CN114735672A - Boron-nitrogen co-doped hard carbon material and preparation method thereof - Google Patents
Boron-nitrogen co-doped hard carbon material and preparation method thereof Download PDFInfo
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Abstract
In order to solve the technical problems that in the prior art, the hard carbon material is too rich in pore structure, large in crystal layer spacing and not beneficial to storage of lithium/sodium ions, and the lithium/sodium ion battery prepared by taking the hard carbon material as a negative electrode material is low in platform capacity and the like, the invention provides a boron-nitrogen co-doped hard carbon material and a preparation method thereof, wherein the preparation method comprises the following steps: obtaining trisodium citrate, urotropine and boron-containing oxide, uniformly mixing, and carrying out carbonization reaction in a protective atmosphere to obtain a composite hard carbon material; the obtained composite hard carbon material is taken out and is sequentially cleaned by hydrochloric acid and ethanol, and the cleaned composite hard carbon material is dried to obtain the boron-nitrogen co-doped hard carbon material with loose and porous interior.
Description
Technical Field
The invention relates to the technical field of hard carbon material preparation, in particular to a boron-nitrogen co-doped hard carbon material and a preparation method thereof.
Background
The specific capacity of the graphite cathode material reaches the limit, and the continuous large-current discharge capacity required by a large-scale power battery cannot be met, so people also begin to look at non-graphite materials, such as hard carbon and other non-carbon materials. Hard carbon materials, which are classified as amorphous carbon, generally refer to carbon that is difficult to completely graphitize at 2800 ℃ or higher, and their disordered structure is difficult to eliminate at high temperatures. The current preparation technology of hard carbon is mainly realized by medium and high temperature pyrolysis of hard carbon precursors (including macromolecular resins, hydrocarbons, biomass materials and the like) with rich oxygen-containing functional groups in an inert gas atmosphere. Compared with the graphite cathode material, the interlayer spacing of the hard carbon is larger, and the metal ions are more favorably embedded and separated. Different from graphite cathode materials, the storage mechanism of metal in hard carbon is mainly adsorption-desorption in a carbon layer, embedding-separation between graphite microcrystal layers and filling of holes formed by mutual staggering of graphite microcrystals. Therefore, as the cathode material, the surface morphology, the structural composition and the defect degree of the hard carbon material all have great influence on the performance of the energy storage device.
The hard carbon material prepared by the existing hard carbon material preparation technology has an excessively rich pore structure and larger crystal layer spacing, is beneficial to the diffusion of metal ions, but is not beneficial to the storage of lithium/sodium ions, and causes the low discharge capacity of the battery when the current hard carbon material is applied to the negative electrode material of the lithium/sodium ion battery.
Disclosure of Invention
The invention provides a boron-nitrogen co-doped hard carbon material and a preparation method thereof, aiming at the technical problems that the existing hard carbon material has an excessively rich pore structure, large crystal layer spacing and is not beneficial to storage of lithium/sodium ions, and a battery prepared by using the hard carbon material as a negative electrode material has low discharge capacity.
In order to solve the technical problem, on one hand, the invention provides a preparation method of a boron-nitrogen co-doped hard carbon material, which comprises the following steps:
1) obtaining trisodium citrate, urotropine and boron-containing oxide, uniformly mixing, and carrying out carbonization reaction in a reducing atmosphere to obtain a composite hard carbon material;
2) taking out the composite hard carbon material obtained in the step 1), washing with acid liquor, eluting sodium borate by-products in the composite hard carbon material, and obtaining the boron-nitrogen co-doped hard carbon material with loose and porous interior.
Preferably, the weight ratio of the trisodium citrate to the urotropine to the boron-containing oxide is (0.5-1.5): 1: (0.1-1.5).
Preferably, the weight ratio of the trisodium citrate to the urotropine to the boron-containing oxide is 1: (0.5-1).
Preferably, the trisodium citrate comprises trisodium citrate anhydrous or trisodium citrate dihydrate; the boron-containing oxide includes at least one of boron oxide, boric acid, or tetraphenylboronic acid.
Preferably, the protective atmosphere comprises at least one of a reducing gas, an inert gas and nitrogen.
Preferably, the reducing gas comprises hydrogen or ammonia;
the inert gas comprises at least one of helium, argon, neon and krypton;
the volume ratio of the hydrogen to the inert gas is (5-10): (90-95).
Preferably, in the step 1), the temperature rise rate of the carbonization reaction is 2-5 ℃/min; the reaction temperature of the carbonization reaction is 700-900 ℃, and the reaction time of the carbonization reaction is 1-3 h.
Preferably, the acid solution comprises hydrochloric acid, and the concentration of the hydrochloric acid is 0.1-0.2 mol/L; the number of washing times by using hydrochloric acid is 1-3.
Preferably, the step 2) is performed by washing with an acid solution and then with absolute ethyl alcohol, and the number of washing with absolute ethyl alcohol is 2-5.
