CN113072051B - Post-treatment method of phosphate system anode material - Google Patents
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Abstract
The invention belongs to the field of lithium ion batteries, and relates to a post-treatment method of a phosphate system anode material, which comprises the following steps: placing a certain amount of phosphate system anode material into a sintering furnace, oxidizing and calcining for a certain temperature and a certain time; mixing the calcined anode material with a carbon source and a lithium supplementing agent with a certain mass, adding deionized water with a certain mass, placing the mixture in a grinding tank, and grinding for a certain time to prepare slurry; and (3) drying the obtained slurry in an oven, taking out, moving to a sintering furnace for sintering, cooling for a certain time under a protective atmosphere after sintering, taking out, air-cooling for a certain time, and grinding and sieving by 20-300 meshes to obtain the phosphate anode material. The synthesized lithium iron phosphate anode material can be oxidized and calcined to burn out a loose carbon layer so as to bridge surface holes; and adding a carbon source and a lithium supplementing agent, and grinding and calcining again to form the positive electrode material with high compaction and low specific surface area.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and belongs to one of anode material modification methods, in particular to a post-treatment method of a phosphate system anode material.
Background
In recent years, phosphate system materials have been widely studied as positive electrode materials of lithium ion batteries because of their low price, high safety performance, large specific capacity and the like. The lithium iron phosphate has the advantages of good cycle performance, wide material sources and the like, and is considered as the preferred positive electrode material of the electric automobile in the future. However, the compacted density of the lithium iron phosphate positive electrode material is far lower than that of the ternary material, which limits the application of the lithium iron phosphate positive electrode material in wider fields.
It is found that in addition to the inherent properties of the active material of the electrode of the lithium ion battery, the microstructure of the electrode has a very important influence on the energy density and electrochemical performance of the battery, and the improvement of the compaction density can effectively improve the volume energy density of the material. Generally, the greater the pole piece compaction density, the higher the capacity of the battery, within the allowable compaction range of the material, so the compaction density is also considered as one of the reference indicators for measuring the energy density of the material. The compaction density of the material is mainly related to the factors such as the particle size, the particle size ratio and the like of the material. Generally, the packing of equal diameter spheres increases the gap between spheres, and if a small volume sphere is not properly filled in the gap, the compaction density of the material is reduced. Therefore, in industrial production, the improvement of the compaction density of the material is mainly to reasonably distribute spheres with different particle diameters, so that the compaction density of the material can be simply and efficiently improved, and the energy density of the battery is improved. In addition, the compacted density of the material can be suitably increased by either increasing the primary particle diameter of the positive electrode material or reducing the carbon coating content. However, both the increase in primary particle size and the decrease in carbon coating amount reduce the lithium ion conductivity of the material, which is contrary to the research direction of lithium batteries today, so that the two methods are applied less frequently in industrial production.
Chen Yanyu et al (Guangdong chemical industry, 2018, 45 (16): 59-60.) propose a preparation method of high-compaction-density nano lithium iron phosphate, which adopts a secondary sintering process on the basis of graphene doping to strictly control various parameters such as sintering temperature, heating rate, carbon coating initial temperature and the like, so that the raw materials have good reactivity and uniform physicochemical properties, and the crystal phase arrangement generated by nano lithium iron phosphate is more compact and ordered in level. The prepared nano lithium iron phosphate has controllable material morphology and compaction density of 2.5g/cm 3 The compaction density is improved by 0.4g/cm compared with the conventional nano lithium iron phosphate 3 。
The secondary sintering process obviously improves the compaction density of the material, but carbon and lithium lost in the sintering process are not compensated, so that the ion diffusion rate of the positive electrode material is slowed down, and the rate capability of the battery is affected.
