CN111646459A - Preparation method and application of boron-doped graphene material - Google Patents
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Abstract
The invention relates to the technical field of electrochemical materials, in particular to a preparation method and application of a boron-doped graphene material. The preparation method provided by the invention comprises the following steps: mixing boric acid and graphene oxide dispersion liquid, and freeze-drying to obtain precursor powder; and calcining the precursor powder in an argon-hydrogen atmosphere to obtain the boron-doped graphene material. The boron-doped graphene material prepared by the preparation method provided by the invention has a longer cycle life when being used as a lithium ion battery cathode material in a charge-discharge cycle process.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a preparation method and application of a boron-doped graphene material.
Background
With the development of society and science and technology, the demand of people for electric vehicles, portable electronic devices, power grid storage and the like is continuously increasing, and high-energy density batteries are an urgent need at present. Since the Lithium Ion Battery (LIB) developed by sony corporation appeared in 1991, people's demand for energy storage devices was met to some extent, but due to its limited theoretical energy density (150-200 Wh/kg) and slow development rate, the lithium ion battery widely used at present cannot meet the current demand for increasing energy density. Since the metallic lithium negative electrode has the highest theoretical specific capacity (3860mAh/g) and the lowest electrochemical potential (minus 3.040V relative to the standard hydrogen electrode), lithium metal batteries based on the metallic lithium negative electrode include lithium sulfur batteries, lithium oxygen batteries and the like, and have received much attention because of their great advantages and potentials in energy density. Of all the problems currently in further development in the manufacture of lithium metal anodes, the most serious is the growth of lithium dendrites during repeated depositions. Therefore, it is critical to obtain a suitable base material for lithium deposition, so that the lithium metal can be uniformly deposited to avoid the growth of lithium dendrites.
Disclosure of Invention
The invention aims to provide a preparation method and application of a boron-doped graphene material. The boron-doped graphene material has good adsorption capacity on lithium, and is beneficial to uniform nucleation and deposition of metal lithium on the surface of an electrode material, so that the cycle life of a lithium battery is prolonged.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a boron-doped graphene material, which comprises the following steps:
mixing boric acid and graphene oxide dispersion liquid, and freeze-drying to obtain precursor powder;
and calcining the precursor powder in an argon-hydrogen atmosphere to obtain the boron-doped graphene material.
Preferably, the concentration of the graphene oxide in the graphene oxide dispersion liquid is 1.5-2.5 mg/L.
Preferably, the mass ratio of the graphene oxide to the boric acid in the graphene oxide dispersion liquid is 1: (0.5-2).
Preferably, the preparation method of the graphene oxide dispersion liquid comprises the following steps:
and under the condition of ice-water bath, mixing the expanded graphite, concentrated sulfuric acid and potassium permanganate to perform oxidation-reduction reaction to obtain the graphene oxide dispersion liquid.
Preferably, the mass concentration of the concentrated sulfuric acid is 98%;
the mass ratio of the expanded graphite to the volume of concentrated sulfuric acid to potassium permanganate is (3.5-4.5) g: (160-200) mL: (15-25) g.
Preferably, the calcining temperature is 900-1000 ℃, and the calcining time is 1-5 h.
Preferably, the heating rate of heating to the calcining temperature is 3-6 ℃/min.
Preferably, after the calcination is completed, the method further comprises the steps of sequentially cleaning and drying the black powder obtained by calcination;
the cleaning comprises sequentially cleaning the black powder in sulfuric acid and water.
The invention also provides application of the boron-doped graphene material prepared by the preparation method in the technical scheme as an active component of a lithium ion battery cathode material in a lithium ion battery.
Preferably, the lithium ion battery negative electrode material comprises a boron-doped graphene material and polyvinylidene fluoride;
the mass ratio of the boron-doped graphene material to the polyvinylidene fluoride is 8: 2.