On the other hand, the application provides a boron-nitrogen co-doped hard carbon material, which comprises the boron-nitrogen co-doped hard carbon material prepared by the preparation method of the boron-nitrogen co-doped hard carbon material.
The invention has the beneficial effects that:
1. according to the preparation method of the boron-nitrogen co-doped hard carbon material, the hard carbon material can be synthesized by a one-step method, the preparation process is simple, the price is low, and the preparation method is suitable for industrial large-scale production;
2. compared with the doping of single atoms of boron atoms or nitrogen atoms, the boron-nitrogen double-atom co-doping can effectively improve the electronic and ionic conductivity of the hard carbon material; compared with the doping of other diatoms such as sulfur atoms and phosphorus atoms, the boron atoms, the carbon atoms and the nitrogen atoms are adjacent, and the co-doping of the boron atoms and the nitrogen atoms can synergistically promote the electronegativity of the boron atoms and the electronegativity of the nitrogen atoms, so that the electrostatic adsorption capacity of the hard carbon material to ions is effectively promoted;
3. the preparation method has the advantages that abundant internal crosslinked carbon networks are formed through respective assembly of polymerization reactions among trisodium citrate, urotropine and boron-containing oxides, ammonia gas formed by reaction decomposition is released in the carbonization process, and sodium borate byproducts generated in the ammonia gas are eluted by acid liquor treatment, so that the hard carbon material has abundant loose porous structures and abundant defect sites are provided, the prepared boron-nitrogen co-doped hard carbon material has a loose surface structure and a porous internal space, the hard carbon material is used as an electrochemical storage device and can be more favorable for improving the adsorption and storage capacities of the hard carbon material on metal ions/metal compounds and the like, and the boron-nitrogen co-doped hard carbon material can be widely applied to lithium/sodium ion battery cathodes, lithium-sulfur battery sulfur carriers or diaphragm coating modified materials for lithium-sulfur batteries and the like, the method is used for improving the discharge capacity and rate capability of the battery.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a scanning electron microscope image of a boron-nitrogen co-doped hard carbon material 1 prepared in comparative example 1;
fig. 2 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 2 prepared in example 1;
fig. 3 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 3 prepared in example 2;
fig. 4 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 4 prepared in example 3;
fig. 5 is Raman graphs of boron-nitrogen co-doped hard carbon materials prepared in comparative example 1 and example 1;
FIG. 6 is XRD patterns of composite hard carbon materials prepared in examples 1-3 and comparative example 1 before cleaning;
FIG. 7 is XRD patterns of the composite hard carbon materials prepared in examples 1 to 3 and comparative example 1 after cleaning;
fig. 8 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 5 prepared in example 4;
fig. 9 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 6 prepared in example 5;
FIG. 10 is an XRD pattern of the composite hard carbon material prepared in examples 1, 4 and 5 before cleaning;
fig. 11 is an XRD pattern of the composite hard carbon material prepared in examples 1, 4 and 5 after cleaning.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a boron-nitrogen co-doped hard carbon material, which comprises the following steps:
1) obtaining trisodium citrate, urotropine and boron-containing oxide, uniformly mixing, and carrying out carbonization reaction in a protective atmosphere to obtain a composite hard carbon material;
2) taking out the composite hard carbon material obtained in the step 1), washing with acid liquor, eluting sodium borate by-products in the composite hard carbon material, and obtaining the boron-nitrogen co-doped hard carbon material with loose and porous interior.
The boron doping belongs to p-type doping, so that the Fermi level of the hard carbon material can be effectively reduced, and the embedding-extracting capacity of metal ions is enhanced; the nitrogen doping can further improve the conductivity of the hard carbon material; compared with single-atom doping, boron atom and nitrogen atom codoping not only maintains respective promotion effect on the hard carbon material, but also further enhances the adsorption capacity on ions through synergistic effect, and is beneficial to promoting the discharge capacity of the hard carbon material serving as a negative electrode of a lithium/sodium ion battery and the inhibition effect of the hard carbon material serving as a sulfur carrier of the lithium-sulfur battery and a diaphragm coating material for the lithium-sulfur battery on the shuttle effect of polysulfide.
According to the preparation method of the boron-nitrogen co-doped hard carbon material, the hard carbon material can be synthesized by a one-step method, the preparation process is simple, the price is low, and the preparation method is suitable for industrial large-scale production. Compared with the doping of single atoms of boron atoms or nitrogen atoms, the co-doping of the boron atoms and the nitrogen atoms can effectively improve the electronic and ionic conductivity of the hard carbon material; compared with other diatom doping such as sulfur atoms and phosphorus atoms, the boron, carbon and nitrogen atoms are adjacent, and the boron atom and nitrogen atom codoping can synergistically promote the electronegativity of the boron atom and the electronegativity of the nitrogen atom, so that the electrostatic adsorption capacity of the hard carbon material to ions is effectively promoted. The preparation method has the advantages that abundant internal crosslinked carbon networks are formed through respective assembly of polymerization reactions among trisodium citrate, urotropine and boron-containing oxides, ammonia gas formed by reaction decomposition is released in the carbonization process, and sodium borate byproducts generated in the ammonia gas are eluted by acid liquor treatment, so that the hard carbon material has abundant loose porous structures and abundant defect sites are provided, the prepared boron-nitrogen co-doped hard carbon material has a loose surface structure and a porous internal space, the hard carbon material is used as an electrochemical storage device and can be more favorable for improving the adsorption and storage capacities of the hard carbon material on metal ions/metal compounds and the like, and the boron-nitrogen co-doped hard carbon material can be widely applied to lithium/sodium ion battery cathodes, lithium-sulfur battery sulfur carriers/lithium-sulfur battery diaphragm coating modified materials and the like, the method is used for improving the discharge capacity and rate capability of the battery.