Patent CN 108706564A proposes a method for increasing the compaction density of a material, comprising the steps of: (1) Mixing a composite iron source consisting of a lithium source, ferric phosphate and metal iron powder, a phosphorus source and a carbon source according to a certain proportion, putting the mixture into a dispersing kettle, adding a solvent for dispersing, coarse grinding and fine grinding to obtain uniformly mixed slurry, and carrying out spray drying on the slurry to obtain spherical precursor powder. (2) And tabletting, granulating and densifying the obtained precursor powder to obtain a granular precursor. (3) Sintering the obtained granular precursor at high temperature under the protection of inert gas, naturally cooling to room temperature, and crushing to obtain a high-compaction lithium iron phosphate product.
The positive electrode material prepared by the method has the compaction density of 2.8-3.0g/cm 3 In the range, the discharge gram capacity at the 1C multiplying power also reaches 155.6mAh/g, and the high compaction density does not influence the discharge capacity of the material. However, since densification occurs in the previous step of high temperature sintering, this results in poor consistency of the cathode materialThereby making the stability of the battery insufficient.
Patent CN 108011104A discloses a method for preparing high-compaction-density lithium iron phosphate, which selects two particle slurries, namely a large particle slurry and a small particle slurry, and the large particle slurry and the small particle slurry are mixed according to a certain proportion in a grinding stage, and then are respectively subjected to drying treatment and heat treatment to prepare the high-compaction-density lithium iron phosphate. The compacted density of the lithium iron phosphate positive electrode material prepared by the method reaches 2.57g/cm 3 . The method has the advantages of simple process flow, low cost and applicability to industrial production. However, the slurry of the large and small particles is mixed to cause uneven slurry dispersion, and the small particles have high specific surface area and are easy to form agglomeration, so that the difficulty of slurry dispersion is increased.
Patent CN 109192948A provides a method for preparing lithium iron phosphate with high compacted density. And sintering the lithium iron phosphate precursor in a protective gas atmosphere, wherein the sintering is three-stage sintering, the sintering temperature of the three-stage sintering is sequentially increased, and cooling is performed after the three-stage sintering is finished to obtain the lithium iron phosphate positive electrode material, and the large particles and the small particles of lithium iron phosphate are uniformly mixed so that the small particles are completely filled in gaps of the large particles. The three-stage sintering process provided by the invention has high requirements on equipment, is complex in flow and is not suitable for industrial production.
Patent CN 102275887A discloses a method for preparing a high-capacity high-compaction-density lithium iron phosphate material, which comprises (1) mixing a lithium source and Fe 3+ The source, phosphate, dopant and organic carbon source are mixed and then spray granulated. (2) preparing a presintered product. (3) And mixing and sanding the presintered product and an inorganic carbon source, and then performing spray drying to obtain secondary spray powder. (4) And (3) heating the secondary spray powder under vacuum or in protective atmosphere, and sintering at constant temperature. (5) And (3) performing secondary ball milling or air flow milling on the sintered semi-finished product to obtain a lithium iron phosphate product. However, the compaction density of the lithium iron phosphate is improved through secondary spraying, the processing process flow is complex, and the cost in actual production is high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and discloses a post-treatment method of a phosphate system anode material, which can burn a loose carbon layer and close surface holes through oxidizing calcination of a synthesized lithium iron phosphate anode material; and adding a carbon source and a lithium supplementing agent, and grinding and calcining again to form the positive electrode material with high compaction and low specific surface area. The method has the advantages of strong applicability and operability for any commercial phosphate system anode material.
The technical scheme who adopts for solving the technical problem that exists among the prior art is to this patent:
the post-treatment method of the phosphate system anode material comprises the following steps:
s1, placing a certain amount of commercial phosphate system anode material into a sintering furnace, oxidizing and calcining for a certain time at a certain temperature, wherein the effect of the anode material is to burn out a loose carbon layer and bridge surface holes;
s2, mixing the calcined anode material with a carbon source with a certain mass and a lithium supplementing agent, adding deionized water with a certain mass, placing the mixture into a grinding tank, and grinding for a certain time to obtain slurry;
and S3, placing the obtained slurry in a baking oven at 200-300 ℃, taking out, moving to a sintering furnace for sintering, introducing protective gas before sintering, cooling for a certain time under the protective atmosphere after sintering, taking out, cooling for a certain time in air, and grinding and sieving by 20-300 meshes to obtain the phosphate anode material.
