CN113889594A - Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material - Google Patents

Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material Download PDF

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CN113889594A
CN113889594A CN202010633943.3A CN202010633943A CN113889594A CN 113889594 A CN113889594 A CN 113889594A CN 202010633943 A CN202010633943 A CN 202010633943A CN 113889594 A CN113889594 A CN 113889594A
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lithium
lanthanum
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徐军红
陈和平
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LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD
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Abstract

The invention belongs to the field of secondary battery cathode materials, and particularly relates to a preparation method of a boron-doped lithium lanthanum zirconate-coated graphite composite material. The method comprises the following steps: 1) mixing inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, glycol, graphene oxide, citric acid and a solvent to prepare a precursor liquid, carrying out hydrothermal reaction on the precursor liquid, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor; 2) and (2) carrying out spray drying on a mixed solution consisting of a graphene/boron-doped lanthanum lithium zirconate precursor, an amorphous carbon precursor, graphite and a solvent, and then carbonizing a spray-dried product. According to the boron-doped lanthanum lithium zirconate-coated graphite composite material obtained by the method, the boron-doped lanthanum lithium zirconate, the amorphous carbon and the graphene in the shell cooperatively show good lithium ion conductivity and electronic conductivity, so that the ion transmission rate and the conductivity of the material can be improved, and the rate capability, the heat dissipation performance and the cycle performance of the graphite cathode material can be effectively improved.

Description

Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material
Technical Field
The invention belongs to the field of secondary battery cathode materials, and particularly relates to a preparation method of a boron-doped lithium lanthanum zirconate-coated graphite composite material.
Background
At present, artificial graphite is mainly used in the commercialized lithium ion battery negative electrode material, the rate performance of the artificial graphite is poor, and at present, the rate of lithium ion insertion/removal of the material is improved by coating soft carbon or hard carbon on the surface of the artificial graphite.
The application publication No. CN110071274A of the invention of China discloses a processing technology for improving the performance of an artificial graphite cathode material by a coating treatment method, which is to coat the artificial graphite by high-temperature asphalt and then coat a layer of amorphous carbon on the surface of the artificial graphite by carbonization treatment, thereby having certain improvement effect on the electrochemical performance of the artificial graphite.
Because the coating is at the charge-discharge in-process, lithium ion can only pass in and out the graphite layer structure from the edge of graphite layer, be on a parallel with the direction of graphite layer promptly, can't pass in and out from the direction of perpendicular graphite layer, so lithium ion business turn over graphite layer's diffusion coefficient is little, directly leads to lithium ion battery's multiplying power performance relatively poor. Meanwhile, during charging and discharging under high magnification, when lithium ions have no time to diffuse into the graphite layers, the lithium ions are concentrated on the surface of the negative electrode and reduced into metal lithium dendrites with extremely high activity, so that safety performance deviation is caused.
Disclosure of Invention
The invention aims to provide a preparation method of a boron-doped lanthanum lithium zirconate-coated graphite composite material, so as to improve the cycle performance and rate capability of a graphite cathode material.
In order to achieve the purpose, the technical scheme of the preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material is as follows:
a preparation method of a boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) mixing inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, glycol, graphene oxide, citric acid and a solvent to prepare a precursor liquid, carrying out hydrothermal reaction on the precursor liquid, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor;
2) and (2) carrying out spray drying on a mixed solution consisting of a graphene/boron-doped lanthanum lithium zirconate precursor, an amorphous carbon precursor, graphite and a solvent, and then carbonizing a spray-dried product.
The boron-doped lanthanum lithium zirconate coated graphite composite material obtained by the method is of a core-shell structure, the core is graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the boron-doped lanthanum lithium zirconate accounts for 10-30% of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon; wherein the molecular formula of the boron-doped lanthanum lithium zirconate is Li2ZrxB1-xO3,0.5≤x≤1。
According to the preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material, the boron-doped lanthanum lithium zirconate, the amorphous carbon and the graphene in the shell cooperatively show good lithium ion conductivity and electronic conductivity, so that the ion transmission rate and the conductivity of the material can be improved, and the rate capability, the heat dissipation performance and the cycle performance of the graphite cathode material can be effectively improved.
