CN113991120A - Lithium iron phosphate anode material and preparation method thereof - Google Patents

Lithium iron phosphate anode material and preparation method thereof Download PDF

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CN113991120A
CN113991120A CN202111608569.2A CN202111608569A CN113991120A CN 113991120 A CN113991120 A CN 113991120A CN 202111608569 A CN202111608569 A CN 202111608569A CN 113991120 A CN113991120 A CN 113991120A
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lithium
iron phosphate
lithium iron
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positive electrode
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CN113991120B (en
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王长伟
罗标
唐红梨
蒋鹏
黄承焕
周友元
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Hunan Changyuan Lithium New Energy Co ltd
Hunan Changyuan Lico Co Ltd
Jinchi Energy Materials Co Ltd
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Hunan Changyuan Lico Co Ltd
Jinchi Energy Materials Co Ltd
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Abstract

The invention belongs to the technical field of battery materials, and particularly relates to a lithium iron phosphate positive electrode material and a preparation method thereof. The lithium iron phosphate anode material provided by the invention has a porous structure and has a chemical general formula of LixFeyNzPO4The discharge capacity at 1C is 146-151 mAh/g, the discharge capacity at 10C is 133-138 mAh/g, and the compaction density is 2.4-2.6 g/cm3. According to the invention, through the selection of raw materials and the optimization of a synthesis process, the lithium iron phosphate material is directly synthesized, and the doping of N and the coating of C are realized. In the aspect of raw material selection, the invention selects the lithium phosphate as the main lithium source,selecting lithium carbonate as a supplementary lithium source; selecting iron powder as a main iron source and selecting ferric nitrate as a supplementary iron source; lithium phosphate and phosphoric acid as phosphorus sources. The selection of the raw materials greatly reduces the production cost, and simultaneously, the iron nitrate is used as a supplementary iron source and provides a dopable N element.

Description

Lithium iron phosphate anode material and preparation method thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method of a lithium iron phosphate anode material.
Background
Owing to excellent structural stability and thermal stability and abundant raw material sources, the lithium iron phosphate material can provide a long service life and good safety for the lithium battery, so the lithium iron phosphate material becomes a preferred anode material of the lithium ion battery and has a wide development space in the application fields of new energy passenger cars, energy storage and the like which are sensitive to the cost of the lithium battery.
Due to the fact that well blowout occurs in the market demands of electric vehicles, light vehicles, energy storage and communication base stations and the like, the material productivity has a large gap. According to market data, the main flow price of the dynamic lithium iron phosphate material is about 5 ten thousand yuan/ton as soon as 26 days at 4 months and 2021, the price is increased by about 30% compared with the initial 1 month, and the price is increased by 44% compared with 3.6 ten thousand yuan/ton at 11 months and 2020. The direct push behind the escalation of material prices is the explosion in the price of battery grade lithium carbonate. Lithium carbonate is the indispensable raw materials of lithium ion battery cathode material and electrolyte at present, and the surge of its price has directly promoted the cost of lithium iron phosphate, has all caused great cost pressure for the upstream enterprise about the lithium iron phosphate trade. In addition, lithium iron phosphate has low conductivity and Li+DiffusionThe defects of weak coefficient and the like restrict the large-scale application of the high-temperature-coefficient-resistance material in low-temperature areas and winter in northern China.
Therefore, it is urgent to reduce the production cost of lithium iron phosphate and expand the application range of lithium iron phosphate in cold regions.
Disclosure of Invention
Aiming at the problems in the prior art, the invention mainly aims to provide a lithium iron phosphate material with excellent performance and a preparation method thereof.
Firstly, the invention provides a lithium iron phosphate anode material which has a porous structure and has a chemical general formula of LixFeyNzPO4C, wherein x is more than 1.0 and less than 1.23, y is more than 0.95 and less than 0.98, and z is more than 0.05 and less than 0.20; the ratio of x to y is 1.05-1.25.
The invention creatively discovers that when the lithium iron phosphate anode material is doped with N, carbon is used for coating, N atoms can be used as electron donors and electron carriers in a conductive network formed by N-C, the electron transition energy gap is reduced, and the C atoms can enhance the conductivity of electrons among material particles and on the surface. That is to say, the electronic conductivity of the lithium iron phosphate material can be more effectively improved by carbon coating and N doping, and the discharge capacity and the low-temperature performance of the material can be favorably improved.
Further, the 1C discharge capacity of the lithium iron phosphate anode material is 146-151 mAh/g, and the 10C discharge capacity is 133-138 mAh/g; the compacted density is 2.4-2.6 g/cm3。
In addition, the invention provides a preparation method of the lithium iron phosphate cathode material.
According to the invention, through the selection of raw materials and the optimization of a synthesis process, the lithium iron phosphate material is directly synthesized, and the doping of N and the coating of C are realized.