Further, the positive electrode material of the phosphate system in the S1 is lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate or lithium manganese iron phosphate.
Further, the phosphate system positive electrode material in S1 is 400-500g in mass parts, the carbon source is 40-50 mass parts, and the lithium supplementing agent is 1-5% of the phosphate positive electrode material in mass.
Further, in the step S1, the oxidizing and calcining time is 3-10h, the calcining temperature is 600-700 ℃, and the oxidizing and calcining atmosphere is air atmosphere.
Further, the carbon source in S2 is one or a mixture of more than one of glucose, PEG and sucrose.
Further, the lithium supplementing agent in S2 is Li 3 N、Li 2 O 2 、Li 2 C 2 One of (a)Or a mixture of several kinds.
Further, the addition amount of the lithium supplementing agent in S2 is generally 1-5% of the mass of the positive electrode material.
Further, the ratio of the mass of deionized water to the mass of the positive electrode material in S2 is (1-20): 1.
Further, the mass ratio of the zirconia balls (diameter: 0.1 to 20 mm) to the positive electrode material in S2 is (1 to 20): 1.
Further, the grinding time in S2 is 1-10h.
And further, the drying temperature in the step S3 is 200-300h, the slurry is sintered for 5-10h at 700-800 ℃, the slurry is cooled for 3-6h under the protection atmosphere after being sintered, and the slurry is taken out and placed in the environment of 10-20 ℃ for continuous cooling for 1-20h.
This patent has advantage and positive effect be:
on the premise of not influencing the capacity and the multiplying power performance of the battery, the compaction density of the anode material is improved; the specific surface area of the material is reduced; the process flow is simple, and the operability is strong; the method can be applied to all commercial phosphate system anode materials.
Detailed Description
For further understanding of the invention, features and efficacy of this patent, the following examples are set forth to illustrate, but are not limited to, the following:
example 1
The post-treatment method of the phosphate system anode material comprises the following steps:
s1, placing 500g of lithium iron phosphate material in a sintering furnace, oxidizing and calcining for 3 hours at 600 ℃, wherein the sintering atmosphere is air atmosphere;
s2, mixing lithium iron phosphate with 50g PEG and 5gLi after calcination 2 O 2 Mixing uniformly, placing into a grinding tank, adding 500g of deionized water and 500g of zirconia balls with the diameter of 1mm, and grinding for 1h in a grinding machine to prepare slurry;
s3, placing the slurry into a baking oven at 200 ℃ for baking, transferring the slurry into a sintering furnace after baking, introducing protective gas nitrogen, sintering at 700 ℃ for 5 hours, cooling for 5 hours in nitrogen atmosphere after sintering, taking out, placing in an environment at 20 ℃ for continuously cooling for 20 hours, and grinding and sieving with a 300-mesh sieve to obtain the high-compaction low-specific-surface area lithium iron phosphate product.
The compacted density of the lithium iron phosphate material treated by the method is changed from original 2.36g/cm 3 Is increased to 2.59g/cm 3 . After the button cell is manufactured, the discharge gram capacity is increased from 159mAh/g to 161mAh/g under the 0.1C multiplying power.
Example 2
S1, placing 400g of lithium iron manganese phosphate material into a sintering furnace, oxidizing and calcining for 10 hours at 700 ℃, wherein the calcining atmosphere is air atmosphere;
s2, calcining and mixing lithium iron manganese phosphate with 40g glucose and 4g Li 3 Mixing N uniformly, placing into a grinding tank, adding 700g of deionized water and 1000g of zirconia balls with the diameter of 2mm, and grinding in a grinding machine for 8 hours to prepare slurry;
s3, placing the slurry into a 250 ℃ oven for drying, transferring the slurry into a sintering furnace after drying, introducing helium as protective gas, sintering at 800 ℃ for 10 hours, cooling for 6 hours in nitrogen atmosphere after sintering, taking out, placing in 15 ℃ for continuously cooling for 10 hours, and grinding and sieving with a 200-mesh sieve to obtain the high-compaction low-specific surface area lithium manganese iron phosphate product.