The invention provides a preparation method of a boron-doped graphene material, which comprises the following steps: mixing boric acid and graphene oxide dispersion liquid, and freeze-drying to obtain precursor powder; and calcining the precursor powder in an argon-hydrogen atmosphere to obtain the boron-doped graphene material. In the preparation method, boric acid can be completely dissolved in the graphene dispersion liquid, so that subsequent boron elements can be doped into graphene lattices uniformly, the solid powder is extracted by adopting a freeze-drying method, the lamellar structure of graphene oxide can be well protected, the graphene oxide is prevented from agglomerating, the electrochemical performance of the graphene oxide is improved, the graphene oxide is calcined in an argon-hydrogen atmosphere, the energy required by boron doping is provided, the graphene can be prevented from being oxidized due to the existence of reducing gas hydrogen, the defects in the prepared boron-doped graphene are reduced, and the electrochemical performance of the graphene oxide is favorably exerted. After boron is successfully doped into graphene, carbon atoms around boron atoms become enrichment centers of electron clouds due to the difference of electronegativity, and the enrichment centers are favorable for adsorption of lithium by the carbon atoms. Therefore, the boron-doped graphene material prepared by the preparation method improves the lithium adsorption capacity of the graphene material, thereby being beneficial to uniform nucleation and deposition of metal lithium on the surface of the electrode material. Meanwhile, the nucleation sites of the lithium metal of the boron-doped graphene are positioned on the carbon atoms, and the proportion of the carbon atoms in the doped graphene is obviously higher than that of the boron-doped atoms, so that the uniform nucleation and deposition of the lithium metal are greatly promoted, the probability of generation of dendrites is reduced, the risks of short circuit caused by the loss of electrolyte and the dendrites in the charge-discharge cycle process of the lithium metal as a lithium ion battery cathode material are reduced, and the cycle life of the lithium battery is further prolonged. Meanwhile, the binding energy of the boron-doped graphene material prepared by the preparation method disclosed by the invention and lithium is far higher than that of graphene and also higher than the cohesive energy of metal lithium, so that the boron-doped graphene material can guide the metal lithium to perform uniform nucleation on the surface of the metal lithium. In addition, almost all the carbon atoms surrounding the boron atoms have high binding energy to lithium, which indicates that the material has uniform lithium-philic properties, which greatly enhances the deposition assistance of the overall material to the nucleation of lithium metal. Thus, the cycle stability of the lithium metal battery can be improved.
Drawings
Fig. 1 is an SEM image of a boron-doped graphene material prepared in example 1;
fig. 2 is a TEM image of a boron-doped graphene material prepared in example 1;
fig. 3 is a Raman spectrum of the graphene prepared in comparative example 1 and the boron-doped graphene material prepared in example 1;
FIG. 4 shows the current density of 0.5mA/cm for the graphene prepared in comparative example 1, the nitrogen-doped graphene prepared in comparative example 2, and the boron-doped graphene material prepared in example 12Depositing a coulombic efficiency cycle map for 2 hours under the conditions (1);
fig. 5 is an SEM image of the boron-doped graphene material prepared in example 2;
FIG. 6 shows graphene prepared in comparative example 1 and nitrogen-doped graphite prepared in comparative example 2Alkene and boron-doped graphene material prepared in example 1 at a current density of 1mA/cm2And 2mAh/cm2Capacity of 2h deposition.
Detailed Description
The invention provides a preparation method of a boron-doped graphene material, which comprises the following steps:
mixing boric acid and graphene oxide dispersion liquid, and freeze-drying to obtain precursor powder;
and calcining the precursor powder in an argon-hydrogen atmosphere to obtain the boron-doped graphene material.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the invention, boric acid and graphene oxide dispersion liquid are mixed, and then are frozen and dried to obtain precursor powder.
In the invention, the concentration of the graphene oxide in the graphene oxide dispersion liquid is preferably 1.5-2.5 mg/L, and more preferably 2.0 mg/L.