In the method, the boron element and the graphene are uniformly doped in the coating layer by a hydrothermal method, and are uniformly mixed with the coating agent and then coated on the surface of the graphite, so that the preparation process is simple, the stability is good, and the product has high quality stability and consistency.
In order to further optimize the rate capability and the cycle performance of the graphite cathode material, preferably, the mass ratio of the boron-doped lanthanum lithium zirconate in the shell to the graphite core is (1-10): 100.
in order to enable the composite material to have higher tap density and improve the energy density of the battery, the particle size of the boron-doped lithium lanthanum zirconate-coated graphite composite material is preferably 10-20 mu m.
The hydrothermal reaction is carried out only by ensuring that all raw materials are fully reacted, and preferably, in terms of reaction efficiency, in the step 1), the temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 1-12 hours.
In order to control the formation of precursor particles with uniform particle size, preferably, in step 1), the inorganic lithium salt is one or more than two of lithium nitrate, lithium carbonate and lithium hydroxide; one or more of inorganic lanthanum salt lanthanum nitrate and lanthanum carbonate; the inorganic zirconium salt is one or more of zirconium nitrate, zirconium phosphate, zirconium carbonate and zirconium hydroxide; the borate is one or two of sodium tetraphenylborate and tetraphenylboronic acid;
the mass ratio of the inorganic lithium salt to the inorganic lanthanum salt to the inorganic zirconium salt to the borate to the ethylene glycol to the graphene oxide is 5: (10-15), (5-10), (1-3): (5-8): (0.5 to 3); the molar ratio of the ethylene glycol to the citric acid is (1-3) to 1. The citric acid has a reduction effect, the glycol can play a role in controlling nucleation and crystallization, and the glycol and the citric acid can be used together to control the generation of the graphene/boron-doped lanthanum lithium zirconate precursor with regular and consistent appearance, so that good conditions are created for the electrical performance of the electrode material.
In order to facilitate the uniform mixing of citric acid and graphene oxide, preferably, in step 1), mixing an inorganic lithium salt, an inorganic lanthanum salt, an inorganic zirconium salt, a borate and a solvent, then adding a citric acid solution, ethylene glycol and a graphene oxide solution, and uniformly mixing, wherein the concentration of the citric acid solution is (1-10)%, and the concentration of the graphene oxide solution is (1-5)%.
In order to improve the coating consistency of the coating layer, preferably, in the step 2), the mass ratio of the graphene/boron-doped lanthanum lithium zirconate precursor to the amorphous carbon precursor to the graphite is (1-10): 5-20): 100.
In order to realize better wrapping and dispersion of boron-doped lanthanum lithium zirconate and graphene, preferably, in the step 2), the amorphous carbon precursor is pitch.
The carbonization reaction can promote the amorphous carbon precursor to be fully converted into the amorphous carbon, preferably, in the step 2), the carbonization is carried out for 1-12 hours at 700-1100 ℃ in a protective atmosphere.
Drawings
Fig. 1 is an SEM image of the boron-doped lanthanum lithium zirconate-coated graphite composite material according to example 1 of the present invention.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
First, a specific embodiment of the preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material
Example 1
The preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) preparation of precursor liquid: adding 5g of lithium nitrate, 12g of lanthanum nitrate, 8g of zirconium nitrate and 2g of sodium tetraphenylborate into 100ml of deionized water, uniformly mixing, adding 760ml of a 5% citric acid solution with a mass concentration, 6.2g of ethylene glycol and 100ml of a 3% graphene oxide solution with a mass concentration (the molar ratio of the ethylene glycol to the citric acid is 2:1), and uniformly dispersing by ultrasonic to obtain a precursor solution.
