CN114864929A - Preparation method of modified micro-nano structure sodium ion battery positive electrode material - Google Patents

Preparation method of modified micro-nano structure sodium ion battery positive electrode material Download PDF

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CN114864929A
CN114864929A CN202210643603.8A CN202210643603A CN114864929A CN 114864929 A CN114864929 A CN 114864929A CN 202210643603 A CN202210643603 A CN 202210643603A CN 114864929 A CN114864929 A CN 114864929A
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sodium
nano
ion battery
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苏方哲
方明
曹栋强
龚丽锋
郝培栋
曹天福
许益伟
邓明
李晓升
丁何磊
柴冠鹏
张旭
王博
郑红
张伟伟
唐嘉梾
李宜薄
张公平
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Lepu Sodium Power Shanghai Technology Co ltd
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Zhejiang Gepai Cobalt Industry New Material Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10Energy storage using batteries

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Abstract

The invention provides a preparation method of a modified micro-nano structure sodium ion battery anode material, which is characterized in that two-fluid spray drying is adopted to obtain smaller primary particles, the stability of product batches is easy to control, 30-100nm primary particles with more lattice defects are formed at the initial stage of sintering, then sintering and heat preservation are carried out to obtain 50-200nm primary particles with better crystal forms, and the average particle size of secondary particles is 2-5 mu m. The coating layer is uniformly distributed on the surface of the positive electrode material and tightly combined, so that sodium ions can be transmitted conveniently, and the obtained aluminum-coated modified micro-nano structure sodium ion battery positive electrode material has higher conductivity, larger specific capacity, good rate capability and cycle performance. The method does not need long-time ball milling or high-pressure resistant equipment, and has the advantages of simple process, environmental friendliness, low cost and easy industrialization.

Description

Preparation method of modified micro-nano structure sodium ion battery positive electrode material
Technical Field
The invention belongs to the field of sodium ion battery anode materials, and particularly relates to a preparation method of a modified micro-nano structure sodium ion battery anode material.
Background
Lithium ion batteries are also the most widely studied energy storage batteries, but because of the limited storage capacity of metallic lithium, the price is rising year by year and the requirement of large-scale energy storage technology, sodium ion batteries become the research and development hot spots of battery technology in recent years due to the characteristics of abundant raw materials, low cost, high safety and the like. Since the radius of sodium ions is larger than that of lithium ions, the current research is critical to develop an electrode material capable of stably and rapidly extracting and intercalating sodium ions. Among many sodium ion battery positive electrode materials, polyanion-type compounds are considered as the most promising electrode materials due to their excellent structural stability, safety and suitable voltage platform. The sodium iron phosphate material has the advantages of abundant raw materials, low price, three-dimensional ion diffusion channels, good safety performance and wide attention. But the problems of poor electronic conductivity, slow ion diffusion rate and the like still influence the further application of the material.
Researchers have made a lot of efforts to improve the electrochemical properties and structural stability of sodium iron phosphate, for example, CN114368736A discloses a preparation method of a sodium iron phosphate positive electrode material, which comprises the steps of preserving heat of lithium iron phosphate at a certain temperature, quenching, mixing with sodium salt, ball milling, molten salt ion exchange sintering, and cooling to obtain a bulk material; and cleaning, solid-liquid separation and drying the obtained bulk material to obtain the required material. The discharge capacity of a battery assembled by electrodes prepared from the olivine type sodium iron phosphate cathode material at 0.1C multiplying power is 148mAh g within the voltage range of 2.1-3.6V -1 The discharge capacity at 2C rate was 110mAh g -1 The capacity retention after 300 cycles at 0.5C was 95.6%. The iron phosphate sodium is prepared by adopting lithium iron phosphate and sodium salt as raw materials and performing molten salt ion exchange, and the discovery shows that the required amount of the sodium salt is large, the consumed time is long, complete replacement is difficult to realize, and the obtained product has impure phases. CN114249311A discloses a preparation method of porous sodium-ion battery anode material sodium iron phosphate, which comprises the steps of preparing a mixture of silver carbonate and ferrous carbonate by a coprecipitation method to obtain silver-iron atom-level doped eutectic, and then co-sintering the eutectic with sodium dihydrogen phosphate and sodium iodide to obtain sodium iron phosphate, wherein when the sodium dihydrogen phosphate and the ferrous carbonate are subjected to solid-phase mixed sintering, silver carbonate is decomposed into carbon dioxide and silver oxide, the silver oxide is decomposed into silver simple substance and oxygen, and the silver single substance is decomposed into silver simple substance and oxygenThe material has appropriate conductivity, the electrochemical performance of the sodium iron phosphate is improved to a certain extent, but the operation process is complex and high in cost, and the conductivity, specific capacity and rate capability of the sodium iron phosphate still have a space for further improving.
