CN116387482B - Graphene anode material and preparation method thereof - Google Patents

Graphene anode material and preparation method thereof Download PDF

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CN116387482B
CN116387482B CN202310325347.2A CN202310325347A CN116387482B CN 116387482 B CN116387482 B CN 116387482B CN 202310325347 A CN202310325347 A CN 202310325347A CN 116387482 B CN116387482 B CN 116387482B
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graphene oxide
graphene
anode material
boron
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张鑫
文钟强
袁强
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Hunan Jinyang Alkene Carbon New Material Co ltd
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Abstract

The invention discloses a graphene anode material and a preparation method thereof. The preparation method of the graphene anode material comprises the following steps: s1, preparing pretreated graphene oxide; s2, adding the pretreated graphene oxide, a boron source and nano particles into a solvent, reacting, spraying and granulating to obtain boron and nano particle doped graphene oxide powder; s3, carrying out reduction treatment on the boron and nano particle doped graphene oxide powder to obtain a graphene anode material; wherein the nanoparticle is selected from at least one of nano germanium and nano tin. The graphene anode material prepared by the preparation method disclosed by the invention has high specific capacity which can reach 1100 mA.h/g, and the capacity retention rate is more than 95% after 200 times of circulation, so that the graphene anode material has a wide application prospect in the field of batteries.

Description

Graphene anode material and preparation method thereof
Technical Field
The invention relates to the technical field of energy storage materials, in particular to a graphene anode material and a preparation method thereof.
Background
Graphene is a two-dimensional material with a honeycomb structure formed by closely arranging carbon atoms, has the characteristics of high mobility, excellent flexibility, good structure, electrochemical stability and the like, and has wide application prospects in the aspect of lithium ion battery materials. However, in practical application, graphene still has certain defects as the electrode material, such as poor interaction between graphene and lithium and poor energy storage performance due to inertia of graphene.
In the related art, in order to enhance the interaction between graphene and lithium, researchers often perform functional modification on graphene, such as introducing defects or functional groups, which improves the storage capacity of lithium to some extent, but the modified graphene material battery has low stability during the cycling process.
Therefore, a graphene anode material with high storage capacity and good cycle performance and a preparation method thereof are needed to be sought.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a graphene anode material and a preparation method thereof, wherein the graphene anode material has high specific capacity and excellent cycle performance.
The invention also provides application of the graphene anode material in preparation of lithium ion batteries.
In a first aspect of the present invention, a preparation method of a graphene anode material is provided, including the following preparation steps:
s1, preparing pretreated graphene oxide;
s2, adding the pretreated graphene oxide, a boron source and nano particles into a solvent, reacting, spraying and granulating to obtain boron and nano particle doped graphene oxide powder;
s3, carrying out reduction treatment on the boron and nano-particle doped graphene oxide powder to obtain a graphene anode material;
Wherein the nanoparticle is selected from at least one of nano germanium and nano tin.
The preparation according to the embodiment of the invention has at least the following beneficial effects:
(1) In the preparation method of the graphene anode material, firstly, the graphene oxide raw material is pretreated, so that the spacing between graphene sheets is increased, and the uniform doping of a follow-up boron source, nano germanium particles or nano tin particles is facilitated; secondly, in order to improve the adsorption stability of nano particles (nano germanium or nano tin) in the graphene, boron doping treatment is carried out at the same time, and as C atoms in the graphene are replaced by boron atoms in the boron doping process to form a boron substitution doping system, boron is one electron less than the C atoms, and holes are introduced, so that the adsorption of nano germanium or nano tin is promoted to a certain extent. In addition, as holes are introduced by doping boron, the fermi level of the boron-doped graphene system moves downwards to the valence band region to become p-type doping, and the system shows metallic property, so that the doping of boron can also improve the conductivity of the system to a certain extent.
(2) In the preparation method of the graphene anode material, germanium or tin is doped in the form of nano material, so that the cycling stability of the graphene anode material is improved. The specific surface area of the nano germanium or tin is large, and the absolute stress caused by expansion of the germanium in the charge and discharge process can be effectively reduced, so that the crushing of active substances can be effectively reduced, and the stabilizing effect is improved; secondly, the nano germanium or tin has small particle size, which is beneficial to improving the dynamic behavior of the material in the charge and discharge process and improving the overall rate capability.