In some embodiments, the trisodium citrate, urotropin, boron-containing oxide, by weight ratio is (0.5-1.5): 1: (0.1-1.5).
In some embodiments of the application, the mass ratio of trisodium citrate to urotropine is 1:1, and the mass ratio of trisodium citrate to urotropine to the boron-containing oxide is 1:1: 0.5-1: 1:1.5, proper boron and nitrogen codoping can obviously reduce the interlayer spacing of the hard carbon material, improve the hole closing degree of the internal pore structure of the material and contribute to increasing the discharge capacity of the lithium/sodium ion battery; meanwhile, the boron-nitrogen doping to a certain degree also improves the graphitization degree of the hard carbon material, increases the short-range order in the hard carbon crystal structure, and improves the electron and ion conduction capability of the hard carbon material. The method researches the influence of the doping content of the boron element on the spacing between hard carbon layers and the defect degree of hard carbon, realizes the adjustment of the surface pore structure, the spacing between carbon material layers and the graphitization degree of the hard carbon material, and can provide positive and beneficial reference for the preparation of the hard carbon material obtained under the doping conditions of other different boron and nitrogen contents. In some embodiments, the present application also discusses trisodium citrate, urotropin, and boron-containing oxide at a mass ratio of (0.5-1.5): 1:0.5, the influence of the trisodium citrate added in different proportions on the structure of the hard carbon material, and the trisodium citrate influences the graphitization degree of the hard carbon material, so that a reference is provided for improving the ion or electron conductivity of the hard carbon material.
Trisodium citrate, urotropine and boron-containing oxide in a mass ratio of (0.5-1.5): 1: (0.1-1.5), in the carbonization process, ammonia gas generated by decomposition of urotropine enables the surface of the material to generate a loose and porous structure; ammonia (NH) generated by decomposition of urotropine with addition of boron3) Will replace the-ONa group in trisodium citrate to form-NH2. The addition of the boron-containing oxide assists ammonia gas generated by the decomposition of the urotropine to replace-ONa groups in trisodium citrate to form-NH2The opening degree of the pore structure in the hard carbon material is further reduced, and more closed structures are formed, so that the storage of the boron-nitrogen co-doped hard carbon material on metal ions/metal compounds is promoted, and the discharge capacity and the rate capability of the battery are improved. Meanwhile, in the doping process, part of the boron-containing oxide and the generated-ONa group can form sodium borate and other byproducts; and subsequently cleaning byproducts such as sodium borate and the like, wherein the byproducts are cleaned to increase the porous structure on the surface of the boron-nitrogen co-doped hard carbon material and increase the defect sites, so that the boron-nitrogen co-doped hard carbon material is more beneficial to the extraction-embedding of metal ions/metal compounds.
The mass ratio of trisodium citrate, urotropine and boron-containing oxide exceeds (0.5-1.5): 1: (0.1-1.5), the content of sodium borate and other by-products in the prepared boron-nitrogen co-doped hard carbon material is increased, the boron and nitrogen are heavily doped excessively, the carbonization reaction of trisodium citrate is obviously influenced, the formation of a hard carbon short-range ordered structure is not facilitated, and the electronic and ionic conductivity of the hard carbon material is further reduced; and in the hard carbon material, the content of boron element is too high, the interlayer spacing of the hard carbon material is reduced, and the excessive boron doping can influence the embedding of the hard carbon material to metal ions/metal compounds, thereby reducing the capacity of the battery.
In some preferred embodiments, the weight ratio of trisodium citrate, urotropin and boron-containing oxide is 1: (0.5-1).
Adding trisodium citrate, urotropine and boron-containing oxide in a mass ratio of 1: (0.5-1), the prepared boron-nitrogen co-doped hard carbon material has better electron/ion conduction performance, is applied to a lithium/sodium ion battery cathode, a lithium-sulfur battery sulfur carrier or a diaphragm coating modified material for a lithium-sulfur battery and the like, and can effectively improve the discharge capacity and the rate capability of the battery.
Further, the mass ratio of the trisodium citrate to the urotropine to the boron-containing oxide can be 1:1:0.1 or 1:1:0.5 or 1:1:0.8 or 1:1: 1.2; it may also be 0.7:1:0.5 or 1.2:1: 0.5.