Disclosure of Invention
The invention aims to provide a preparation method of a modified micro-nano structure sodium ion battery anode material, which is simple in process and low in cost, and the obtained micro-nano structure sodium iron phosphate anode material has high conductivity, high specific capacity and good rate performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a modified micro-nano structure sodium ion battery anode material comprises the following steps:
(1) adding a sodium source, a carbon source, iron phosphate, a dispersing agent and a solvent into a ball milling tank, and uniformly ball-milling;
(2) carrying out two-fluid spray drying on the slurry obtained in the step (1), controlling the feeding frequency to be 9-11Hz and the air inlet speed to be 3.5-4.5m 3 /h;
(3) Uniformly mixing the material obtained in the step (2) and the nano oxide in a mixer;
(4) sintering the mixed material obtained in the step (3) in an inert gas atmosphere, and screening to obtain a positive electrode material; the sintering is carried out at the temperature rise rate of 3 ℃/min and the temperature preservation time is 8-10 h; primary particles with the particle size of 30-100nm are formed in the initial sintering stage, primary particles with the particle size of 50-200nm and the crystal form is better are obtained through sintering and heat preservation, the average particle size of the secondary particles is 2-5 mu m, and the largest secondary particle size is less than 20 mu m.
In the step (1), the sodium source is any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose or sodium lactate.
In the step (1), the carbon source is any one or a combination of at least two of glucose, sucrose, fructose, starch, citric acid, ascorbic acid, tartaric acid or oxalic acid.
In the step (1), the dispersant is one or more than two of polyethylene glycol, polyvinyl alcohol, tween-80, tween-60, span-80 or triton x-100.
In the step (1), the solvent is one or more than two of pure water, ethanol, propanol or acetone.
The molar ratio of the P/Fe element to the Na element in the step (1) is 1: 1-1.05.
The content of the carbon source in the step (1) is 1-10% of the mass of the anode material; the content of the dispersing agent is 1-20% of the mass of the positive electrode material; the content of the solvent is 20-80% of the mass of the positive electrode material.
In the step (2), the feeding frequency is controlled to be 10Hz, and the air inlet speed is controlled to be 4.0m 3 /h。
In the step (3), the nano oxide is at least one of nano vanadium pentoxide, nano titanium dioxide, nano zirconium oxide, nano cerium oxide, nano zinc oxide, nano aluminum oxide, nano manganese dioxide or nano tungsten oxide, and the coating amount is 0.1-0.8%.
In the step (4), the inert gas is one or more than two of nitrogen, helium, neon, argon, krypton, xenon or radon.
And (3) making the buckle electric: respectively assembling the obtained modified sodium iron phosphate composite materials into button cells, mixing the obtained positive electrode material of the sodium ion battery with conductive carbon black and a binder PVDF according to the mass ratio of 7:2:1, adding an N-methyl pyrrolidone solution, and uniformly mixing to prepare the positive electrode slurry of the battery. Coating the slurry on an aluminum foil, vacuum drying and rolling to prepare a positive pole piece, taking a sodium metal piece as a negative pole, and taking 1mol/L NaPF 6 The button cell was assembled in a glove box filled with argon gas using Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio 1:1) solution as electrolyte and glass fiber as separator.
