is finished, and finally tapping, crushing and screening to obtain a sintered product;
in the step 1, the nickel source is nickel hydroxide or nickel oxide after further presintering, the morphology is loose and porous, the nickel source is a secondary sphere or sphere-like structure formed by stacking primary particles, wherein the primary particles are in a flake shape or a plate shape, the particle size of the secondary particles is 1-10 mu m,the specific table is 5-150m 2 /g; the sodium source is one or more of anhydrous sodium carbonate, sodium sulfate, sodium hydroxide, sodium nitrate or sodium acetate; the manganese source is one or more of manganese dioxide, manganese sesquioxide or manganese tetraoxide; the iron source is one or more of ferric oxide or ferroferric oxide; the Me source is TiO 2 、Al 2 O 3 、CuO、ZrO 2 、MgO、ZnO 2 One of the following; the auxiliary agent is NaNO 3 The molar ratio m of the auxiliary agent to the sum of sodium sources is more than or equal to 0 and less than or equal to 1, the metal element in the doping agent is one or more of Mg, zr, W, ti, Y, cu, al, sr, mo, V, and the metal element in the doping agent accounts for 10-10000 ppm of the total mass of the anode material.
In the step 1, the mixing ratio of the nickel source, the sodium source, the manganese source, the iron source, the Me source, the auxiliary agent and the doping agent meets the following conditions: na (Na) x Ni a Fe b Mn c Me d O 2 Wherein x, a, b, c and d are the mole percentages of the corresponding elements respectively, and the following conditions are satisfied at the same time: x is more than or equal to 0.6 and less than or equal to 1.5,0<a≤0.6，0≤b≤0.5，0<c is less than or equal to 0.5, d is less than or equal to 0.4, and a+b+c+d=1.
The temperature of the first sintering in the step 1 is 200-500 ℃, the sintering time is 1-10 h, the temperature of the continuous sintering after the temperature is raised again is 800-1100 ℃, and the sintering time is 4-24 h; the temperature rising rate of the two times of temperature rising is 0.5-10 ℃/min, and the temperature reducing rate is 0.5-10 ℃/min.
Step 2, mixing the primary combustion product obtained in the step 1 with a surface modifier, heating to a reaction temperature in an air or oxygen atmosphere after uniformly mixing, performing secondary sintering, cooling to a tapping temperature after the secondary sintering is finished, discharging from a furnace, crushing, and screening to obtain a secondary combustion product;
in step 2, the surface modifier is (NH) 4 ) 2 HPO 4 、NH4H2PO4、H 3 PO 4 、HPO 3 、H 3 BO 3 、NH 4 HB 4 O 7 ·3H 2 One or more of O, a second sinteringThe temperature is 100-700 ℃, the second sintering time is 2-20 h, the cooling rate is 0.5-10 ℃/min, and the surface modifier accounts for 100-10000 ppm of the total mass of the anode material.
And step 3, uniformly mixing the product obtained in the step 2 with a coating agent, performing third sintering under air or oxygen atmosphere, and screening the third sintering product to obtain the O3 or P2 layered oxide anode material.
In the step 3, the third sintering temperature is 100-700 ℃ and the sintering time is 2-20 h.
The coating agent in the step 3 is Al 2 O 3 、TiO 2 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 The metal element in the coating agent accounts for 10 to 10000ppm of the total mass of the anode material.
Compared with the conventional method, the method takes specific spherical nickel or further presintered nickel oxide as a nickel source, then carries out solid-phase reaction with solid-phase iron sources, manganese sources, sodium sources, auxiliary agents and the like, and utilizes eutectic substances to form between solid-phase substances so as to reduce the energy barrier of monocrystal formation, so that the monocrystal can be formed at lower temperature and lower reaction time, and the morphology and the grain size of the product are well controlled.
In the invention, an auxiliary agent and a doping agent are simultaneously used in the primary sintering process. The sintering temperature is reduced by using the auxiliary agent, so that the realization difficulty of high-temperature conditions is reduced and the energy consumption is reduced to a certain extent; the structural stability, particularly the air stability, of the material is improved through the use of the doping agent, and the long-time storage and use of the material are facilitated.