(3) The preparation method of the graphene anode material is simple and is suitable for industrial production.
In some embodiments of the invention, the method of preparing pretreated graphene oxide comprises: preparing graphene oxide aqueous solution, performing ultrasonic dispersion, adding ethanol, performing solid-liquid separation after reaction, collecting a solid phase, and drying to obtain the graphene oxide aqueous solution.
In some embodiments of the invention, the graphene oxide aqueous solution has a mass concentration of 0.2 to 0.5mg/mL.
In some embodiments of the invention, in step S2, the solvent is selected from at least one of water, ethylene glycol, N-dimethylpyrrolidone.
In some embodiments of the present invention, in step S2, the weight part ratio of the pretreated graphene oxide, the boron source, and the nanoparticles is 20:2 to 5:5 to 10;
preferably, the boron source is selected from diboron trioxide or boric acid.
In some embodiments of the invention, in step S2, the temperature of the reaction is 250-450 ℃;
preferably, the pressure of the reaction is 2-5 MPa;
Preferably, the reaction time is 8 to 15 minutes.
In some embodiments of the present invention, in step S3, the specific steps of the reduction treatment are: placing boron and nano-particle doped graphene oxide powder in a reducing atmosphere, heating to 800-1000 ℃, preserving heat, then introducing organic alkane gas, and reacting at 1000-1500 ℃;
preferably, the reducing atmosphere is hydrogen or an inert gas;
Preferably, the organic alkane gas is at least one of methane, ethane, propane, ethylene, and propylene.
In some embodiments of the invention, the nanoparticle has a particle size of 40 to 80nm.
In a second aspect of the present invention, a graphene anode material is provided, and the graphene anode material is prepared by the preparation method.
The graphene anode material provided by the embodiment of the invention has at least the following beneficial effects: the graphene anode material has high specific capacity which can reach 1100 mA.h/g, and the capacity retention rate is more than 95% after 200 times of circulation.
The invention provides an application of a graphene anode material in preparing a lithium ion battery.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In an embodiment of the present invention, the Ge nanoparticles are purchased from macro-martial materials technology, inc, guangzhou, and have a particle size of about 50nm;
the tin nanoparticles were purchased from macro materials technology limited, guangzhou and have a particle size of about 70nm.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a graphene anode material, which specifically comprises the following steps:
Step S1, weighing a proper amount of graphene oxide, adding deionized water to prepare a graphene oxide aqueous solution with the concentration of 0.2mg/mL, performing ultrasonic dispersion for 30min at the temperature of 80 ℃ and the temperature of 60kHz to swell the graphene oxide, performing preliminary stripping to obtain graphene oxide slurry, adding 3 times volume of ethanol solvent into the graphene oxide slurry, stirring at the stirring speed of 500rpm for reaction for 15min, performing solid-liquid separation, collecting a solid phase, washing the solid phase with deionized water for 2-3 times, and drying the washed solid phase to constant weight at the temperature of 110 ℃ to obtain pretreated graphene oxide;
s2, dispersing 20 parts of the pretreated graphene oxide, 2 parts of diboron trioxide and 5 parts of Ge nano particles in 100 parts of water according to parts by weight, then putting the mixed solution into a high-temperature high-pressure reaction kettle, sealing the mixed solution, heating the mixed solution to 400 ℃, keeping the mixed solution for 10 minutes under the condition of 5MPa, discharging the pressure in the reaction kettle, cooling the mixed solution to room temperature, then introducing the mixed solution into a spray dryer at the speed of 20g/min, and carrying out spray granulation under the condition that the air inlet temperature is 100-150 ℃ and the air outlet temperature is 75-85 ℃ to obtain boron and germanium doped graphene oxide powder;
And S3, heating the boron and germanium doped graphene oxide powder to 800 ℃ in a hydrogen atmosphere, preserving heat for 60min, then introducing methane gas, and reacting at a high temperature for 2-3h under the condition of 1000 ℃ to obtain the graphene battery anode material.