Compared with the prior art, the preparation method for preparing the aluminum-coated micro-nano structure sodium ion battery anode material has the following advantages:
(1) the conventional centrifugal spray drying and static drying granulation has larger granularity, the product performance consistency is difficult to control through the working procedures of crushing, screening and the like after the conventional centrifugal spray drying and static drying granulation are carried out, the material capacity is low, the multiplying power and the cycle performance are poor, and if small primary particles are obtained, the primary particles need to be prepared by adopting a long-time ball milling or liquid phase method, the cost is higher; the preparation method of the invention uses two-fluid spray drying to obtain smaller primary particles by controlling the feeding frequency and the air inlet rate, can be directly applied, has less working procedures and easier control of the stability of product batches, forms 30-100nm primary particles with more lattice defects at the initial stage of sintering, and then obtains 50-200nm primary particles with better crystal forms through sintering and heat preservation, wherein the average particle size of the secondary particles is 2-5 mu m, and the maximum secondary particle size is less than 20 mu m, so that the prepared anode material has the performances of high conductivity, high specific capacity and the like.
(2) The coating layer is uniformly distributed on the surface of the positive electrode material and tightly combined, so that sodium ions can be transmitted conveniently, the circulating stability of the positive electrode material of the sodium ion battery is improved, good stability can be realized in electrolyte and air, and the obtained modified micro-nano ferric sodium phosphate positive electrode material has high conductivity, large specific capacity, good rate capability and good circulating performance.
The method does not need long-time ball milling or high-pressure resistant equipment, and has the advantages of simple process, environmental friendliness, low cost and easy industrialization.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1;
FIG. 3 is an XRD diffraction spectrum of the modified micro-nano structure sodium ion battery anode material prepared in example 1;
FIG. 4 is a graph comparing the 1C cycle performance of example 1 and comparative example 2;
fig. 5 is a graph comparing the rate performance of example 1 and comparative example 1.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. For a further understanding of the invention, reference is made to the following description and specific preferred examples, which are not intended to limit the scope of the invention as claimed.
Example 1
The embodiment provides a modified micro-nano structure sodium ion battery anode material, and a preparation method of the anode material comprises the following steps:
weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-200nm, and the average particle size of the secondary particles is 2.0 mu m.
Wherein, fig. 1 is a Scanning Electron Microscope (SEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1; FIG. 2 is a Transmission Electron Microscope (TEM) image of the modified micro-nano structure sodium ion battery cathode material prepared in example 1; FIG. 3 is an XRD diffraction spectrum of the modified micro-nano structure sodium ion battery anode material prepared in example 1;
example 2
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 8h, naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material,the material has primary particle of 50-100nm and secondary particle of average size of 1.8 micron.
Example 3
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 15Hz and the air inlet rate of 5.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-200nm, and the average particle size of the secondary particles is 2.3 mu m.
Example 4
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10% of Tween-60, 6% of citric acid and 50% of pure water in the total weight of the positive electrode material respectively, ball-milling for 8 hours in a ball mill, taking out slurry, and feeding at the frequency of 10Hz and the air inlet rate of 3.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min under the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the material has the primary particle size of 100 plus materials of 200nm, and the average particle size of the secondary particles of 4.6 mu m.
Example 5
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and feeding at the frequency of 2Hz and the air inlet rate of 3.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-300nm, and the average particle size of the secondary particles is 3.8 mu m.
Example 6
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and feeding at the frequency of 5Hz and the air inlet rate of 3.6m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-300nm, and the average particle size of the secondary particles is 4.1 mu m.
Example 7
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 850 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, calcining for 8h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-250nm, and the average particle size of the secondary particles is 3.0 mu m.
Example 8
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 900 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 100-250nm, and the average particle size of the secondary particles is 3.2 mu m.
Example 9
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 280 ℃ at 3 ℃/min in a nitrogen atmosphere, calcining for 15h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-150nm, and the average particle size of the secondary particles is 1.9 mu m.