The compacted density of the lithium iron manganese phosphate material treated by the method is changed from original 2.31g/cm 3 Raised to 2.48g/cm 3 . After the button cell is manufactured, the discharge gram capacity is increased from 154mAh/g to 157mAh/g under the 0.1C multiplying power.
Example 3
S1, placing 420g of lithium manganese phosphate material in a sintering furnace, oxidizing and calcining for 10 hours at 700 ℃, wherein the calcining atmosphere is air atmosphere;
s2, calcining and mixing lithium manganese phosphate with 40g of sucrose and 4g of Li 2 C 2 Mixing uniformly, placing into a grinding tank, adding 800g of deionized water and 1000g of zirconia balls with the diameter of 3mm, and grinding for 10 hours in a grinding machine to prepare slurry;
s3, placing the slurry into a baking oven at 280 ℃ for baking, transferring the slurry into a sintering furnace after baking, introducing helium as protective gas, sintering for 7h at 700 ℃, cooling for 3h in nitrogen atmosphere after sintering, taking out, placing in an environment at 10 ℃ for continuously cooling for 1h, and grinding and sieving with a 150-mesh sieve to obtain the high-compaction low-specific-surface-area lithium manganese phosphate product.
The compacted density of the lithium manganese phosphate material treated by the method is changed from original 2.17g/cm 3 Raised to 2.32g/cm 3 . After the button cell is manufactured, the discharge gram capacity is increased from 141mAh/g to 147mAh/g under the 0.1C multiplying power.
Example 4
S1, placing 450g of lithium vanadium phosphate material in a sintering furnace, oxidizing and calcining for 5 hours at 650 ℃, wherein the calcining atmosphere is air atmosphere;
s2, calcining and mixing lithium vanadium phosphate with 45g of glucose and 5g of Li 2 C 2 Mixing uniformly, placing into a grinding tank, adding 500g of deionized water and 700g of zirconia balls with the diameter of 2mm, and grinding for 4 hours in a grinding machine to prepare slurry;
s3, placing the slurry into a 260 ℃ oven for drying, transferring the slurry into a sintering furnace after drying, introducing helium as protective gas, sintering at 750 ℃ for 8 hours, cooling for 4 hours in nitrogen atmosphere after sintering, taking out, placing in 15 ℃ for continuously cooling for 15 hours, and grinding and sieving by a 180-mesh sieve to obtain the high-compaction low-specific surface area vanadium lithium phosphate product.
The compaction density of the lithium vanadium phosphate material treated by the method is changed from original 1.98g/cm 3 Is increased to 2.11g/cm 3 . After the button cell is manufactured, the discharge gram capacity is increased from 149mAh/g to 151mAh/g under the 0.1C multiplying power.
The positive electrode material is made into a button cell, a lithium sheet is adopted as a counter electrode, and the manufacturing method of the electrode and the assembling method of the button cell are as follows:
electrode manufacturing and button cell assembly
a. Manufacturing of positive pole piece
The active substance and the conductive agent acetylene black are weighed according to the mass ratio of 16:3, then are put into a 50mL small beaker, a proper amount of absolute ethyl alcohol is added to the mixture to submerge the powder material, and the mixture is placed into an ultrasonic dispersion instrument for ultrasonic treatment for 15min. Stirring continuously in the ultrasonic process to uniformly mix the raw materials, and then taking out and dripping a proper amount of PTFE (active substance: PTFE mass ratio is 16:1). Stirred into a bulk shape, and then repeatedly rolled into a film with the thickness of about 0.14mm by a film pressing machine. And (3) placing the pressed film in a vacuum drying oven to dry for 40min at 80 ℃, then stamping out a wafer with the diameter of about 1cm by using a film stamping device, weighing, and then placing the wafer into a vacuum glove box filled with argon for 4h to assemble the button cell.
b. Assembly of button cell
The button cell is assembled in a vacuum glove box filled with argon atmosphere, the manufactured diaphragm is taken as an anode, a counter electrode adopts a metal lithium sheet, a diaphragm adopts Celgard2400 microporous polypropylene film, and the molecular weight is 1 mol.L -1 LiPF 6 Dimethyl carbonate (DMC) +ethylene carbonate (EC) +ethylmethyl carbonate (EMC) (1:1:1, vol) is used as electrolyte, the components are assembled into a CR2032 type button cell, the assembled button cell is placed into a copper mold to be screwed tightly, and electrochemical tests are carried out by taking the button cell as a measuring monomer.