2) Transferring the precursor liquid into a high-pressure reaction kettle, reacting for 6 hours at 180 ℃, then naturally cooling to room temperature, and drying to obtain a graphene/boron-doped lithium lanthanum zirconate precursor; and then uniformly mixing 5g of graphene/boron-doped lanthanum lithium zirconate precursor with 10g of pitch, dispersing the mixture in 1000ml of n-hexane organic solvent, adding 100g of artificial graphite, uniformly stirring, carrying out spray drying, heating the obtained spray-dried particles to 800 ℃ in an argon inert gas environment, keeping the temperature at the constant temperature for 6 hours, and naturally cooling to room temperature to obtain the graphene/boron-doped lanthanum lithium zirconate/amorphous carbon coated modified artificial graphite cathode material.
The boron-doped lanthanum lithium zirconate-coated graphite composite material prepared by the method has a core-shell structure, the inner core is artificial graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the boron-doped lanthanum lithium zirconate Li is2ZrxB1- xO3(x is more than or equal to 0.5 and less than or equal to 1), the boron-doped lanthanum lithium zirconate accounts for 20 percent of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon, and the mass ratio of the boron-doped lanthanum lithium zirconate in the artificial graphite core to the shell is 100: 5.
Example 2
The preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) preparation of precursor liquid: adding 5g of lithium carbonate, 10g of lanthanum carbonate, 5g of zirconium phosphate and 1g of tetraphenyl boric acid into 100ml of deionized water, uniformly mixing, then adding 192ml of a 1% citric acid solution with a mass concentration, 6.2g of ethylene glycol and 50ml of a 1% graphene oxide solution with a mass concentration (the molar ratio of the ethylene glycol to the citric acid is 1:1), and uniformly dispersing by ultrasonic to obtain a precursor solution;
2) transferring the precursor liquid into a high-pressure reaction kettle, reacting at 150 ℃ for 12h, naturally cooling to room temperature, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor; and then uniformly mixing 1g of graphene/boron-doped lanthanum lithium zirconate precursor with 5g of pitch, dispersing the mixture in 1000ml of tetrahydrofuran organic solvent, adding 100g of artificial graphite, uniformly stirring, carrying out spray drying, heating the spray-dried particles to 700 ℃ in an argon inert gas environment, keeping the temperature at a constant temperature for 12h, and naturally cooling to room temperature to obtain the graphene/boron-doped lanthanum lithium zirconate/carbon-coated modified artificial graphite cathode material.
The boron-doped lanthanum lithium zirconate-coated graphite composite material obtained by the method of the embodiment has a core-shell structure, the inner core is artificial graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the molecular formula of the boron-doped lanthanum lithium zirconate is Li2ZrxB1-xO3(x is more than or equal to 0.5 and less than or equal to 1), the boron-doped lanthanum lithium zirconate accounts for 10 percent of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon, and the mass ratio of the boron-doped lanthanum lithium zirconate in the artificial graphite core to the shell is 100: 1.
Example 3
The preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) preparation of precursor liquid: adding 5g of lithium hydroxide, 15g of lanthanum nitrate, 10g of zirconium carbonate and 3g of sodium tetraphenylborate into 100ml of deionized water, uniformly mixing, adding 57ml of a 10% citric acid solution, 6.2g of ethylene glycol and 40ml of a 5% graphene oxide solution (the molar ratio of the ethylene glycol to the citric acid is 3:1), and uniformly dispersing by ultrasonic to obtain a precursor solution;
2) transferring the precursor liquid into a high-pressure reaction kettle, reacting at 200 ℃ for 1h, naturally cooling to room temperature, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor; and then, uniformly mixing 10g of graphene/boron-doped lanthanum lithium zirconate precursor with 20g of asphalt, dispersing the mixture in 1000ml of carbon disulfide organic solvent, adding 100g of artificial graphite, uniformly stirring, carrying out spray drying, heating the spray-dried particles to 1100 ℃ in an argon inert gas environment, keeping the temperature at a constant temperature for 1h, and naturally cooling to room temperature to obtain the graphene/boron-doped lanthanum lithium zirconate/carbon-coated modified artificial graphite cathode material.