Example 2
The embodiment provides a preparation method of a graphene anode material, which specifically comprises the following steps:
Step S1, weighing a proper amount of graphene oxide, adding deionized water to prepare a graphene oxide aqueous solution with the concentration of 0.2mg/mL, performing ultrasonic dispersion for 30min at the temperature of 80 ℃ and the temperature of 60kHz to swell the graphene oxide, performing preliminary stripping to obtain graphene oxide slurry, adding 3 times volume of ethanol solvent into the graphene oxide slurry, stirring at the stirring speed of 500rpm for reaction for 15min, performing solid-liquid separation, collecting a solid phase, washing the solid phase with deionized water for 2-3 times, and drying the washed solid phase to constant weight at the temperature of 110 ℃ to obtain pretreated graphene oxide;
S2, dispersing 20 parts of the pretreated graphene oxide, 2 parts of diboron trioxide and 5 parts of Ge nano particles in 100 parts of ethylene glycol according to parts by weight, then putting the mixed solution into a high-temperature high-pressure reaction kettle, sealing the mixed solution, heating the mixed solution to 400 ℃, keeping the temperature for 10 minutes under the condition of 5MPa, discharging the pressure in the reaction kettle, cooling the mixed solution to room temperature, then introducing the mixed solution into a spray dryer at the speed of 20g/min, and carrying out spray granulation under the condition of 100-150 ℃ of air inlet temperature and 75-85 ℃ of air outlet temperature to obtain boron and germanium doped graphene oxide powder;
And S3, heating the boron and germanium doped graphene oxide powder to 800 ℃ in a hydrogen atmosphere, preserving heat for 60min, then introducing methane gas, and reacting at a high temperature for 2-3h under the condition of 1000 ℃ to obtain the graphene battery anode material.
Example 3
The embodiment provides a preparation method of a graphene anode material, which specifically comprises the following steps:
Step S1, weighing a proper amount of graphene oxide, adding deionized water to prepare a graphene oxide aqueous solution with the concentration of 0.2mg/mL, performing ultrasonic dispersion for 30min at the temperature of 80 ℃ and the temperature of 60kHz to swell the graphene oxide, performing preliminary stripping to obtain graphene oxide slurry, adding 3 times volume of ethanol solvent into the graphene oxide slurry, stirring at the stirring speed of 500rpm for reaction for 15min, performing solid-liquid separation, collecting a solid phase, washing the solid phase with deionized water for 2-3 times, and drying the washed solid phase to constant weight at the temperature of 110 ℃ to obtain pretreated graphene oxide;
S2, dispersing 20 parts of the pretreated graphene oxide, 2 parts of boric acid and 5 parts of Ge nano particles in 100 parts of water according to parts by weight, then putting the mixed solution into a high-temperature high-pressure reaction kettle, sealing the mixed solution, heating the mixed solution to 400 ℃, keeping the mixed solution for 10 minutes under the condition of 5MPa, discharging the pressure in the reaction kettle, cooling the mixed solution to room temperature, then introducing the mixed solution into a spray dryer at a rate of 20g/min, and carrying out spray granulation under the condition that the air inlet temperature is 100-150 ℃ and the air outlet temperature is 75-85 ℃ to obtain boron-germanium doped graphene oxide powder;
And S3, heating the boron and germanium doped graphene oxide powder to 800 ℃ in a hydrogen atmosphere, preserving heat for 60min, then introducing methane gas, and reacting at a high temperature for 2-3h under the condition of 1000 ℃ to obtain the graphene battery anode material.