In the present invention, the graphene oxide dispersion is preferably prepared by a method, and the method for preparing the graphene oxide dispersion preferably includes the following steps:
and under the condition of ice-water bath, mixing the expanded graphite, concentrated sulfuric acid and potassium permanganate to perform oxidation-reduction reaction to obtain the graphene oxide.
In the present invention, the mass concentration of the concentrated sulfuric acid is preferably 98%. In the present invention, the mass ratio of the expanded graphite to the volume of concentrated sulfuric acid to potassium permanganate is preferably (3.5 to 4.5) g: (160-200) mL: (15-25) g, more preferably 4 g: 180 mL: 20 g.
In the invention, the mixing sequence is preferably to drop concentrated sulfuric acid into the expanded graphite till the completion, and after the reaction is carried out for 30min, potassium permanganate is continuously added. The dropping speed is not limited in any way, and the speed known by the person skilled in the art can be adopted; in the invention, the potassium permanganate is preferably added in batches, and the mass of each batch is preferably less than or equal to 1 g; the invention has no special limitation on the number of the added batches, and can ensure that the potassium permanganate is added according to the proportion of the expanded graphene and the concentrated sulfuric acid. In the present invention, the addition is preferably carried out under stirring; the stirring is not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art.
In the present invention, the redox reaction is preferably carried out under stirring conditions; the stirring is not particularly limited in the present invention, and may be carried out by a procedure well known to those skilled in the art. In the present invention, the temperature of the redox reaction is preferably room temperature; the time of the oxidation-reduction reaction is preferably 1.5-2.5 h, and more preferably 2 h.
After the redox reaction is completed, the invention also preferably comprises the step of carrying out post-treatment on the obtained product system; in the present invention, the post-treatment is preferably: and mixing the obtained product system with deionized water for dilution, adding a hydrogen peroxide solution to remove excessive potassium permanganate, removing supernatant, repeatedly cleaning and suction-filtering the reaction product by using dilute hydrochloric acid and deionized water in sequence, and keeping the lower graphene oxide colloidal precipitate until the solution is neutral. In the present invention, the volume ratio of the deionized water to the concentrated sulfuric acid is preferably 20: 9; the mass concentration of the hydrogen peroxide solution is preferably 5%; the volume ratio of the hydrogen peroxide solution to the concentrated sulfuric acid is preferably 5: 18. In the present invention, the concentration of the dilute hydrochloric acid is preferably 0.5 mol/L; the cleaning is not particularly limited in the present invention, and may be carried out by a process known to those skilled in the art.
In the present invention, the mass ratio of the graphene oxide to the boric acid in the graphene oxide dispersion liquid is preferably 1: (0.5 to 2), and more preferably 1: 1.
In the present invention, the mixing of the boric acid and the graphene oxide dispersion liquid is preferably performed by adding the boric acid to the graphene oxide dispersion liquid under stirring. The stirring is not particularly limited in the present invention, and may be carried out under conditions known to those skilled in the art.
In the present invention, after the mixing of the boric acid and the graphene oxide dispersion is completed, the obtained solution is preferably prefreezed; the pre-freezing temperature is preferably-60 ℃, and the pre-freezing time is preferably 24 h.
In the present invention, the temperature of the freeze-drying is preferably-55 to-65 ℃, more preferably-60 ℃; the freeze drying time is preferably 18-36 h, and more preferably 24 h.
After precursor powder is obtained, the precursor powder is calcined under argon-hydrogen atmosphere to obtain the boron-doped graphene material.
In the invention, the calcining temperature is preferably 900-1000 ℃, and more preferably 950 ℃; the calcination time is preferably 1-5 h, and more preferably 3 h. The heating rate of the temperature to the calcining temperature is preferably 3-6 ℃/min, and more preferably 5 ℃/min.