In the aspect of raw material selection, lithium phosphate is selected as a main lithium source, and lithium carbonate is selected as a supplementary lithium source; selecting iron powder as a main iron source and selecting ferric nitrate as a supplementary iron source; lithium phosphate and phosphoric acid as phosphorus sources. The selection of the raw materials greatly reduces the production cost, and simultaneously, the iron nitrate is used as a supplementary iron source and provides a dopable N element.
The preparation method of the lithium iron phosphate anode material provided by the invention comprises the following steps:
step S1, adding phosphoric acid solution into a reaction kettle, then simultaneously adding iron powder, an additive and hydrogen peroxide for reaction, and controlling the pH value of a reaction system to be 2.0-4.0 in the reaction process; when the reaction system is light red, continuing to react for 1-2h on the basis, and stopping the reaction; obtaining a suspension A after the reaction is finished; the additive is P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) and polyethylene glycol;
step S2, mixing lithium phosphate or a mixture of lithium phosphate and lithium carbonate, ferric nitrate and a carbon source, and grinding the mixture in a grinder to obtain slurry B with a certain particle size distribution;
step S3, adding the slurry B into the slurry A for reaction to obtain slurry C;
and step S4, spray drying the slurry C, and then sintering, crushing and grading to prepare the lithium iron phosphate material.
Further, in the above preparation method, the concentration of the phosphoric acid solution is 40wt% to 85wt%, preferably 40wt% to 60 wt%.
Further, in the preparation method, the molar ratio of the added amounts of phosphoric acid, iron powder, an additive P123, an additive polyethylene glycol and hydrogen peroxide is 0.5-0.9: 1: 0.01-0.1: 0.001-0.005: 0.1-0.2, preferably 0.68-0.77: 1: 0.03-0.05: 0.002-0.003: 0.15-0.18.
Further, in the above preparation method, in step S2, the molar ratio of lithium phosphate to ferric nitrate is 2.3 to 4.6: 1.
in the present invention, lithium carbonate may be selectively supplemented. If the lithium content in the lithium phosphate meets the lithium iron ratio, additional lithium carbonate does not need to be supplemented; if not, lithium carbonate is supplemented.
Further, the carbon source is selected from more than one of glucose, sucrose, polyethylene glycol, graphite, carbon nanotubes and graphene, and accounts for 8-20% of the total iron source by mass. The residual carbon content of the lithium iron phosphate anode material is controlled to be 1.45-2.0%, preferably 1.65-1.85%.
Further, in the above preparation method, in step S2, the particle size of slurry B is D50=0.05-0.5 μm, preferably 0.1-0.3 μm.
Further, in the above preparation method, in step S3, the reaction temperature is 30 to 90 ℃, preferably 50 to 68 ℃; the stirring speed is 300-1000rpm, preferably 400-550 rpm.
Further, in the above preparation method, in step S4, the spray drying conditions are as follows: the air inlet temperature is 230-350 ℃, and preferably 260-290 ℃; the air outlet temperature is 80-120 ℃, and the preferable temperature is 90-110 ℃.
Further, in the above preparation method, in step S4, the sintering temperature is 600-; the constant temperature time of the sintering is 7-15h, preferably 8-10 h.
Further, the sintering atmosphere is an inert atmosphere or a nitrogen atmosphere.
The invention adds the additive in step S1 to obtain the amorphous ferric phosphate with nanometer level and porous inside.
According to the invention, ferric nitrate is selected as a supplementary iron source and is also a source doped with N, and the slurry C is sintered after spray drying to obtain a uniform N-doped material; ferric nitrate is used as a supplementary iron source and a source for N doping, and the adding amount of the ferric nitrate can be controlled according to the situation.
The invention selects additive and carbon source, the slurry C is sintered after spray drying, and a C coating layer is formed on the surface of the material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the raw materials with low cost are selected, so that the preparation cost of the lithium iron phosphate is greatly reduced;
(2) no wastewater, waste gas and the like are discharged in the process of preparing the lithium iron phosphate cathode material, and the method is safe and environment-friendly;
(3) in the preparation process, the N element in the raw material is doped into the anode material, so that the performance of the material is improved; moreover, the invention can realize the controllable doping amount of N. Meanwhile, the addition of C can enhance the conductivity of electrons among material particles and on the surface of the material particles in a conductive network formed by N-C because N atoms can be used as electron donors and electron carriers and reduce electron transition energy gaps. The combination of C and N effectively improves the electronic conductivity of the lithium iron phosphate material, and is beneficial to improving the discharge capacity and low-temperature performance of the material.
Drawings
Fig. 1 is an SEM image of the lithium iron phosphate material prepared in example 1.
Fig. 2 is a cross-sectional SEM image of the lithium iron phosphate material prepared in example 1.