The boron-doped lanthanum lithium zirconate-coated graphite composite material obtained by the method of the embodiment has a core-shell structure, the inner core is artificial graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the molecular formula of the boron-doped lanthanum lithium zirconate is Li2ZrxB1-xO3(x is more than or equal to 0.5 and less than or equal to 1), the boron-doped lanthanum lithium zirconate accounts for 30 percent of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon, and the mass ratio of the boron-doped lanthanum lithium zirconate in the artificial graphite core to the shell is 100: 10.
Second, comparative example
Comparative example 1
Adding 20g of pitch and 40ml of graphene oxide solution with the mass concentration of 5% into 1000ml of tetrahydrofuran, uniformly stirring, adding 100g of artificial graphite, uniformly stirring, performing spray drying to obtain a precursor material, transferring the precursor material into a tubular furnace, heating to 800 ℃ under the argon atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the amorphous carbon coated artificial graphite composite material.
Third, Experimental example
Experimental example 1SEM test
The boron-doped lanthanum lithium zirconate-coated graphite composite material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from figure 1, the obtained boron-doped lanthanum lithium zirconate-coated graphite composite material is granular, the particle size is between 10 and 20 microns, and the size distribution is uniform and reasonable.
Experimental example 2 button cell test
The graphite composites of the examples and comparative examples were assembled into button cells, respectively, and labeled: the button cell assembled from the graphite composite material of example 1 was labeled a1, the button cell assembled from the graphite composite material of example 2 was labeled a2, the button cell assembled from the graphite composite material of example 3 was labeled A3, and the button cell assembled from the graphite composite material of comparative example was labeled B1.
The preparation method of the button cell comprises the following steps: and adding a binder, a conductive agent and a solvent into the graphite composite material, stirring and mixing uniformly for pulping, coating the obtained slurry on a copper foil, drying and rolling to obtain the button cell. The adhesive is LA132 adhesive, the conductive agent is conductive agent SP, and the solvent is secondary distilled water; and the weight ratio of the graphite composite material, the conductive agent SP, the LA132 adhesive and the secondary distilled water is as follows: 95:1:4:220.
The lithium metal sheet is used as a counter electrode, a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite membrane is used as a diaphragm, and LiPF is used6The electrolyte solution of/EC + DEC (1:1) was used to simulate cell assembly in a hydrogen-filled glove box. Button cells A1, A2, A3 and B1 are respectively installed on a Wuhan blue electricity CT2001A type battery tester, charging is carried out at 0.1C multiplying power, the charging and discharging voltage range is 0.005V to 2.0V, and the measured first discharge capacity and first discharge efficiency are shown in table 1:
TABLE 1 Studies of the Properties of examples 1-3 and comparative graphite composites
Figure BDA0002567092160000051
As can be seen from Table 1, the discharge capacities of the composite anode materials prepared in examples 1 to 3 were significantly higher than those of the comparative examples; the reason is that the surface of the graphite material is coated with the boron-doped lanthanum lithium zirconate material with high lithium ion conductivity, so that the irreversible loss of the material is reduced, the ion conductivity of the material is improved, and the first efficiency of the material is improved; meanwhile, the electronic conductivity of the lanthanum lithium zirconate solid electrolyte is improved after the boron and the graphene are doped, so that the multiplying power performance of the lanthanum lithium zirconate solid electrolyte is improved.
Experimental example 3 pouch cell test
The materials prepared in examples 1 to 3 and comparative example were used as anode materials, respectively, and a ternary material (LiNi) was used1/3Co1/ 3Mn1/3O2) As the positive electrode, LiPF6(the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/L) is electrolyte, and celegard2400 is a diaphragm to prepare the 2Ah soft package battery.