After the calcination is completed, the invention also preferably comprises the step of carrying out post-treatment on the black powder obtained after the calcination; the post-treatment preferably comprises cooling, soaking, suction filtration and freeze drying which are sequentially carried out; the cooling mode is not limited in any way, and the temperature can be reduced to room temperature by adopting a mode well known to those skilled in the art. In the invention, the soaking preferably comprises soaking in dilute sulfuric acid and deionized water for 1 hour respectively in sequence; the concentration of the dilute sulfuric acid is preferably 0.5mol/L, and the temperature of the dilute sulfuric acid is preferably 90 ℃; the temperature of the deionized water is preferably 90 ℃. The suction filtration is not particularly limited in the present invention, and may be carried out by a process known to those skilled in the art. In the present invention, the temperature of the freeze-drying is preferably-60 ℃ and the time of the freeze-drying is preferably 24 hours.
The invention also provides application of the boron-doped graphene material prepared by the preparation method in the technical scheme as an active component of a lithium ion battery cathode material in a lithium ion battery.
In the invention, when the boron-doped graphene material is used as an active component of a lithium ion battery negative electrode material, the lithium ion battery negative electrode material preferably comprises the boron-doped graphene material and polyvinylidene fluoride; the mass ratio of the boron-doped graphene material to the polyvinylidene fluoride is preferably 8: 2.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Under the condition of ice-water bath, dropwise adding 180mL of 98% concentrated sulfuric acid into 4g of expanded graphite, reacting for 30min, adding 20g of potassium permanganate, reacting for 2h under the condition of stirring, adding 400mL of deionized water, diluting, and adding 50mL of 5% hydrogen peroxide solution to remove potassium permanganate; sequentially washing the reaction product with dilute hydrochloric acid (the concentration is 0.5mol/L) and deionized water until the solution is neutral to obtain graphene oxide dispersion liquid (2 mg/mL);
under the condition of stirring, adding 100mg of boric acid (the mass ratio of the boric acid to the graphene oxide is 1:1) into 50mL of graphene oxide dispersion liquid, pre-freezing to (-60 ℃ for 24h), and freeze-drying (the condition is that the temperature is 60 ℃ below zero for 24h) to obtain precursor powder;
calcining the precursor powder in argon-hydrogen atmosphere (950 ℃,3h, the heating rate is 5 ℃/min), cooling to room temperature, sequentially soaking in 90 ℃ dilute sulfuric acid (0.5mol/L) and deionized water for 1h respectively, and then sequentially performing suction filtration and freeze drying (60 ℃ below zero, 24h) to obtain a boron-doped graphene material;
performing SEM test on the boron-doped graphene material, wherein the test result is shown in figure 1, and as can be seen from figure 1, the boron-doped graphene material keeps the layered structure of graphene, no agglomeration occurs, and no boron oxide residue exists on the surface of the graphene;
the boron-doped graphene material is subjected to a TEM test, and the test result is shown in fig. 2, as can be seen from fig. 2, the boron-doped graphene material has a layered folded structure of graphene, stacking of few layers of graphene can be observed under TEM, the height of the stacked graphene conforms to the characteristics of the graphene material, and no boron oxide residue exists on the surface of the graphene.
Example 2
The preparation method of the graphene oxide dispersion was the same as in example 1;
under the condition of stirring, adding 50mg of boric acid (the mass ratio of the boric acid to the graphene oxide is 0.5:1) into 50mL of graphene oxide dispersion liquid (2mg/mL), prefreezing at (-60 ℃ for 24h), and freeze-drying at (-60 ℃ for 24h) to obtain precursor powder;
calcining the precursor powder in argon-hydrogen atmosphere (950 ℃,3h, the heating rate of 5 ℃/min), cooling to room temperature, sequentially soaking in 90 ℃ dilute sulfuric acid (0.5mol/L) and deionized water for 1 hour respectively, and then sequentially performing suction filtration and freeze drying to obtain a boron-doped graphene material;
the boron-doped graphene material is subjected to SEM test, and the test result is shown in fig. 5, and it can be seen from fig. 5 that the prepared boron-doped graphene material has the same morphology as that in example 1, the layered structure of graphene is retained, no aggregation occurs, and no boron oxide residue exists on the surface of graphene.