Example 4
The embodiment provides a preparation method of a graphene anode material, which specifically comprises the following steps:
step S1, weighing a proper amount of graphene oxide, adding deionized water to prepare a graphene oxide aqueous solution with the concentration of 0.2mg/mL, performing ultrasonic dispersion for 30min at the temperature of 80 ℃ and the temperature of 60kHz to swell the graphene oxide, performing preliminary stripping to obtain graphene oxide slurry, adding an ethanol solvent with the volume of 4 times into the graphene oxide slurry, stirring at the stirring speed of 500rpm for reaction for 15min, performing solid-liquid separation, collecting a solid phase, washing the solid phase with deionized water for 2-3 times, and drying the washed solid phase to constant weight at the temperature of 110 ℃ to obtain pretreated graphene oxide;
S2, dispersing 20 parts of the pretreated graphene oxide, 2 parts of diboron trioxide and 2 parts of tin nano particles in 100 parts of water according to parts by weight, then putting the mixed solution into a high-temperature high-pressure reaction kettle, sealing the mixed solution, heating the mixed solution to 400 ℃, keeping the mixed solution for 10 minutes under the condition of 5MPa, discharging the pressure in the reaction kettle, cooling the mixed solution to room temperature, then introducing the mixed solution into a spray dryer at the speed of 20g/min, and carrying out spray granulation under the condition of 100-150 ℃ of air inlet temperature and 75-85 ℃ of air outlet temperature to obtain boron and tin doped graphene oxide powder;
and S3, heating the boron and tin doped graphene oxide powder to 800 ℃ in a hydrogen atmosphere, preserving heat for 60min, then introducing methane gas, and reacting at a high temperature for 2-3h under the condition of 1000 ℃ to obtain the graphene battery anode material.
Example 5
The embodiment provides a preparation method of a graphene anode material, which specifically comprises the following steps:
Step S1, weighing a proper amount of graphene oxide, adding deionized water to prepare a graphene oxide aqueous solution with the concentration of 0.2mg/mL, performing ultrasonic dispersion for 30min at the temperature of 80 ℃ and the temperature of 60kHz to swell the graphene oxide, performing preliminary stripping to obtain graphene oxide slurry, adding 3 times volume of ethanol solvent into the graphene oxide slurry, stirring at the stirring speed of 500rpm for reaction for 15min, performing solid-liquid separation, collecting a solid phase, washing the solid phase with deionized water for 2-3 times, and drying the washed solid phase to constant weight at the temperature of 110 ℃ to obtain pretreated graphene oxide;
S2, dispersing 20 parts of the pretreated graphene oxide, 2 parts of diboron trioxide and 5 parts of Ge nano particles in 100 parts of water according to parts by weight, then putting the mixed solution into a high-temperature high-pressure reaction kettle, sealing the mixed solution, heating the mixed solution to 400 ℃, keeping the mixed solution for 10 minutes under the condition of 3MPa, discharging the pressure in the reaction kettle, cooling the mixed solution to room temperature, then introducing the mixed solution into a spray dryer at the speed of 20g/min, and carrying out spray granulation under the condition that the air inlet temperature is 100-150 ℃ and the air outlet temperature is 75-85 ℃ to obtain boron and germanium doped graphene oxide powder;
And S3, heating the boron and germanium doped graphene oxide powder to 800 ℃ in a hydrogen atmosphere, preserving heat for 60min, then introducing ethylene gas, and reacting at a high temperature for 4h under the condition of 1000 ℃ to obtain the graphene battery anode material.
Comparative example 1
The difference between this comparative example and example 1 is that: the graphene oxide is not pretreated.
Comparative example 2
The difference between this comparative example and example 1 is that: the graphene battery cathode material is not added with a diboron trioxide raw material in the preparation process.
Comparative example 3
The difference between this comparative example and example 1 is that: the Ge nano particles are not added in the preparation process of the graphene battery anode material.
Test case
The present test example carried out electrochemical performance tests on the graphene battery anode materials prepared in examples 1 to 5 and comparative examples 1 to 3. Firstly, mixing the graphene battery anode material prepared by the invention with Super P carbon black, sodium carboxymethyl cellulose, styrene-butadiene rubber and water according to the mass ratio of 95:1.0:1.5:2.5, stirring for 2 hours at the speed of 2000r/min, uniformly coating the mixture on a copper foil with the thickness of 15 mu m, coating the thickness of 40 mu m, rolling, slicing and baking to obtain a battery pole piece, and assembling the battery pole piece, an anode, a diaphragm and electrolyte into the CR2032 button half battery.
The battery prepared by the invention is subjected to charge and discharge test, constant current charge and discharge is carried out under the 3C multiplying power, the lower limit voltage is 0.001V, and the upper limit voltage is 2.0V. The test results are shown in Table 1.