Example 10
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10 percent of triton x-100, 6 percent of citric acid and 50 percent of pure water of the total weight of the anode material into a ball mill for ball milling for 8 hours, taking out slurry, and performing ball milling at the feeding frequency of 10Hz and the air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 250 ℃ at 6 ℃/min in a nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-100nm, and the average particle size of the secondary particles is 1.7 mu m.
Comparative example 1
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, adding 10% triton x-100, 6% citric acid and 50% pure water of the total weight of the positive electrode material respectively, ball-milling for 8 hours in a ball mill, taking out slurry, and carrying out centrifugal drying. Mixing the obtained dried material with nano-alumina according to the mass ratio of 1:0.006, heating to 600 ℃ at 3 ℃/min in the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate anode material, wherein the primary particles of the material are 300-700nm, and the average particle size of the secondary particles is 18.7 mu m.
Comparative example 2
Weighing iron phosphate and sodium carbonate according to the molar ratio of P/Fe element to Na element of 1:1.03, and respectively adding 10 percent of the total weight of the positive electrode materialBall milling Triton x-100, 6% citric acid and 50% pure water in a ball mill for 8h, taking out slurry, and feeding at a feeding frequency of 10Hz and an air inlet rate of 4.0m 3 Two-fluid spray drying was carried out. And heating the obtained dried material to 600 ℃ at a speed of 3 ℃/min under the nitrogen atmosphere, calcining for 10h, and naturally cooling to room temperature to obtain the modified micro-nano structure sodium iron phosphate cathode material, wherein the primary particles of the material are 50-200nm, and the average particle size of the secondary particles is 2.0 mu m.
And (3) performance testing:
1) testing the first discharge capacity and the coulombic efficiency: the button cells prepared from the positive electrode materials in examples 1-6 and comparative examples 1-2 were tested by a blue tester, the voltage range was 2.0-4.5V, the charge and discharge were activated for one turn at 0.1C, the first charge and discharge specific capacity and the first coulombic efficiency were obtained, and the test results are shown in table 1.
2)1C cycle performance: the button cell prepared by the anode materials in the embodiments 1-6 and the comparative examples 1-2 is tested by using a blue tester, the voltage range is 2.0-4.5V, the button cell is charged and discharged for one circle at 0.1C, then the button cell is charged at constant current and constant voltage at 0.5C, the cut-off current is 0.05C, constant current discharge is carried out at 1C, and 200 circles are circulated, so that relevant data of parameters such as the 100 th circle discharge capacity and the 100 th circle capacity retention ratio, the 200 th circle discharge capacity and the 200 th circle capacity retention ratio are respectively obtained. The test results are shown in table 2 and fig. 4.
3) Rate capability: the button cells prepared by the positive electrode materials in the examples 1-6 and the comparative examples 1-2 were tested by a blue tester, the voltage range was 2.0-4.5V, constant current and constant voltage charging was performed at a current of 0.5C, and the charge cutoff current was 0.05C; constant current discharge was performed at 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, and 0.1C currents, respectively, with a discharge cutoff voltage of 2V.
The test results are shown in table 3 and fig. 5.
Evaluation of
TABLE 1
Figure BDA0003685056690000091
Figure BDA0003685056690000101
As can be seen from table 1, the conventional centrifugal spray drying employed in comparative example 1 has a low material capacity and a low first discharge efficiency. In the examples 1 to 6, smaller primary particles are obtained by two-fluid spray drying, the initial charge specific capacity is increased from 89.5mAh/g to 151.3mAh/g after sintering, the discharge specific capacity is increased from 75.2mAh/g to 149.7mAh/g, and the initial charge-discharge efficiency is 98.94%, while the initial charge specific capacity, the discharge specific capacity and the initial charge-discharge efficiency are reduced to different degrees after sintering at different temperatures in the examples 7 to 10.
TABLE 2
Figure BDA0003685056690000102
Table 2 is data on cycle performance of examples 1 to 6 and comparative examples 1 to 2, and it can be seen from the table that the capacity retention of the sodium ion positive electrode material prepared in example 1 is improved from 71.54% to 98.10% after 100 cycles, and the capacity retention is improved from 67.4% to 95.30% after 200 cycles.