3.1 Rate Performance test
The charging and discharging voltage range is 2.8-4.2V, and charging is carried out at 1.0C, 3.0C, 5.0C and 8.0C and discharging is carried out at 1.0C under the condition that the temperature is 25 +/-3.0 ℃; the cells were tested for constant current ratio and temperature in different charging modes and the results are shown in table 2:
TABLE 2 Rate Performance of examples 1-3 and comparative examples
Figure BDA0002567092160000061
As can be seen from table 2, the rate charging performance of the pouch cell of the example is significantly better than that of the comparative example, and the charging time is shorter, indicating that the graphite composite material of the present invention has good quick charging performance. The battery needs lithium ion migration in the charging process, the surface of the graphite composite material of the embodiment contains more lithium ions, so that convenience is provided for lithium ion insertion and extraction, the multiplying power performance of the battery is improved, meanwhile, the electronic conductivity of the lanthanum lithium zirconate is improved after boron doping, and the temperature rise of the lanthanum lithium zirconate is reduced.
3.2 cycle Performance test
The following experiments were carried out on the pouch batteries prepared from the negative electrode materials of examples 1 to 3 and comparative example: the capacity retention rate was measured by sequentially performing 50, 100, and 200 cycles of charge and discharge with a charge and discharge current of 2C/2C and a voltage range of 2.8-4.2V, and the results are shown in Table 3:
TABLE 3 cyclability of the lithium ion batteries of examples 1-3 and comparative example
Figure BDA0002567092160000062
As can be seen from Table 3, the cycle performance of the lithium ion batteries prepared by using the graphite composite negative electrode materials obtained in examples 1-3 is obviously superior to that of the comparative examples at each stage. The fact that the boron-doped lanthanum lithium zirconate, the amorphous carbon and the graphene are coated on the surface of the graphite proves that the transmission rate of lithium ions can be improved, so that the cycle performance of the lithium ions is improved.

Claims (7)

1. The preparation method of the boron-doped lithium lanthanum zirconate-coated graphite composite material is characterized by comprising the following steps of:
1) mixing inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, glycol, graphene oxide, citric acid and a solvent to prepare a precursor liquid, carrying out hydrothermal reaction on the precursor liquid, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor;
2) and (2) carrying out spray drying on a mixed solution consisting of a graphene/boron-doped lanthanum lithium zirconate precursor, an amorphous carbon precursor, graphite and a solvent, and then carbonizing a spray-dried product.
2. The method for preparing the boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1, wherein in the step 1), the hydrothermal reaction temperature is 150-200 ℃ and the reaction time is 1-12 h.
3. The method for preparing the boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1, wherein in the step 1), the inorganic lithium salt is one or more of lithium nitrate, lithium carbonate and lithium hydroxide; one or more of inorganic lanthanum salt lanthanum nitrate and lanthanum carbonate; the inorganic zirconium salt is one or more of zirconium nitrate, zirconium phosphate, zirconium carbonate and zirconium hydroxide; the borate is one or two of sodium tetraphenylborate and tetraphenylboronic acid;
the mass ratio of the inorganic lithium salt to the inorganic lanthanum salt to the inorganic zirconium salt to the borate to the ethylene glycol to the graphene oxide is 5: (10-15), (5-10), (1-3): (5-8): (0.5 to 3); the molar ratio of the ethylene glycol to the citric acid is (1-3) to 1.
4. The method for preparing the boron-doped lithium lanthanum zirconate-coated graphite composite material according to any one of claims 1 to 3, wherein in the step 1), the inorganic lithium salt, the inorganic lanthanum salt, the inorganic zirconium salt, the borate and the solvent are mixed, and then the citric acid solution, the ethylene glycol and the graphene oxide solution are added and mixed uniformly, wherein the concentration of the citric acid solution is (1-10)%, and the concentration of the graphene oxide solution is (1-5)%.
5. The method for preparing the boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1, wherein in the step 2), the mass ratio of the graphene/boron-doped lithium lanthanum zirconate precursor to the amorphous carbon precursor to the graphite is (1-10): (5-20): 100.
6. The method for preparing the boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1, wherein in the step 2), the amorphous carbon precursor is pitch.
7. The method for preparing the boron-doped lithium lanthanum zirconate-coated graphite composite material according to any one of claims 1 to 3, 5 and 6, wherein in the step 2), the carbonization is performed at 700 to 1100 ℃ for 1 to 12 hours in a protective atmosphere.
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