In some embodiments, the trisodium citrate comprises trisodium citrate anhydrous or trisodium citrate dihydrate; the boron-containing oxide comprises at least one of boron oxide, boric acid, or tetraphenylboronic acid.
And carrying out carbonization reaction by using trisodium citrate as a carbon source, urotropine as a nitrogen source and a boron-containing oxide as a boron source to prepare the boron-nitrogen co-doped hard carbon material, wherein the boron-containing oxide is in a powder shape and is mixed by grinding.
In some embodiments, preferably, the protective atmosphere comprises at least one of a reducing gas, an inert gas, and nitrogen.
Preferably, the reducing gas comprises hydrogen or ammonia;
the inert gas comprises at least one of helium, argon, neon and krypton;
the volume ratio of the hydrogen to the inert gas is (5-10): (90-95).
During the carbonization reaction of the reactant trisodium citrate, urotropine and boron-containing oxide, the carbonization reaction is carried out in the atmosphere of reducing gas, and simultaneously, the generated hard carbon material is prevented from being oxidized under the action of inert gas or nitrogen or ammonia. Ammonia gas can be used as both a reducing gas in the carbonization reaction and a protective gas to prevent oxidation of the hard carbon material. When the hydrogen is a reducing gas, the hydrogen needs to be mixed with an inert gas or ammonia gas to prevent explosion.
In some embodiments, in the step 1), the temperature rise rate of the carbonization reaction is 2-5 ℃/min; the reaction temperature of the carbonization reaction is 700-900 ℃, and the reaction time of the carbonization reaction is 1-3 h.
The carbonization reaction temperature can be 700 ℃, 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃, 860 ℃, 890 ℃, 900 ℃, trisodium citrate, urotropine and boron-containing oxide can carry out carbonization reaction at 700-900 ℃; the carbonization reaction time can be 1h, 1.5h, 2h, 2.5h and 3 h. The temperature rise rate of the carbonization reaction is 2-5 ℃/min, and the slow temperature rise rate is beneficial to the polymerization carbonization reaction of trisodium citrate, urotropine and boron-containing oxide.
In some embodiments, the acid solution comprises hydrochloric acid, and the concentration of the hydrochloric acid is 0.1mol/L to 0.2 mol/L; the number of washing times by using hydrochloric acid is 1-3.
In some embodiments, the step 2) is performed by washing with an acid solution and then washing with absolute ethanol; the washing times by using absolute ethyl alcohol are 2-5 times.
The sodium borate by-product reacts with hydrochloric acid, and is cleaned by hydrochloric acid, and the method is mainly used for removing the sodium borate by-product. And then, washing with absolute ethyl alcohol to remove impurities adhered to the boron-nitrogen co-doped hard carbon material, such as sodium chloride adhered to the surface of the hard carbon material.
On the other hand, the application provides a boron-nitrogen co-doped hard carbon material, which comprises the boron-nitrogen co-doped hard carbon material prepared by the preparation method of the boron-nitrogen co-doped hard carbon material.
The boron-nitrogen co-doped hard carbon material prepared by the preparation method of the boron-nitrogen co-doped hard carbon material is used as an electrochemical storage device, and is more favorable for improving the adsorption and storage capacities of the electrochemical storage device on metal ions/metal compounds and the like; the method is applied to the battery field such as lithium/sodium ion battery cathodes, lithium-sulfur battery sulfur carriers or diaphragm coating modified materials for lithium-sulfur batteries, and the like, and can effectively improve the discharge capacity and rate capability of the batteries.
The technical solutions of the present application will be described in further detail below with reference to specific embodiments, but it should not be construed that the scope of the present application is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method described above.
Example 1
1) According to the mass ratio of 1:1:0.5, weighing trisodium citrate dihydrate, urotropine and boron oxide powder, grinding by using a mortar in a fume hood, and uniformly mixing;
2) putting the mixed powder into a square boat, putting the square boat into a tube furnace, and putting the square boat in Ar/H of 5% hydrogen2Heating to 800 ℃ at the heating rate of 3 ℃/min under the mixed atmosphere, and carrying out carbonization reaction for 2 hours to obtain a composite hard carbon material;
3) after natural cooling, taking out the composite hard carbon material prepared in the step 2) from the tube furnace, firstly washing the composite hard carbon material for 3 times by using hydrochloric acid solution with the concentration of 0.1mol/L, and then washing the composite hard carbon material for 2 times by using absolute ethyl alcohol. After cleaning, the sample is placed in an air-blast drying oven and dried at the temperature of 60 ℃ to obtain the boron-nitrogen co-doped hard carbon material 2 (the number is HC-0.5) with the porous microstructure.
As can be seen from fig. 2, which is a scanning electron micrograph of the boron-nitrogen co-doped hard carbon material 2 (numbered HC-0.5) synthesized in example 1: the hard carbon material is formed by stacking graphite like sheets, compared with the boron-nitrogen co-doped hard carbon material 1 (the number is HC-0) prepared in the comparative example 1, the thickness of the graphite sheet forming the material in the embodiment 1 is slightly increased (about 80 nm), and because the thickness of the graphite sheet is increased, the opening degree of the pore structure of the material in the embodiment 1 is obviously reduced, more closed pore structures are formed, so that the de-intercalation and adsorption of the boron-nitrogen co-doped hard carbon material 2 on metal ions/metal compounds are favorably promoted, and the discharge capacity and the rate capability of the battery are promoted.