According to the invention, the material is subjected to surface modification at a lower temperature through secondary sintering, and the surface modifier is utilized to perform chemical reaction with residual alkali, so that the residual alkali on the surface of the material is consumed, thereby greatly reducing the residual alkali number of the material, improving the later processing performance of the material, improving the comprehensive performance of the material, and greatly improving the production efficiency. Therefore, the method is suitable for large-scale industrial production.
Example 1
The preparation method of the layered oxide cathode material of the sodium ion battery comprises the following steps:
(1) 0.66mol of Ni source Ni (OH) 2 With 1.02mol of Na source 2 CO 3 0.66mol of Fe source 2 O 3 MnO of 0.66mol manganese source 2 0.02mol of Me source TiO 2 20% of auxiliary NaF and 1500ppm of doping agent ZrO 2 Uniformly mixing, sintering in an air atmosphere, heating to a first sintering temperature of 500 ℃ at 2 ℃/min for 7 hours, heating to a second sintering temperature of 860 ℃ at 2 ℃/min for 12 hours, cooling with a furnace at 5 ℃/min after sintering, and crushing and screening after discharging the product to obtain the layered oxide anode material;
(2) Mixing the obtained layered oxide positive electrode material with 100ppm of surface modifier H 3 PO 4 Uniformly mixing, performing secondary sintering under air atmosphere at 650 ℃ for 8 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain the modified layered oxide anode material;
(3) Mixing the modified layered oxide positive electrode material with 300ppm of Al 2 O 3 And (3) carrying out three times of sintering under an air atmosphere after mixing, wherein the sintering temperature is 300 ℃, the sintering time is 6 hours, cooling along with a furnace after sintering is finished, and sieving after discharging the product from the furnace to obtain a final product, wherein the result of a product electron microscope is shown in figure 1, the result of XRD is shown in figure 2, and the primary charge-discharge curve of the button cell is shown in figure 3.
Example 2
The preparation method of the layered oxide cathode material of the sodium ion battery comprises the following steps:
(1) 4.8mol of NiO as a nickel source and 2.5mol of Na as a sodium source 2 SO 4 1.8mol of Fe source 2 O 3 Mn as a manganese source 1mol 3 O 4 0.6mol of Me source Al 2 O 3 Mixing uniformly, sintering in air atmosphere at a speed of 3 ℃/miHeating to the first sintering temperature of 200 ℃ for 10 hours, heating to the second sintering temperature of 800 ℃ at 3 ℃/min for 4 hours, cooling with a furnace at 5 ℃/min after sintering, and crushing and screening after discharging the product from the furnace to obtain the layered oxide anode material;
(2) The resulting layered oxide cathode material was combined with 3000ppm of a surface modifier (NH 4 ) 2 HPO 4 +H 3 BO 3 Uniformly mixing, performing secondary sintering under air atmosphere at the sintering temperature of 100 ℃ for 2 hours, cooling along with a furnace after sintering is completed, and sieving after discharging the product from the furnace to obtain the modified layered oxide anode material;
(3) Mixing the modified layered oxide positive electrode material with 2000ppm of WO 3 And (3) carrying out three times of sintering under the air atmosphere after mixing, wherein the sintering temperature is 420 ℃, the sintering time is 8 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain a final product, as shown in fig. 4.
Example 3
The preparation method of the layered oxide cathode material of the sodium ion battery comprises the following steps:
(1) 3.4mol of Ni source Ni (OH) 2 With 7.6mol of Na source 2 CO 3 3.4mol of Fe source 2 O 3 MnO of 4.8mol manganese source 2 3000ppm of dopant Y 2 O 3 Uniformly mixing, sintering in an air atmosphere, heating to a first sintering temperature of 500 ℃ at 5 ℃/min for 1h, heating to a second sintering temperature of 1100 ℃ at 5 ℃/min for 24h, cooling with a furnace at 1 ℃/min after sintering, and crushing and screening after discharging the product to obtain the layered oxide anode material;
(2) Mixing the obtained layered oxide positive electrode material with 500ppm of surface modifier H 3 BO 3 Uniformly mixing, performing secondary sintering under air atmosphere at 700 ℃ for 20 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain a modified layered oxide anode material;
(3) The modified lamellar oxygenPositive electrode material of oxide and 800ppm of Li 3 PO 4 And (3) carrying out three times of sintering under the air atmosphere after mixing, wherein the sintering temperature is 700 ℃, the sintering time is 20 hours, cooling along with a furnace after the sintering is finished, and sieving after the product is taken out of the furnace to obtain the final product.