TABLE 3
Figure BDA0003685056690000111
Table 3 is data on rate performance of examples 1 to 6 and comparative examples 1 to 2, and it can be seen from the table that the capacity retention rate of the positive electrode material for sodium ion battery prepared in example 1 at 5C rate is increased from 70.84% to 89.94%, and the 0.1C capacity retention rate after testing over-rate is still 97.64%.
The comparison between the examples and the comparative examples shows that the positive electrode material prepared by two-fluid spray drying has the performances of high conductivity, high specific capacity and the like. The coating layer is uniformly distributed on the surface of the anode material and tightly combined, so that sodium ions can be transmitted conveniently, and the obtained modified micro-nano iron sodium phosphate anode material has high conductivity, large specific capacity, good rate performance and good cycle performance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A preparation method of a modified micro-nano structure sodium ion battery anode material is characterized in that,
the preparation method comprises the following steps:
(1) adding a sodium source, a carbon source, iron phosphate, a dispersing agent and a solvent into a ball milling tank, and uniformly ball-milling;
(2) carrying out two-fluid spray drying on the slurry obtained in the step (1), controlling the feeding frequency to be 9-11Hz and the air inlet speed to be 3.5-4.5m 3 /h;
(3) Uniformly mixing the material obtained in the step (2) and the nano oxide in a mixer;
(4) sintering the mixed material obtained in the step (3) in an inert gas atmosphere, and screening to obtain a positive electrode material; the sintering is carried out at the temperature rise rate of 3 ℃/min and the temperature preservation time is 8-10 h; primary particles with the particle size of 30-100nm are formed in the initial sintering stage, primary particles with the particle size of 50-200nm and the crystal form is better are obtained through sintering and heat preservation, the average particle size of the secondary particles is 2-5 mu m, and the largest secondary particle size is less than 20 mu m.
2. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the sodium source is any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium oxalate, sodium nitrite, disodium hydrogen phosphate, sodium bicarbonate, sodium citrate, anhydrous sodium sulfate, sodium stearate, sodium oleate, sodium tartrate, sodium alginate, sodium carboxymethylcellulose or sodium lactate.
3. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the carbon source is any one or a combination of at least two of glucose, sucrose, fructose, starch, citric acid, ascorbic acid, tartaric acid or oxalic acid.
4. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the dispersant is one or more than two of polyethylene glycol, polyvinyl alcohol, tween-80, tween-60, span-80 or triton x-100.
5. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (1), the solvent is one or more than two of pure water, ethanol, propanol or acetone.
6. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: the molar ratio of the P/Fe element to the Na element in the step (1) is 1: 1-1.05.
7. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: the content of the carbon source in the step (1) is 1-10% of the mass of the anode material; the content of the dispersing agent is 1-20% of the mass of the positive electrode material; the content of the solvent is 20-80% of the mass of the positive electrode material.
8. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (2), the feeding frequency is controlled to be 10Hz, and the air inlet speed is controlled to be 4.0m 3 /h。
9. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (3), the nano oxide is at least one of nano vanadium pentoxide, nano titanium dioxide, nano zirconium oxide, nano cerium oxide, nano zinc oxide, nano aluminum oxide, nano manganese dioxide or nano tungsten oxide, and the coating amount is 0.1-0.8%.
10. The preparation method of the modified micro-nano structure sodium ion battery anode material according to claim 1, characterized by comprising the following steps: in the step (4), the inert gas is one or more than two of nitrogen, helium, neon, argon, krypton, xenon or radon.
CN202210643603.8A 2022-06-09 2022-06-09 Preparation method of modified micro-nano structure sodium ion battery positive electrode material Pending CN114864929A (en)

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JP2008004317A (en) * 2006-06-21 2008-01-10 Gs Yuasa Corporation:Kk Manufacturing method of iron lithium phosphate for battery and battery using it
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