Example 3
The preparation method of the graphene oxide dispersion was the same as in example 1;
under the condition of stirring, 200mg of boric acid (the mass ratio of the boric acid to the graphene oxide is 2:1) is added into 50mL of graphene oxide dispersion liquid (2mg/mL), prefreezing is carried out at (-60 ℃ for 24h), and freeze drying is carried out (the condition is that the temperature is 60 ℃ below zero for 24h) to obtain precursor powder;
calcining the precursor powder in argon-hydrogen atmosphere (950 ℃,3h, the heating rate of 5 ℃/min), cooling to room temperature, sequentially soaking in 90 ℃ dilute sulfuric acid (0.5mol/L) and deionized water for 1 hour respectively, and sequentially performing suction filtration and freeze drying to obtain the boron-doped graphene material.
Comparative example 1
Preparing graphene: the preparation process is referred to example 1, except that the addition of boric acid is omitted.
Doping the boron with a graphene materialAnd the graphene prepared in the comparative example 1 is subjected to Raman spectrum test, the test result is shown in FIG. 3, and as can be seen from FIG. 3, the I of the boron-doped graphene materialD:IG(reflecting the defect content in the graphene, the defect content of the doped graphene material is higher than that of the graphene), the doped graphene material is obviously higher than that of the graphene, and the successful doping of the boron element is shown.
Comparative example 2
Preparation of graphene oxide reference example 1;
pre-freezing 50mL of graphene oxide dispersion liquid at (-60 ℃ for 24h), and freeze-drying (the conditions are that the temperature is 60 ℃ below zero and the temperature is 24h) to obtain precursor powder;
and calcining the precursor powder in an ammonia atmosphere (900 ℃,2h, the heating rate of 5 ℃/min), and cooling to room temperature to obtain the nitrogen-doped graphene material.
Test example
Respectively mixing the boron-doped graphene material prepared in examples 1-3, the graphene prepared in comparative example 1 and the nitrogen-doped graphene prepared in comparative example 2 with polyvinylidene fluoride according to a mass ratio of 8:2, adding the mixture into 2 mLN-methyl pyrrolidone, and stirring for 3 hours to obtain viscous slurry;
coating the viscous slurry on the surface of a clean and smooth copper foil, performing vacuum drying (85 ℃,12h), cooling, and cutting a pole piece into a wafer with the diameter of 14mm by using a pole piece punching machine to serve as the negative electrode of the button cell;
and (3) performing electrochemical performance test on the cathode by adopting a standard CR2032 button battery: the electrode is used as a positive electrode, a lithium sheet is used as a negative electrode, a polypropylene porous membrane (Celgard2400) is used as a diaphragm, 1M lithium bistrifluoromethylenesulfonamide is used as electrolyte salt in the electrolyte, 1, 3-dioxolane and glycol dimethyl ether (the volume ratio is 1:1) are used as mixed solvents, and 1% of LiNO is added3. The whole assembling process is carried out in a glove box, and the oxygen content and the water content are both controlled to be less than or equal to 0.1ppm in the assembling process. The charge and discharge test is completed on a constant current blue CT2001A test system, and the test current of the boron-doped graphene material prepared in the example 1, the test current of the graphene prepared in the comparative example 1 and the test current of the nitrogen-doped graphene prepared in the comparative example 2 are 0.5mA/cm2The deposition time is 2h, the test temperature is 25 ℃, the test result is shown in fig. 4, and as can be seen from fig. 4, the performance indexes such as the cycle number and the stability of the battery prepared from the boron-doped graphene electrode material are superior to those of graphene and nitrogen-doped graphene.