Table 1: electrochemical performance test results of the anode materials prepared in examples 1 to 5 and comparative examples 1 to 3 of the present invention.
From the test results, the graphene battery anode material prepared by the preparation method disclosed by the invention has high specific capacity which can reach 1100 mA.h/g, and the capacity retention rate is more than 95% after 200 times of circulation.
Among them, the detection results of examples 1,2, 3 and 5 and example 4 show that: the doping of boron and germanium or boron and tin can be used for improving the specific capacity of the graphene battery anode material.
The detection results of example 1 and comparative example 1 show that: the pretreatment of the graphene oxide is beneficial to improving the lamellar spacing of the graphene oxide, promoting boron and germanium doping, and further improving the specific capacity of the graphene battery cathode material.
The detection results of example 1 and comparative example 2 show that: the doping of boron is beneficial to improving the specific capacity of the graphene battery cathode material, mainly because C atoms in graphene are replaced by boron atoms in the doping process to form a boron substitution doping system, and boron is one electron less than C, and a hole is introduced, so that the adsorption of nano germanium or nano tin is promoted to a certain extent. In addition, as holes are introduced by doping boron, the fermi level of the boron-doped graphene system moves downwards to the valence band region to become p-type doping, and the system shows metallic property, so that the doping of boron can also improve the conductivity of the system to a certain extent.
The detection results of example 1 and comparative example 3 show that: the doping of nano germanium can obviously improve the specific capacity of the graphene battery cathode material, mainly because germanium has high specific volume capacity and mass specific capacity.
In summary, the graphene anode material and the preparation method thereof are provided, the graphene anode material is used for improving the inter-sheet distance by preprocessing graphene oxide in the preparation process, then holes are introduced by doping boron atoms, the adsorption of nano germanium in graphene is promoted, and the specific capacity and the cycle stability of the battery can be remarkably improved by adopting the graphene anode material prepared by the preparation method disclosed by the invention to prepare the lithium battery, so that the graphene anode material has a wide application prospect in the field of batteries.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (9)

1. The preparation method of the graphene anode material is characterized by comprising the following preparation steps:
s1, preparing graphene oxide aqueous solution, performing ultrasonic dispersion, adding ethanol, performing solid-liquid separation after reaction, collecting a solid phase, and drying to obtain pretreated graphene oxide;
S2, adding the pretreated graphene oxide, a boron source and nano particles into a solvent, reacting, spraying and granulating to obtain boron and nano particle doped graphene oxide powder, wherein the weight part ratio of the pretreated graphene oxide to the boron source to the nano particles is 20: 2-5: 5-10; the temperature of the reaction is 250-450 ℃, the pressure of the reaction is 2-5 MPa, and the reaction time is 8-15 min;
S3, carrying out reduction treatment on the boron and nano particle doped graphene oxide powder to obtain a graphene anode material;
Wherein the nanoparticle is selected from at least one of nano germanium and nano tin;
The specific steps of the reduction treatment are as follows: and (3) placing the boron and nano-particle doped graphene oxide powder in a reducing atmosphere, heating to 800-1000 ℃, preserving heat, then introducing organic alkane gas, and reacting at 1000-1500 ℃.
2. The preparation method of claim 1, wherein the mass concentration of the graphene oxide aqueous solution is 0.2-0.5 mg/mL.
3. The method according to claim 1, wherein in step S2, the solvent is at least one selected from the group consisting of water, ethylene glycol, and N, N-dimethylpyrrolidone.
4. The method according to claim 1, wherein in step S2, the boron source is selected from the group consisting of diboron trioxide and boric acid.
5. The method according to claim 1, wherein the reducing atmosphere is hydrogen or an inert gas.
6. The method according to claim 1, wherein the organic alkane gas is at least one of methane, ethane, propane, ethylene, and propylene.
7. The method according to any one of claims 1 to 6, wherein the nanoparticle has a particle size of 40 to 80nm.
8. A graphene anode material characterized by being prepared by the preparation method of any one of claims 1 to 6.
9. Use of the graphene anode material according to claim 8 in the preparation of a lithium ion battery.
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Citations (12)

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