Example 2
1) According to the mass ratio of 1:1: weighing trisodium citrate dihydrate, urotropine and boric acid powder, grinding in a mortar in a fume hood, and uniformly mixing;
2) putting the mixed powder into a square boat, putting the boat in a tube furnace, and putting the boat in Ar/H of 5 percent hydrogen2Heating to 800 ℃ at the heating rate of 3 ℃/min under the mixed atmosphere, and carrying out carbonization reaction for 2 hours to obtain a composite hard carbon material;
3) naturally cooling, taking out the carbon-based composite material prepared in the step 2) from the tubular furnace, cleaning for 3 times by using a hydrochloric acid solution with the concentration of 0.1mol/L, and cleaning for 2 times by using absolute ethyl alcohol. After cleaning, the sample is placed in an air-blast drying oven and dried at the temperature of 60 ℃ to obtain the boron-nitrogen co-doped hard carbon material 3 (the number is HC-1).
From the scanning electron micrograph of the boron-nitrogen co-doped hard carbon 3 (numbered HC-1) synthesized in example 2 shown in fig. 3, it can be seen that: the hard carbon material is also composed of graphite-like flakes, and the thickness of the flakes increases to about 120nm with increasing boron content. Compared with the trumpet-shaped opening presented by the HC-0 material shown in the figure 1 corresponding to the comparative example 1, the hard carbon material in the example 2 has a cross-linked net structure inside, the opening is a straight-through type instead of a trumpet-shaped type, and compared with the material numbered HC-0, the material numbered HC-1 has the advantages that the closed pore degree is increased, more pore structures are provided, and the storage capacity of the material to metal ions/metal compounds is favorably improved when the material is applied to an electrochemical energy storage device, so that the discharge capacity and the rate capability of a battery are further improved.
Example 3
1) According to the mass ratio of 1:1:1.5, weighing anhydrous trisodium citrate, urotropine and tetraphenylboronic acid powder, and grinding and mixing uniformly in a fume hood by using a mortar;
2) putting the mixed powder into a square boat, putting the square boat into a tubular furnace, heating to 900 ℃ at a heating rate of 5 ℃/min in an ammonia atmosphere, and carrying out carbonization reaction for 2 hours to obtain a carbon-based composite material;
3) and (3) after natural cooling, taking out the composite hard carbon material prepared in the step 2) from the tubular furnace, cleaning for 3 times by using a hydrochloric acid solution with the concentration of 0.2mol/L, and then cleaning for 3 times by using absolute ethyl alcohol. After the cleaning, the sample is placed in an air drying oven and dried at the temperature of 60 ℃ to obtain the hard boron-nitrogen co-doped hard carbon material 4 (the number is HC-1.5).
From the scanning electron micrograph of the boron-nitrogen co-doped hard carbon 4 (No. HC-1.5) synthesized in example 3 shown in fig. 4, it can be seen that: the hard carbon material is mainly composed of graphite-like sheets, and the pore structure of the material is significantly reduced and a part is formed by stacking, compared with the materials obtained in comparative example 1, example 1 and example 2. Pore structure influences metal ion's desorption and storage, the boron nitrogen codope hard carbon material's that embodiment 3 obtained pore structure quantity obviously reduces, the inventor reachs through a large amount of experiments, when the mass content who contains boron oxide is greater than embodiment 3, the boron nitrogen doping hard carbon material pore structure that the preparation obtained is unfavorable for the absorption of lithium/sodium ion and polysulfide, and then can restrict the application effect of hard carbon material in lithium/sodium ion battery, lithium/sulphur battery, be unfavorable for promoting battery discharge capacity and multiplying power performance.
Example 4:
1) according to the mass ratio of 0.5: 1:0.5, weighing trisodium citrate dihydrate, urotropine and boron oxide powder, grinding by using a mortar in a fume hood, and uniformly mixing;
2) putting the mixed powder into a square boat, putting the boat in a tube furnace, and putting the boat in Ar/H of 5 percent hydrogen2Mixing at 3 deg.C for min-1Heating to 800 ℃ at the heating rate, carrying out carbonization reaction, and annealing for 2 hours to obtain a composite hard carbon material;
3) and (3) after natural cooling, taking out the composite hard carbon material prepared in the step 2) from the tube furnace, cleaning for 3 times by using a hydrochloric acid solution with the concentration of 0.1mol/L, and then cleaning for 3 times by using absolute ethyl alcohol. And after cleaning, placing the sample in a forced air drying oven, and drying at the temperature of 60 ℃ to obtain the boron-nitrogen co-doped hard carbon material 5 (No. NM-0.5).