Wherein the test current of the boron-doped graphene material prepared in the embodiment 2 is 1mA/cm2Capacity of 2mAh/cm2The test temperature is 25 ℃, the test result is shown in fig. 6, and as can be seen from fig. 6, the battery prepared from the boron-doped graphene electrode material prepared in example 2 can stably circulate for 140 cycles.
Wherein the test current of the boron-doped graphene material prepared in the embodiment 3 is 0.5mA/cm2Capacity of 1mAh/cm2The test temperature is 25 ℃, and the test result is as follows: the battery prepared from the boron-doped graphene electrode material prepared in the embodiment 3 can stably circulate for more than 200 circles, the number of cycles of the battery prepared from the nitrogen-doped graphene does not exceed 150 circles, and the number of cycles of the battery prepared from the graphene does not exceed 100 circles.
As can be seen from the above examples and comparative examples, the performance indexes such as cycle number and stability of the Peng-doped graphene prepared by the preparation method are superior to those of graphene and nitrogen-doped graphene, and the potential of the material applied to a lithium metal cathode material is proved.
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. A preparation method of a boron-doped graphene material is characterized by comprising the following steps:
mixing boric acid and graphene oxide dispersion liquid, and freeze-drying to obtain precursor powder;
and calcining the precursor powder in an argon-hydrogen atmosphere to obtain the boron-doped graphene material.
2. The preparation method according to claim 1, wherein the concentration of the graphene oxide in the graphene oxide dispersion liquid is 1.5 to 2.5 mg/L.
3. The production method according to claim 1 or 2, wherein the mass ratio of the graphene oxide and the boric acid in the graphene oxide dispersion liquid is 1: (0.5-2).
4. The method according to claim 3, wherein the graphene oxide dispersion liquid is prepared by a method comprising the steps of:
and under the condition of ice-water bath, mixing the expanded graphite, concentrated sulfuric acid and potassium permanganate to perform oxidation-reduction reaction to obtain the graphene oxide dispersion liquid.
5. The method according to claim 4, wherein the concentrated sulfuric acid has a mass concentration of 98%;
the mass ratio of the expanded graphite to the volume of concentrated sulfuric acid to potassium permanganate is (3.5-4.5) g: (160-200) mL: (15-25) g.
6. The preparation method according to claim 1, wherein the calcination temperature is 900 to 1000 ℃ and the calcination time is 1 to 5 hours.
7. The method according to claim 6, wherein the rate of temperature increase to the calcination temperature is 3 to 6 ℃/min.
8. The method according to claim 1, further comprising, after the calcining, sequentially washing and drying the black powder obtained by calcining;
the cleaning comprises sequentially cleaning the black powder in sulfuric acid and water.
9. The boron-doped graphene material prepared by the preparation method of any one of claims 1 to 8 is used as an active component of a lithium ion battery negative electrode material in a lithium ion battery.
10. The use of claim 9, wherein the lithium ion battery negative electrode material comprises a boron doped graphene material and polyvinylidene fluoride;
the mass ratio of the boron-doped graphene material to the polyvinylidene fluoride is 8: 2.
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| CN113403644A (en) * | 2021-06-25 | 2021-09-17 | 北京航空航天大学 | Catalyst for electrocatalytic carbon dioxide reduction reaction and preparation method and application thereof |
| CN113430540A (en) * | 2021-06-25 | 2021-09-24 | 北京航空航天大学 | Monoatomic catalyst, preparation method and application thereof |
| CN116219469A (en) * | 2023-05-06 | 2023-06-06 | 东莞理工学院 | Electrocatalytic nitrogen reduction catalyst and preparation method thereof |
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| CN113403644A (en) * | 2021-06-25 | 2021-09-17 | 北京航空航天大学 | Catalyst for electrocatalytic carbon dioxide reduction reaction and preparation method and application thereof |
| CN113430540A (en) * | 2021-06-25 | 2021-09-24 | 北京航空航天大学 | Monoatomic catalyst, preparation method and application thereof |
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