Fig. 3 is an XPS chart of the lithium iron phosphate material prepared in example 1.
Detailed Description
In order to facilitate understanding of the objects and technical solutions of the present invention, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The lithium iron phosphate cathode material is prepared by the following method:
(1) fully dispersing 0.75mol of phosphoric acid and pure water in a reaction kettle, heating to 60 ℃, stirring, slowly adding 1mol of iron powder into a phosphoric acid solution (the molar ratio of the phosphoric acid to the iron powder is 0.75), simultaneously adding 0.05mol of additives P123, 0.002mol of polyethylene glycol and 0.1mol of hydrogen peroxide for oxidation treatment, and accurately controlling the pH value in the reaction process to be 3.0. After the reaction system was observed to appear pale red, the reaction was continued for 2 hours, and then stopped to obtain slurry A.
(2) 0.425mol of lithium phosphate and 0.14mol of iron nitrate (3.035: 1 molar ratio) were added to the mill, while sucrose and carbon nanotubes were used as carbon sources. The adding amount of the carbon source is 12 percent of the total mass of the materials. Pure water is used as a solvent, the solid content is controlled at 60%, and high-speed grinding is started to obtain slurry B. The particle size of slurry B was D50=0.1 μm.
(3) Adding the slurry B into the slurry A, controlling the reaction temperature to be 50 ℃, controlling the rotating speed of a stirring motor to be 500rpm, and fully mixing for 1h to obtain slurry C.
(4) And drying the slurry C by a spray dryer, wherein the air inlet temperature is 280 ℃ and the air outlet temperature is 105 ℃. Drying to obtain the material to be sintered.
(5) The material to be sintered is heat treated for 8 hours at a temperature of 720 ℃. The heat treatment was performed in a nitrogen atmosphere. Then crushing and grading to prepare lithium iron phosphate Li1.08Fe0.97N0.12PO4And C, material.
Fig. 1 and fig. 2 are an SEM image and a cross-sectional SEM image of the lithium iron phosphate positive electrode material prepared in this example, respectively. As can be seen from the cross-sectional SEM image, the lithium iron phosphate positive electrode material has a porous structure.
Fig. 3 is an XPS chart of the lithium iron phosphate positive electrode material prepared in example 1. It can be seen that the N atoms and the C atoms in the lithium iron phosphate positive electrode material form three different types of C-N structures, namely a pyridine C-N structure, a pyrrole C-N structure and a graphite C-N structure.
Example 2
In this embodiment, a lithium iron phosphate positive electrode material is prepared by the following method:
(1) fully dispersing 0.8mol of phosphoric acid and pure water in a reaction kettle, heating to 60 ℃, stirring, slowly adding 1mol of iron powder into a phosphoric acid solution (the molar ratio of the phosphoric acid to the iron powder is 0.8), simultaneously adding 0.01mol of additive P123, 0.001mol of additive polyethylene glycol and 0.15mol of hydrogen peroxide for oxidation treatment, and accurately controlling the pH value in the reaction process to be 2. After the reaction system was observed to appear pale red, the reaction was continued for 2 hours, and then stopped to obtain slurry A.
(2) 0.4248 mol of lithium phosphate, 0.18 mol of iron nitrate and 0.0054 mol of lithium carbonate (molar ratio of 2.36: 1: 0.03) were fed into the mill while sucrose and carbon nanotubes were used as carbon sources. The carbon source accounts for 12 percent of the total mass of the material. Pure water was used as a solvent, the solid content was controlled at 60%, and high-speed grinding was started to obtain slurry B having a particle size of D50=0.1 μm.
(3) Adding the slurry B into the slurry A for reaction, controlling the reaction temperature to be 40 ℃, controlling the rotating speed of a stirring motor to be 400rpm, and fully mixing for 1h to obtain slurry C, wherein the Cde particle size D50=1.0 μm.
(4) And drying the slurry C by a spray dryer, wherein the air inlet temperature is 280 ℃, the air outlet temperature is 105 ℃, and thus obtaining the material to be sintered.
(5) The material to be sintered is heat treated for 8 hours at the temperature of 720 ℃. The heat treatment was performed in a nitrogen atmosphere. Crushing and grading to prepare lithium iron phosphate Li1.04Fe0.96N0.14PO4And C, material.
Example 3
The lithium iron phosphate cathode material is prepared by the following method:
(1) fully dispersing 0.75mol of phosphoric acid and pure water in a reaction kettle, stirring, slowly adding 1mol of iron powder into a phosphoric acid solution (the molar ratio of the phosphoric acid to the iron powder is 0.75), simultaneously adding 0.1mol of additive P123, 0.005mol of additive polyethylene glycol and 0.2mol of hydrogen peroxide for oxidation treatment, and accurately controlling the pH value in the reaction process to be 2. After the reaction system was observed to appear pale red, the reaction was continued for 1 hour, and then stopped to obtain slurry A.