Example 5:
1) according to the mass ratio of 1.5: 1:0.5, weighing trisodium citrate dihydrate, urotropine and boric acid powder, grinding the trisodium citrate dihydrate, urotropine and boric acid powder in a fume hood, and uniformly mixing the trisodium citrate dihydrate, the urotropine and the boric acid powder;
2) putting the mixed powder into a square boat, putting the boat in a tube furnace, and putting the boat in Ar/H of 5 percent hydrogen2Heating to 800 ℃ at the heating rate of 3 ℃/min under the mixed atmosphere, carrying out carbonization reaction, and annealing for 2 hours to obtain a composite hard carbon material;
3) and (3) after natural cooling, taking out the composite hard carbon material prepared in the step 2) from the tube furnace, cleaning for 3 times by using a hydrochloric acid solution with the concentration of 0.2mol/L, and cleaning for 5 times by using absolute ethyl alcohol. And after cleaning, placing the sample in a forced air drying oven, and drying at the temperature of 60 ℃ to obtain the boron-nitrogen co-doped hard carbon material 6 (NM-1.5).
In examples 1, 4 and 5, the effect on the hard carbon material was examined by adjusting the amount ratio of trisodium citrate under the condition that the amounts of urotropin and the boron oxide-containing substance were the same. Wherein FIG. 2 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 5 (No. HC-0.5) prepared in example 1,
FIG. 8 is a scanning electron microscope image of boron-nitrogen co-doped hard carbon material 5 (No. NM-0.5) prepared in example 4,
fig. 9 is a scanning electron microscope image of the boron-nitrogen co-doped hard carbon material 6 (No. NM-1.5) prepared in example 5, and comparing fig. 2, 8 and 9, it is clear that the hard carbon materials obtained in fig. 8 and 9 are morphologically stacked similarly to graphite flakes, and the hard carbon materials obtained in fig. 8 and 9 have fewer surface pore structures than those obtained in fig. 2. The comparison shows that the effect of adjusting the proportion of the trisodium citrate on improving the pore structure of the hard carbon material is small.
Comparative example 1
1) According to the mass ratio of 1:1:0, weighing anhydrous trisodium citrate, urotropine and boron oxide powder, grinding the anhydrous trisodium citrate, urotropine and boron oxide powder in a fume hood, and uniformly mixing the ground trisodium citrate, urotropine and boron oxide powder;
2) loading the mixed powder into a square boat, placing in a tube furnace, and adding 8% Ar/H of hydrogen2Heating to 700 ℃ at the heating rate of 2 ℃/min under the mixed atmosphere, and carrying out carbonization reaction for 2 hours to obtain the carbon-based composite material;
3) after natural cooling, the sample was taken out of the tube furnace, washed 3 times with a hydrochloric acid solution having a concentration of 0.1mol/L, and then washed 2 times with absolute ethanol. After cleaning, the sample is placed in an air-blast drying oven and dried at the temperature of 60 ℃ to obtain the boron-nitrogen co-doped hard carbon material 1 (the number is HC-0) with the porous microstructure.
As can be seen from the scanning electron micrograph of the boron-nitrogen co-doped hard carbon material 1 (numbered HC-0) synthesized in FIG. 1, comparative example 1: the hard carbon material is composed of two-dimensional graphite flakes, and the thickness of the graphite flakes forming a pore structure is about 50 nm. The internal structure is mainly a series of large and small many types of horn-shaped open pore structures, the structures are favorable for the diffusion and shuttle of metal ions or polysulfide, but the internal few closed pore structures are possibly unfavorable for the storage of metal ions/metal compounds, so that the improvement of the battery discharge capacity and the rate capability of the boron-nitrogen co-doped hard carbon material 1 when applied to a lithium/sodium ion battery cathode material, a lithium-sulfur battery sulfur-carrying body or a lithium-sulfur battery diaphragm coating modified material is not favorable.
FIG. 5 is a Raman plot of the final product obtained in example 1 and comparative example 1 at 1354cm-1And 1590cm-1The two peaks are respectively a D peak and a G peak, which respectively represent the disorder degree and the graphitization degree of the carbon material, IG/IDA larger value indicates a higher degree of graphitization of the carbon material. As can be seen by calculation, I of comparative example 1 obtained without boron-nitrogen co-dopingG/IDValue 1.02, and I of example 1 obtained after boron-nitrogen co-dopingG/IDThe value is 1.08, and the result shows that boron-nitrogen co-doping is more favorable for improving the short-range order of the hard carbon material, improving the graphitization degree of the hard carbon material and enhancing the ion/electron conduction capability, thereby being favorable for increasing the storage capability of metal ions/metal compounds.