Example 4
The preparation method of the layered oxide cathode material of the sodium ion battery comprises the following steps:
(1) 2.6mol of Ni source Ni (OH) 2 With 8mol of Na source 2 CO 3 1.8mol of Fe source 2 O 3 2.7mol manganese source MnO 2 Uniformly mixing, sintering in an oxygen atmosphere, heating to a first sintering temperature of 500 ℃ at 2 ℃/min for 7 hours, heating to a second sintering temperature of 860 ℃ at 2 ℃/min for 12 hours, cooling with a furnace at 5 ℃/min after sintering, and crushing and screening after discharging the product to obtain the layered oxide anode material;
(2) Mixing the obtained layered oxide positive electrode material with 500ppm of surface modifier HPO 3 Uniformly mixing, performing secondary sintering under air atmosphere at 650 ℃ for 8 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain the modified layered oxide anode material;
(3) Mixing the modified layered oxide positive electrode material with 1200ppm of Al 2 O 3 And (3) carrying out three times of sintering under the air atmosphere after mixing, wherein the sintering temperature is 300 ℃, the sintering time is 6 hours, cooling along with a furnace after the sintering is finished, and sieving after the product is taken out of the furnace to obtain the final product.
Comparative example 1
The method comprises the following steps:
(1) 0.66mol of nickel source amorphous NiO and 1.02mol of sodium source Na 2 CO 3 0.66mol of Fe source 2 O 3 MnO of 0.66mol manganese source 2 0.02mol of Me source TiO 2 20% of auxiliary NaF and 1500ppm of doping agent ZrO 2 Mixing, sintering in air atmosphere at 2 deg.c/min to the first sintering temperature of 500 deg.c for 7 hr, and heating at 2 deg.c/min to the first sintering temperatureThe second sintering temperature is 860 ℃ and the sintering time is 12 hours, cooling is carried out with the furnace at 5 ℃/min after sintering is finished, and crushing and screening are carried out after the product is taken out of the furnace, so as to obtain the layered oxide anode material;
(2) Mixing the obtained layered oxide positive electrode material with 400ppm of surface modifier H 3 PO 4 Uniformly mixing, performing secondary sintering under air atmosphere at 650 ℃ for 8 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain the modified layered oxide anode material;
(3) Mixing the modified layered oxide positive electrode material with 300ppm of Al 2 O 3 And (3) carrying out three times of sintering under the air atmosphere after mixing, wherein the sintering temperature is 300 ℃, the sintering time is 6 hours, cooling along with a furnace after the sintering is finished, and sieving after the product is taken out of the furnace to obtain a final product, as shown in figure 5.
Comparative example 2
The method comprises the following steps:
(1) 3mol of Ni source Ni (OH) 2 With 1.02mol of Na source 2 CO 3 1.5mol of Fe source 2 O 3 3mol manganese source MnO 2 1mol of Me source Al 2 O 3 13% of auxiliary NaF, 5000ppm of doping agent Y 2 O 3 Uniformly mixing, sintering in an air atmosphere, heating to a first sintering temperature of 500 ℃ at 2 ℃/min for 7 hours, heating to a second sintering temperature of 860 ℃ at 2 ℃/min for 12 hours, cooling with a furnace at 5 ℃/min after sintering, and crushing and screening after discharging the product to obtain the layered oxide anode material;
(2) Mixing the obtained layered oxide positive electrode material with 6200ppm TiO 2 And (3) carrying out three times of sintering under the air atmosphere after mixing, wherein the sintering temperature is 300 ℃, the sintering time is 6 hours, cooling along with a furnace after the sintering is finished, and sieving after the product is taken out of the furnace to obtain a final product, as shown in figure 6.