(2) 0.39 mol of lithium phosphate and 0.1mol of iron nitrate (molar ratio 3.9: 1) were added to the mill while sucrose and carbon nanotubes were used as carbon sources. The adding amount of the carbon source is 10.5 percent of the total mass of the materials, pure water is used as a solvent, the solid content is controlled at 60 percent, and high-speed grinding is started. The particle size of slurry B after grinding was D50=0.1 μm.
(3) Adding the slurry B into the slurry A, controlling the reaction temperature to be 45 ℃, controlling the rotating speed of a stirring motor to be 500rpm, and fully mixing for 1h to obtain slurry C. The particle size D50=1.0 μm for slurry C.
(4) And drying the slurry C by a spray dryer, wherein the air inlet temperature is 280 ℃, the air outlet temperature is 105 ℃, and thus the material to be sintered is obtained.
(5) The material to be sintered is heat treated for 8 hours at the temperature of 720 ℃. The heat treatment was performed in a nitrogen atmosphere. Then crushing and grading to prepare lithium iron phosphate Li1.02Fe0.965N0.088PO4And C, material.
The lithium iron phosphate materials prepared in examples 1 to 3 and other materials were assembled into button cells by a conventional method in the art, and electrochemical properties of the button cells were tested, and the results are shown in table 1.
TABLE 1 electrochemical performance of button cell
Figure 324169DEST_PATH_IMAGE001
As can be seen from table 1, the lithium iron phosphate positive electrode material prepared by the technical scheme provided by the invention has good discharge capacity and low-temperature performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The lithium iron phosphate anode material is characterized by having a porous structure and a chemical general formula of LixFeyNzPO4C, wherein x is more than 1.0 and less than 1.23, y is more than 0.95 and less than 0.98, and z is more than 0.05 and less than 0.20; the ratio of x to y is 1.05-1.25.
2. The lithium iron phosphate positive electrode material as claimed in claim 1, wherein the lithium iron phosphate positive electrode material has 1C discharge capacity of 146-; the compacted density is 2.4-2.6 g/cm3。
3. A preparation method of a lithium iron phosphate positive electrode material is characterized by comprising the following steps:
step S1, adding phosphoric acid solution into a reaction kettle, then simultaneously adding iron powder, an additive and hydrogen peroxide for reaction, and controlling the pH value of a reaction system to be 2.0-4.0 in the reaction process; when the reaction system is light red, continuing to react for 1-2h on the basis, and stopping the reaction; obtaining a suspension A after the reaction is finished; the additives are P123 and polyethylene glycol;
step S2, mixing lithium phosphate or a mixture of lithium phosphate and lithium carbonate, ferric nitrate and a carbon source, and grinding in a grinder to obtain slurry B;
step S3, adding the slurry B into the suspension A for reaction to obtain slurry C;
and step S4, spray drying the slurry C, and then sintering, crushing and grading to prepare the lithium iron phosphate material.
4. The method for preparing a lithium iron phosphate positive electrode material according to claim 3, wherein the concentration of the phosphoric acid solution is 40wt% to 85 wt%.
5. The method for preparing a lithium iron phosphate positive electrode material according to claim 3, wherein in step S1, the molar ratio of the added amounts of phosphoric acid, iron powder, additive P123, additive polyethylene glycol and hydrogen peroxide is 0.5-0.9: 1: 0.01-0.1: 0.001-0.005: 0.1-0.2.
6. The method for preparing a lithium iron phosphate positive electrode material according to claim 3, wherein in step S2, the molar ratio of lithium phosphate to ferric nitrate is 2.3-4.6: slurry B has a particle size of D50=0.05-0.5 μm.
7. The method for preparing the lithium iron phosphate cathode material according to claim 3, wherein the carbon source is selected from one or more of glucose, sucrose, polyethylene glycol, graphite, carbon nanotubes and graphene, and the carbon source accounts for 8-20% of the total iron source by mass.
8. The method for preparing a lithium iron phosphate positive electrode material according to claim 3, wherein in step S3, the reaction temperature is 30-90 ℃; the stirring speed was 300 and 1000 rpm.
9. The method for preparing a lithium iron phosphate positive electrode material according to claim 3, wherein in step S4, the spray drying conditions are as follows: the air inlet temperature is 230-350 ℃, and the air outlet temperature is 80-120 ℃.
10. The method for preparing the lithium iron phosphate cathode material as claimed in claim 3, wherein in step S4, the sintering temperature is 600-850 ℃, the constant temperature time of the sintering is 7-15h, and the sintering atmosphere is an inert atmosphere or a nitrogen atmosphere.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN116639674A (en) * 2023-05-31 2023-08-25 河南工程学院 Preparation method of low-cost high-capacity lithium iron phosphate positive electrode material

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