FIG. 6 is an XRD pattern of samples of examples 1, 2, 3 and comparative example 1 after synthesis, before acid and water washing. As can be seen from FIG. 6, when the lemon is usedWhen the content of boron-containing oxide in the mixture of trisodium citrate, urotropine and boron-containing oxide is 0, the formed hard carbon material contains a small amount of sodium carbonate (Na) through the crosslinking reaction between the trisodium citrate and urotropine2CO3) Meanwhile, during the carbonization process, ammonia gas generated by decomposition of urotropine can also form a loose and porous structure on the surface of the material (as shown in fig. 1). When the mass ratio of the trisodium citrate to the mixture of the urotropine and the boron-containing compound is 1:1:0.5, ammonia (NH) generated by decomposition of the urotropine is added along with the boron element3) Will replace the-ONa group to form-NH2(ii) a Meanwhile, during the doping process, part of boron-containing oxide can form sodium metaborate (NaBO) as a byproduct with-ONa groups generated by trisodium citrate2) The compound of (1). Along with the increase of the content of the boron-containing compound for doping, when the mass ratio of the mixture of the trisodium citrate, the urotropine and the boron-containing compound is 1:1:1, the by-product is converted into sodium tetraborate (Na)2B4O7) (the characteristic peak is positioned at 19.2 ℃), but the peak intensity is lower, which indicates that the boron-containing compound fully participates in the reaction at the ratio, the boron doping content of the obtained product is obviously improved, and the carbon content of the product is correspondingly improved. When the mass ratio of the trisodium citrate, the urotropine and the boron-containing compound is 1:1:1.5, the by-product Na is generated2B4O7The peak intensity of the sodium citrate is obvious, which indicates that the carbonization of trisodium citrate is obviously influenced by the serious excessive boron doping, and the obtained product has hand feeling similar to borax and hard texture.
Fig. 7 is an XRD pattern of the final product after synthesis for the samples of examples 1, 2, 3 and comparative example 1. Because of the by-product Na2CO3、NaBO2And Na2B4O7Both dissolved in hydrochloric acid, so that examples 1 and 2 only had amorphous carbon diffraction peaks at the 26.7 ° and 41.8 ° positions, respectively, and example 3 had a slightly larger amount of boron-containing compound substance added, and the by-products generated affected the test results, and the values of the amorphous carbon diffraction peaks could not be accurately obtained.
The results of the calculation of the interplanar spacing of the hard carbon materials obtained in comparative example 1, example 1 and example 2 are 0.378nm, 0.336nm and 0.330nm respectively, which shows that the spacing of the hard carbon layers is reduced and the closed pore structure is increased with the increase of boron-nitrogen co-doping, and the platform capacity during lithium/sodium ion storage is improved when the boron-nitrogen co-doping hard carbon material is applied to a negative electrode. Meanwhile, as can be seen from fig. 7, the (002) diffraction peak of examples 1 and 2 in the XRD spectrum is significantly shifted to a higher angle than the (002) diffraction peak of comparative example 1, and it is laterally demonstrated that the interlayer spacing of the hard carbon material becomes smaller with the addition of boron element, thereby facilitating the formation of more short-range ordered structures and increasing the electron and ion conductivity of the hard carbon material. In contrast, the (002) diffraction peak angle of comparative example 1 and example 2 is smaller as the content of boron element is increased, indicating that too much boron doping affects the intercalation of the hard carbon material into metal ions.
According to the preparation method of boron-nitrogen co-doped hard carbon provided by the invention, a proper amount of boron-nitrogen co-doping (trisodium citrate: urotropin: boron-containing oxide: 1:0.5) can enrich the internal pore structure of the hard carbon material, obviously reduce the interlayer spacing of the hard carbon material and improve the pore closing degree of the material. When the hard carbon material is used as a battery cathode material or a diaphragm coating modified material, the de-intercalation and storage of metal ions/metal compounds can be further promoted, so that the discharge capacity of the battery can be increased, and the capacity platform and the rate capability of the battery can be improved; meanwhile, boron-nitrogen co-doping to a certain degree also promotes the graphitization degree of the hard carbon material, increases the short-range order in the hard carbon crystal structure, and promotes the electron and ion conduction capability of the material.
Fig. 10 is an XRD pattern before acid washing and water washing of the composite hard carbon materials prepared in examples 1, 4 and 5. As can be seen from fig. 10, when trisodium citrate as a carbon source is added in a small amount, the mixture ratio of trisodium citrate, urotropin and a boron-containing compound as in example 4 is 0.5: 1: at 0.5, the composite hard carbon material product formed has partial trisodium citrate and Na formed by boron-containing compound except the characteristic hard carbon peak (located at 26.5 degrees)2B4O7By-products(characteristic peak at 18.9 ℃). Example 4 in comparison with example 1 (the mass ratio of the mixture of trisodium citrate, urotropine and boron-containing compound is 1:1:0.5), the product has a preference for Na formation in addition to the formation of hard carbon material2B4O7By-products, the formation of which consumes more trisodium citrate, in turn affecting the carbon content of the hard carbon material. When the content of trisodium citrate is moderate (example 1: the mass ratio of the mixture of trisodium citrate, urotropin and the boron-containing compound is 1:1:0.5), the byproduct is NaBO2Indicating that the consumed carbon source is significantly reduced; when the trisodium citrate is added in an excessive amount (example 5: the mixture of trisodium citrate, urotropin and boron-containing compound has a mass ratio of 1.5: 1:0.5), more by-products are produced, except for NaBO2In addition, sodium diborate (Na)4B2O5) Significantly affects the carbonization process of the material.