Comparative example 3
The preparation method of the layered oxide cathode material of the sodium ion battery comprises the following steps:
(1) 3mol of Ni source Ni (OH) 2 With 0.8mol of Na source 2 CO 3 Iron source Fe of 4mol 3 O 4 Mn as a manganese source in an amount of 3mol 2 O 3 Uniformly mixing, sintering in an air atmosphere, heating to a first sintering temperature of 500 ℃ at 2 ℃/min for 7 hours, heating to a second sintering temperature of 860 ℃ at 2 ℃/min for 12 hours, cooling with a furnace at 5 ℃/min after sintering, and crushing and screening after discharging the product to obtain the layered oxide anode material;
(2) Uniformly mixing the obtained layered oxide cathode material with 1100ppm of surface modifier NH4H2PO4, performing secondary sintering under the air atmosphere at 650 ℃ for 8 hours, cooling along with a furnace after sintering, and sieving after discharging the product from the furnace to obtain the modified layered oxide cathode material;
(3) Mixing the modified layered oxide positive electrode material with 500ppm of Al 2 O 3 And (3) carrying out three times of sintering under the air atmosphere after mixing, wherein the sintering temperature is 300 ℃, the sintering time is 6 hours, cooling along with a furnace after the sintering is finished, and sieving after the product is taken out of the furnace to obtain a final product, as shown in figure 7.
Electrochemical performance test: the positive electrode materials obtained in examples 1 to 4 and comparative examples 1 to 3 were used as active materials according to the following active materials: conductive agent (Super P): the mass ratio of the binder (PVDF) is 80:10:10, adding an appropriate amount of solvent NMP to adjust the solid content, stirring into slurry by a pulping machine, coating the slurry on an aluminum foil, and drying the pole piece in a drying oven at 100 ℃ for 4 hours after coating. A button cell was assembled in a glove box using a sodium sheet as the negative electrode, glass fiber as the separator, and 1m NaClO4 (solvent EC: dec=1:1 vol%) as the electrolyte. The battery was tested in a voltage range of 2.0-4.2V, and after activation for three weeks at 0.2C, the rate test and cycle performance test were performed.
The results of the performance tests of the products obtained in examples and comparative examples are shown in the following table:
Figure BDA0003966973390000131
as can be seen from the table, the positive electrode material prepared by the method has good pH value, first charge and discharge efficiency, discharge capacity and capacity retention rate, and is greatly improved compared with comparative examples 1-3.

Claims (10)

1. The layered oxide positive electrode material of the sodium ion battery is characterized by comprising the following chemical formula: na (Na) x Ni a Fe b Mn c Me d O 2 Wherein x, a, b, c and d are mole percentages of the corresponding elements respectively.
2. The layered oxide cathode material for sodium ion batteries according to claim 1, wherein x, a, b, c, d satisfy the following conditions simultaneously: x is more than or equal to 0.6 and less than or equal to 1.5, b is more than or equal to 0< a and less than or equal to 0.6,0 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.5, d is more than or equal to 0 and less than or equal to 0.4, and a+b+c+d=1.
3. The layered oxide cathode material of a sodium ion battery of claim 1, wherein Me is one of Ti, al, cu, mg, zr or Zn.
4. The preparation method of the sodium ion battery layered oxide cathode material is characterized by comprising the following steps:
step 1, uniformly mixing a nickel source, a sodium source, a manganese source, an iron source, a Me source, an auxiliary agent and a doping agent according to a proportion to obtain a mixture, performing primary sintering on the mixture in air or oxygen atmosphere, then heating up for reaction for a period of time, heating up again, continuously performing sintering, cooling to a tapping temperature after sintering is finished, and finally tapping, crushing and screening to obtain a sintered product;
step 2, mixing the primary combustion product obtained in the step 1 with a surface modifier, heating to a reaction temperature in an air or oxygen atmosphere after uniformly mixing, performing secondary sintering, cooling to a tapping temperature after the secondary sintering is finished, discharging from a furnace, crushing, and screening to obtain a secondary combustion product;
and step 3, uniformly mixing the product obtained in the step 2 with a coating agent, performing third sintering under air or oxygen atmosphere, and screening the third sintering product to obtain the O3 or P2 layered oxide anode material.