Charge and discharge performance test
In this experiment, the LAND CT2001A battery test system was used to test the rate and cycling performance of CR2032 coin cells. The temperature has a great influence on the electrochemical performance of the battery, so the test environment temperature of the battery should be strictly controlled at 25 + -1 deg.c. The test voltage range is 2.5-4.3V (vs. Li/Li) + ). The specific test system is as follows:
(1) Standing for 1min.
(2) Constant current is charged to a voltage of more than or equal to 4.3V.
(3) And charging for 15min at constant voltage.
(4) Standing for 1min.
(5) Constant current discharge is carried out until the voltage is less than or equal to 2.5V.
(6) And if the cycle performance is measured, repeating the steps.
The compacted density of the lithium manganese phosphate material treated by the method is changed from original 2.17g/cm 3 Raised to 2.32g/cm 3 . After the button cell is manufactured, the discharge gram capacity is increased from 141mAh/g to 147mAh/g under the 0.1C multiplying power.
Examples 1-3 are compared to comparative experimental data in the following table:
TABLE 1
As can be seen from Table 1, the phosphate cathode material prepared by the present invention has a greater improvement in the compacted density than the conventional commercial phosphate cathode material. Meanwhile, the design of the invention does not influence the discharge performance of the material.
The foregoing description is only of the preferred embodiments of the present patent, and is not intended to limit the present patent in any way, and any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present patent are all within the scope of the technical solution of the present patent.
Claims (1)
1. The post-treatment method of the phosphate system anode material is characterized by comprising the following steps of:
s1, placing a certain amount of commercial phosphate system anode material into a sintering furnace, and oxidizing and calcining for a certain temperature and a certain time;
s2, mixing the calcined anode material with a carbon source with a certain mass and a lithium supplementing agent, adding deionized water with a certain mass, placing the mixture into a grinding tank, and grinding for a certain time to obtain slurry;
s3, placing the obtained slurry in a baking oven at 200-300 ℃, taking out, moving to a sintering furnace for sintering, introducing protective gas before sintering, cooling for a certain time under a protective atmosphere after sintering, taking out, cooling for a certain time in air, and grinding and sieving by 20-300 meshes to obtain a phosphate anode material;
the positive electrode material of the phosphate system in the S1 is lithium iron phosphate, lithium manganese phosphate, lithium vanadium phosphate or lithium manganese iron phosphate;
the phosphate system positive electrode material in S1 is 400-500g in mass parts, the carbon source is 40-50 mass parts, and the lithium supplementing agent is 1-5% of the phosphate positive electrode material in mass parts;
s1, oxidizing and calcining for 3-10h, wherein the calcining temperature is 600-700 ℃, and the oxidizing and calcining atmosphere is air atmosphere;
the carbon source in S2 is one or a mixture of more of glucose, PEG and sucrose;
the lithium supplementing agent in S2 is Li 3 N、Li 2 O 2 、Li 2 C 2 One or a mixture of more than one of the following materials;
the ratio of the mass of the deionized water to the mass of the positive electrode material in the S2 is (1-20): 1;
s3, sintering the slurry at 700-800 ℃ for 5-10h, cooling for 3-6h under a protective atmosphere after sintering, taking out, and placing in an environment of 10-20 ℃ for continuous cooling for 1-20h;
the compacted density of the lithium iron phosphate material treated by the method is 2.59g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compacted density of the lithium iron manganese phosphate material is 2.48g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compacted density of the lithium manganese phosphate material is 2.32g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The compacted density of the lithium vanadium phosphate material is 2.11g/cm 3 。
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