As shown by comparison in FIG. 10, in the reaction process of trisodium citrate, urotropin and boron-containing compound, Na is generated when the content of trisodium citrate is too low2B4O7By-products, when the content of the trisodium citrate is excessive, the generated by-products are increased, and the carbonization process of the hard carbon material is influenced; from the comparison, it is known that, when the amount ratio of trisodium citrate, urotropin and the boron-containing compound substance is 1:1:0.5, the by-products generated by the carbonization reaction are less, and the influence on the carbonization process of the hard carbon material is less.
Figure 11 is an XRD pattern of the final product synthesized from the samples of examples 1, 4 and 5. Because of the by-product Na2B4O7、NaBO2、Na4B2O5All dissolved in strong acid, so that after washing with hydrochloric acid and absolute ethanol before and after washing, typical carbon material peaks at 26.7 ° and 41.8 ° were present in examples 1, 4 and 5. As can be seen from the observation of the peak intensity and half-peak width of the XRD pattern in FIG. 11, the hard carbon material obtained in example 4 has a stronger graphitization degree when the citric acid content is low, and the half-peak widths of examples 1 and 5 increase as the content of trisodium citrate increases, indicating that the amorphous state of the obtained hard carbon material increasesMuch more. By further comparing the interplanar spacings of examples 4, 1 and 5, the results were 0.334nm, 0.336nm and 0.335nm, respectively, and the interplanar spacings of the three samples were relatively close, indicating that the trisodium citrate content primarily regulates the graphitization degree of the hard carbon material with less influence on the interplanar spacings.
By comparison of the above examples 1, 4, 5, trisodium citrate: urotropin: when the boron-containing compound is 1:1:0.5, the content of the produced by-products is low in the carbonization reaction process of the three, the influence degree on the carbonization reaction is small, the graphitization degree of the prepared boron-nitrogen co-doped hard carbon material is high, the ionic and electronic conduction capability of the material is favorably improved, and the discharge capacity and the rate capability of the battery are improved. The proportion of trisodium citrate is adjusted, the change of the spacing between the hard carbon material layers is not influenced, and the method has certain guiding significance for researching and improving the graphitization degree of the boron-nitrogen co-doped hard carbon material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a boron-nitrogen co-doped hard carbon material is characterized by comprising the following steps:
1) obtaining trisodium citrate, urotropine and boron-containing oxide, uniformly mixing, and carrying out carbonization reaction in a protective atmosphere to obtain a composite hard carbon material;
2) taking out the composite hard carbon material obtained in the step 1), washing with acid liquor, eluting sodium borate by-products in the composite hard carbon material, and obtaining the boron-nitrogen co-doped hard carbon material with loose and porous interior.
2. The method for preparing the boron-nitrogen co-doped hard carbon material according to claim 1, wherein the mass ratio of the trisodium citrate to the urotropine to the boron-containing oxide is (0.5-1.5): 1: (0.1-1.5).
3. The preparation method of the boron-nitrogen co-doped hard carbon material as claimed in claim 2, wherein the mass ratio of the trisodium citrate to the urotropine to the boron-containing oxide is 1:1 (0.5-1).
4. The method for preparing boron-nitrogen co-doped hard carbon material according to claim 1, wherein the trisodium citrate comprises trisodium citrate anhydrous or trisodium citrate dihydrate; the boron-containing oxide comprises at least one of boron oxide, boric acid, or tetraphenylboronic acid.
5. The method according to claim 1, wherein the protective atmosphere comprises at least one of a reducing gas, an inert gas and nitrogen.
6. The method for preparing the boron-nitrogen co-doped hard carbon material according to claim 5, wherein the reducing gas comprises hydrogen or ammonia;
the inert gas comprises at least one of helium, argon, neon and krypton;
the volume ratio of the hydrogen to the inert gas is (5-10): (90-95).
7. The preparation method of the boron-nitrogen co-doped hard carbon material according to claim 1, wherein in the step 1), the temperature rise rate of the carbonization reaction is 2-5 ℃/min; the reaction temperature of the carbonization reaction is 700-900 ℃, and the reaction time of the carbonization reaction is 1-3 h.
8. The method for preparing the boron-nitrogen co-doped hard carbon material according to claim 1, wherein the acid solution comprises hydrochloric acid, and the concentration of the hydrochloric acid is 0.1mol/L-0.2 mol/L; the number of washing times by using hydrochloric acid is 1-3.
9. The method for preparing the boron-nitrogen co-doped hard carbon material according to claim 8, wherein the cleaning with the acid solution in the step 2) is followed by cleaning with absolute ethyl alcohol, and the number of times of cleaning with absolute ethyl alcohol is 2-5.
10. A boron-nitrogen co-doped hard carbon material, which is characterized by comprising the boron-nitrogen co-doped hard carbon material prepared by the preparation method of the boron-nitrogen co-doped hard carbon material of any one of claims 1 to 9.
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