5. The method for preparing a layered oxide cathode material for sodium ion battery according to claim 4, wherein in the step 1, the nickel source is nickel hydroxide or nickel oxide after further presintering, the morphology is loose and porous, the nickel source is a secondary sphere or spheroid formed by stacking primary particles, wherein the primary particles are in a flake shape or a plate shape, the particle size of the secondary particles is 1-10 μm, and the specific surface is 5-150m 2 /g; the sodium source is one or more of anhydrous sodium carbonate, sodium sulfate, sodium hydroxide, sodium nitrate or sodium acetate; the manganese source is one or more of manganese dioxide, manganese sesquioxide or manganese tetraoxide; the iron source is one or more of ferric oxide or ferroferric oxide; the Me source is TiO 2 、Al 2 O 3 、CuO、ZrO 2 、MgO、ZnO 2 One of the following; the auxiliary agent is NaNO 3 The molar ratio m of the auxiliary agent to the sum of sodium sources is more than or equal to 0 and less than or equal to 1, the metal element in the doping agent is one or more of Mg, zr, W, ti, Y, cu, al, sr, mo, V, and the metal element in the doping agent accounts for 10-10000 ppm of the total mass of the anode material.
6. The method for preparing a layered oxide cathode material for sodium ion battery according to claim 4, wherein in the step 1, the mixing ratio of the nickel source, the sodium source, the manganese source, the iron source, the Me source, the auxiliary agent and the dopant satisfies the following conditions: na (Na) x Ni a Fe b Mn c Me d O 2 Wherein x, a, b, c and d are the mole percentages of the corresponding elements respectively, and the following conditions are satisfied at the same time: x is more than or equal to 0.6 and less than or equal to 1.5,0<a≤0.6，0≤b≤0.5，0<c is less than or equal to 0.5, d is less than or equal to 0.4, and a+b+c+d=1.
7. The method for preparing a layered oxide cathode material for a sodium ion battery according to claim 4, wherein the temperature of the first sintering in the step 1 is 200-500 ℃, the sintering time is 1-10 hours, the continuous sintering temperature after the temperature is raised again is 800-1100 ℃, and the sintering time is 4-24 hours; the temperature rising rate of the two times of temperature rising is 0.5-10 ℃/min, and the temperature reducing rate is 0.5-10 ℃/min.
8. The method for preparing a layered oxide cathode material for sodium-ion battery according to claim 4, wherein in the step 2, the surface modifier is (NH 4 ) 2 HPO 4 、NH4H2PO4、H 3 PO 4 、HPO 3 、H 3 BO 3 、NH 4 HB 4 O 7 ·3H 2 One or more of O, the temperature of the second sintering is 100-700 ℃, the second sintering time is 2-20 h, the cooling rate is 0.5-10 ℃/min, and the surface modifier accounts for 100-10000 ppm of the total mass of the anode material.
9. The method for preparing a layered oxide cathode material for sodium ion battery according to claim 4, wherein in the step 3, the third sintering temperature is 100-700 ℃ and the sintering time is 2-20 h.
10. The method for preparing a layered oxide cathode material for a sodium ion battery according to claim 4, wherein the coating agent in the step 3 is Al 2 O 3 、TiO 2 、H 3 PO 4 、Li 3 PO 4 、H 3 BO 3 、C、B 2 O 3 、ZrO 2 The metal element in the coating agent accounts for 10 to 10000ppm of the total mass of the anode material.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525813A (en) * 2023-06-27 2023-08-01 宁波容百新能源科技股份有限公司 Layered oxide, preparation method thereof and sodium ion battery positive electrode plate
CN117383627A (en) * 2023-12-13 2024-01-12 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of sodium-electricity layered anode material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525813A (en) * 2023-06-27 2023-08-01 宁波容百新能源科技股份有限公司 Layered oxide, preparation method thereof and sodium ion battery positive electrode plate
CN116525813B (en) * 2023-06-27 2023-10-27 宁波容百新能源科技股份有限公司 Layered oxide, preparation method thereof and sodium ion battery positive electrode plate
CN117383627A (en) * 2023-12-13 2024-01-12 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of sodium-electricity layered anode material
CN117383627B (en) * 2023-12-13 2024-03-12 泾河新城陕煤技术研究院新能源材料有限公司 Preparation method of sodium-electricity layered anode material

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